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

PubMed

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

2012-09-06

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

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.

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

Separations by supported liquid membrane cascades

DOEpatents

Danesi, P.R.

1983-09-01

The invention describes a new separation technique which leads to multi-stage operations by the use of a series (a cascade) of alternated carrier-containing supported-liquid cation exchanger extractant and a liquid anion exchanger extractant (or a neutral extractant) as carrier. The membranes are spaced between alternated aqueous electrolytic solutions of different composition which alternatively provide positively charged extractable species and negatively charged (or zero charged) extractable species, of the chemical species to be separated. The alternated aqueous electrolytic solutions in addition to providing the driving force to the process, simultaneously function as a stripping solution from one type of membrane and as an extraction-promoting solution for the other type of membrane. The aqueous electrolytic solution and the supported liquid membranes are arranged to provide a continuous process.

Electrostatic Separator for Beneficiation of Lunar Soil

NASA Technical Reports Server (NTRS)

Quinn, Jacqueline; Arens, Ellen; Trigwell, Steve; Captain, James

2010-01-01

A charge separator has been constructed for use in a lunar environment that will allow for separation of minerals from lunar soil. In the present experiments, whole lunar dust as received was used. The approach taken here was that beneficiation of ores into an industrial feedstock grade may be more efficient. Refinement or enrichment of specific minerals in the soil before it is chemically processed may be more desirable as it would reduce the size and energy requirements necessary to produce the virgin material, and it may significantly reduce the process complexity. The principle is that minerals of different composition and work function will charge differently when tribocharged against different materials, and hence be separated in an electric field.

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

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.

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.

Quantum modeling of ultrafast photoinduced charge separation

NASA Astrophysics Data System (ADS)

Rozzi, Carlo Andrea; Troiani, Filippo; Tavernelli, Ivano

2018-01-01

Phenomena involving electron transfer are ubiquitous in nature, photosynthesis and enzymes or protein activity being prominent examples. Their deep understanding thus represents a mandatory scientific goal. Moreover, controlling the separation of photogenerated charges is a crucial prerequisite in many applicative contexts, including quantum electronics, photo-electrochemical water splitting, photocatalytic dye degradation, and energy conversion. In particular, photoinduced charge separation is the pivotal step driving the storage of sun light into electrical or chemical energy. If properly mastered, these processes may also allow us to achieve a better command of information storage at the nanoscale, as required for the development of molecular electronics, optical switching, or quantum technologies, amongst others. In this Topical Review we survey recent progress in the understanding of ultrafast charge separation from photoexcited states. We report the state-of-the-art of the observation and theoretical description of charge separation phenomena in the ultrafast regime mainly focusing on molecular- and nano-sized solar energy conversion systems. In particular, we examine different proposed mechanisms driving ultrafast charge dynamics, with particular regard to the role of quantum coherence and electron-nuclear coupling, and link experimental observations to theoretical approaches based either on model Hamiltonians or on first principles simulations.

Electrokinetic Supercapacitor for Simultaneous Harvesting and Storage of Mechanical Energy.

PubMed

Yang, Peihua; Qu, Xiaopeng; Liu, Kang; Duan, Jiangjiang; Li, Jia; Chen, Qian; Xue, Guobin; Xie, Wenke; Xu, Zhimou; Zhou, Jun

2018-03-07

Energy harvesting and storage are two distinct processes that are generally achieved using two separated parts based on different physical and chemical principles. Here we report a self-charging electrokinetic supercapacitor that directly couples the energy harvesting and storage processes into one device. The device consists of two identical carbon nanotube/titanium electrodes, separated by a piece of anodic aluminum oxide nanochannels membrane. Pressure-driven electrolyte flow through the nanochannels generates streaming potential, which can be used to charge the capacitive electrodes, accomplishing simultaneous energy generation and storage. The device stores electric charge density of 0.4 mC cm -2 after fully charging under pressure of 2.5 bar. This work may offer a train of thought for the development of a new type of energy unit for self-powered systems.

Quantum design of photosynthesis for bio-inspired solar-energy conversion.

PubMed

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

2017-03-15

Photosynthesis is the natural process that converts solar photons into energy-rich products that are needed to drive the biochemistry of life. Two ultrafast processes form the basis of photosynthesis: excitation energy transfer and charge separation. Under optimal conditions, every photon that is absorbed is used by the photosynthetic organism. Fundamental quantum mechanics phenomena, including delocalization, underlie the speed, efficiency and directionality of the charge-separation process. At least four design principles are active in natural photosynthesis, and these can be applied practically to stimulate the development of bio-inspired, human-made energy conversion systems.

Dissociation of doubly charged clusters of lithium acetate: Asymmetric fission and breakdown of the liquid drop model: Dissociation of doubly charged clusters of lithium acetate

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

Shukla, Anil

2016-06-08

Unimolecular and collision-induced dissociation of doubly charged lithium acetate clusters, (CH3COOLi)nLi22+, demonstrated that Coulomb fission via charge separation is the dominant dissociation process with no contribution from the neutral evaporation processes for all such ions from the critical limit to larger cluster ions, although latter process have normally been observed in all earlier studies. These results are clearly in disagreement with the Rayleigh’s liquid drop model that has been used successfully to predict the critical size and explain the fragmentation behavior of multiply charged clusters.

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

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

Hybridizing energy conversion and storage in a mechanical-to-electrochemical process for self-charging power cell.

PubMed

Xue, Xinyu; Wang, Sihong; Guo, Wenxi; Zhang, Yan; Wang, Zhong Lin

2012-09-12

Energy generation and energy storage are two distinct processes that are usually accomplished using two separated units designed on the basis of different physical principles, such as piezoelectric nanogenerator and Li-ion battery; the former converts mechanical energy into electricity, and the latter stores electric energy as chemical energy. Here, we introduce a fundamental mechanism that directly hybridizes the two processes into one, in which the mechanical energy is directly converted and simultaneously stored as chemical energy without going through the intermediate step of first converting into electricity. By replacing the polyethylene (PE) separator as for conventional Li battery with a piezoelectric poly(vinylidene fluoride) (PVDF) film, the piezoelectric potential from the PVDF film as created by mechanical straining acts as a charge pump to drive Li ions to migrate from the cathode to the anode accompanying charging reactions at electrodes. This new approach can be applied to fabricating a self-charging power cell (SCPC) for sustainable driving micro/nanosystems and personal electronics.

ELECTROSTATIC SURFACE STRUCTURES OF COAL AND MINERAL PARTICLES

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

NONE

It is the purpose of this research to study electrostatic charging mechanisms related to electrostatic beneficiation of coal with the goal of improving models of separation and the design of electrostatic separators. Areas addressed in this technical progress report are (a) electrostatic beneficiation of Pittsburgh #8 coal powders as a function of grind size and processing atmosphere; (b) the use of fluorescent micro-spheres to probe the charge distribution on the surfaces of coal particles; (c) the use of electrostatic beneficiation to recover unburned carbon from flyash; (d) the development of research instruments for investigation of charging properties of coal. Pittsburghmore » #8 powders were beneficiated as a function of grind size and under three atmosphere conditions: fresh ground in air , after 24 hours of air exposure, or under N2 atmosphere. The feed and processed powders were analyzed by a variety of methods including moisture, ash, total sulfur, and pyritic sulfur content. Mass distribution and cumulative charge of the processed powders were also measured. Fresh ground coal performed the best in electrostatic beneficiation. Results are compared with those of similar studies conducted on Pittsburgh #8 powders last year (April 1, 1997 to September 30, 1997). Polystyrene latex spheres were charged and deposited onto coal particles that had been passed through the electrostatic separator and collected onto insulating filters. The observations suggest bipolar charging of individual particles and patches of charge on the particles which may be associated with particular maceral types or with mineral inclusions. A preliminary investigation was performed on eletrostatic separation of unburned carbon particles from flyash. Approximately 25% of the flyash acquired positive charge in the copper tribocharger. This compares with 75% of fresh ground coal. The negatively charged material had a slightly reduced ash content suggesting some enrichment of carbonaceous material. There was also evidence that the carbon is present at a higher ratio in larger particles than in small particles. An ultraviolet photoelectron counter for use in ambient atmosphere is nearing completion. The counter will be used to measure work functions of different maceral and mineral types in the coal matrix. A Particle Image Analyzer for measuring size and charge of airborne particles is also under contruction and its current status is presented. A charged, monodisperse, droplet generator is also being constructed for calibration of the Particle Image Analyzer and other airborne particle analyzers in our labs.« less

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.

Separations by supported liquid membrane cascades

DOEpatents

Danesi, Pier R.

1986-01-01

The invention describes a new separation technique which leads to multi-stage operations by the use of a series (a cascade) of alternated carrier-containing supported-liquid membranes. The membranes contain alternatively a liquid cation exchanger extractant and a liquid anion exchanger extractant (or a neutral extractant) as carrier. The membranes are spaced between alternated aqueous electrolytic solutions of different composition which alternatively provide positively charged extractable species and negatively charged (or zero charged) extractable species, of the chemical species to be separated. The alternated aqueous electrolytic solutions in addition to providing the driving force to the process, simultaneously function as a stripping solution from one type of membrane and as an extraction-promoting solution for the other type of membrane. The aqueous electrolytic solutions and the supported liquid membranes are arranged in such a way to provide a continuous process which leads to the continuous enrichment of the species which show the highest permeability coefficients. By virtue of the very high number of stages which can be arranged, even chemical species having very similar chemical behavior (and consequently very similar permeability coefficients) can be completely separated. The invention also provide a way to concentrate the separated species.

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

Understanding the free energy barrier and multiple timescale dynamics of charge separation in organic photovoltaic cells.

PubMed

Yan, Yaming; Song, Linze; Shi, Qiang

2018-02-28

By employing several lattice model systems, we investigate the free energy barrier and real-time dynamics of charge separation in organic photovoltaic (OPV) cells. It is found that the combined effects of the external electric field, entropy, and charge delocalization reduce the free energy barrier significantly. The dynamic disorder reduces charge carrier delocalization and results in the increased charge separation barrier, while the effect of static disorder is more complicated. Simulation of the real-time dynamics indicates that the free charge generation process involves multiple time scales, including an ultrafast component within hundreds of femtoseconds, an intermediate component related to the relaxation of the hot charge transfer (CT) state, and a slow component on the time scale of tens of picoseconds from the thermally equilibrated CT state. Effects of hot exciton dissociation as well as its dependence on the energy offset between the Frenkel exciton and the CT state are also analyzed. The current results indicate that only a small energy offset between the band gap and the lowest energy CT state is needed to achieve efficient free charge generation in OPV devices, which agrees with recent experimental findings.

Understanding the free energy barrier and multiple timescale dynamics of charge separation in organic photovoltaic cells

NASA Astrophysics Data System (ADS)

Yan, Yaming; Song, Linze; Shi, Qiang

2018-02-01

By employing several lattice model systems, we investigate the free energy barrier and real-time dynamics of charge separation in organic photovoltaic (OPV) cells. It is found that the combined effects of the external electric field, entropy, and charge delocalization reduce the free energy barrier significantly. The dynamic disorder reduces charge carrier delocalization and results in the increased charge separation barrier, while the effect of static disorder is more complicated. Simulation of the real-time dynamics indicates that the free charge generation process involves multiple time scales, including an ultrafast component within hundreds of femtoseconds, an intermediate component related to the relaxation of the hot charge transfer (CT) state, and a slow component on the time scale of tens of picoseconds from the thermally equilibrated CT state. Effects of hot exciton dissociation as well as its dependence on the energy offset between the Frenkel exciton and the CT state are also analyzed. The current results indicate that only a small energy offset between the band gap and the lowest energy CT state is needed to achieve efficient free charge generation in OPV devices, which agrees with recent experimental findings.

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.

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.

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

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

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

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.

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.

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.

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.

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.

4 CFR 28.98 - Individual charges in EEO cases.

Code of Federal Regulations, 2013 CFR

2013-01-01

... complaint process. (d) Special rules for RIF based actions. An individual alleging discrimination issues in connection with a RIF-based separation may follow the procedures outlined above in paragraph (c) of this.... (2) A charging party challenging a RIF action by filing directly with the PAB shall follow the...

4 CFR 28.98 - Individual charges in EEO cases.

Code of Federal Regulations, 2012 CFR

2012-01-01

... complaint process. (d) Special rules for RIF based actions. An individual alleging discrimination issues in connection with a RIF-based separation may follow the procedures outlined above in paragraph (c) of this.... (2) A charging party challenging a RIF action by filing directly with the PAB shall follow the...

4 CFR 28.98 - Individual charges in EEO cases.

Code of Federal Regulations, 2014 CFR

2014-01-01

... complaint process. (d) Special rules for RIF based actions. An individual alleging discrimination issues in connection with a RIF-based separation may follow the procedures outlined above in paragraph (c) of this.... (2) A charging party challenging a RIF action by filing directly with the PAB shall follow the...

Electrochemical force microscopy

DOEpatents

Kalinin, Sergei V.; Jesse, Stephen; Collins, Liam F.; Rodriguez, Brian J.

2017-01-10

A system and method for electrochemical force microscopy are provided. The system and method are based on a multidimensional detection scheme that is sensitive to forces experienced by a biased electrode in a solution. The multidimensional approach allows separation of fast processes, such as double layer charging, and charge relaxation, and slow processes, such as diffusion and faradaic reactions, as well as capturing the bias dependence of the response. The time-resolved and bias measurements can also allow probing both linear (small bias range) and non-linear (large bias range) electrochemical regimes and potentially the de-convolution of charge dynamics and diffusion processes from steric effects and electrochemical reactivity.

An Electrostatic Charge Partitioning Model for the Dissociation of Protein Complexes in the Gas Phase

NASA Astrophysics Data System (ADS)

Sciuto, Stephen V.; Liu, Jiangjiang; Konermann, Lars

2011-10-01

Electrosprayed multi-protein complexes can be dissociated by collisional activation in the gas phase. Typically, these processes follow a mechanism whereby a single subunit gets ejected with a disproportionately high amount of charge relative to its mass. This asymmetric behavior suggests that the departing subunit undergoes some degree of unfolding prior to being separated from the residual complex. These structural changes occur concomitantly with charge (proton) transfer towards the subunit that is being unraveled. Charge accumulation takes place up to the point where the subunit loses physical contact with the residual complex. This work develops a simple electrostatic model for studying the relationship between conformational changes and charge enrichment during collisional activation. Folded subunits are described as spheres that carry continuum surface charge. The unfolded chain is envisioned as random coil bead string. Simulations are guided by the principle that the system will adopt the charge configuration with the lowest potential energy for any backbone conformation. A finite-difference gradient algorithm is used to determine the charge on each subunit throughout the dissociation process. Both dimeric and tetrameric protein complexes are investigated. The model reproduces the occurrence of asymmetric charge partitioning for dissociation events that are preceded by subunit unfolding. Quantitative comparisons of experimental MS/MS data with model predictions yield estimates of the structural changes that occur during collisional activation. Our findings suggest that subunit separation can occur over a wide range of scission point structures that correspond to different degrees of unfolding.

77 FR 5178 - Fees

Federal Register 2010, 2011, 2012, 2013, 2014

2012-02-02

... penalty from the fee calculation is not adopted. 514.17 How are fingerprint processing fees collected by the Commission? Comment: Two commenters objected to fingerprint fees being included as a separate... fingerprints and not all tribes utilize the service. The service will continue to be charged as a separate fee...

Stick slip, charge separation and decay

USGS Publications Warehouse

Lockner, D.A.; Byerlee, J.D.; Kuksenko, V.S.; Ponomarev, A.V.

1986-01-01

Measurements of charge separation in rock during stable and unstable deformation give unexpectedly large decay times of 50 sec. Time-domain induced polarization experiments on wet and dry rocks give similar decay times and suggest that the same decay mechanisms operate in the induced polarization response as in the relaxation of charge generated by mechanical deformation. These large decay times are attributed to electrochemical processes in the rocks, and they require low-frequency relative permittivity to be very large, in excess of 105. One consequence of large permittivity, and therefore long decay times, is that a significant portion of any electrical charge generated during an earthquake can persist for tens or hundreds of seconds. As a result, electrical disturbances associated with earthquakes should be observable for these lengths of time rather than for the milliseconds previously suggested. ?? 1986 Birka??user Verlag.

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

NASA Astrophysics Data System (ADS)

Cai, Yongqing; Feng, Yuan Ping

2016-12-01

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

Interaction of an ion bunch with a plasma slab

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

Krasovitskiy, V. B., E-mail: krasovit@mail.ru; Turikov, V. A.

2016-11-15

Charge neutralization of a short ion bunch passing through a plasma slab is studied by means of numerical simulation. It is shown that a fraction of plasma electrons are trapped by the bunch under the action of the collective charge separation field. The accelerated electrons generated in this process excite beam−plasma instability, thereby violating the trapping conditions. The process of electron trapping is also strongly affected by the high-frequency electric field caused by plasma oscillations at the slab boundaries. It is examined how the degree of charge neutralization depends on the parameters of the bunch and plasma slab.

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.

A quantitative structure–function relationship for the Photosystem II reaction center: Supermolecular behavior in natural photosynthesis

PubMed Central

Barter, Laura M. C.; Durrant, James R.; Klug, David R.

2003-01-01

Light-induced charge separation is the primary photochemical event of photosynthesis. Efficient charge separation in photosynthetic reaction centers requires the balancing of electron and excitation energy transfer processes, and in Photosystem II (PSII), these processes are particularly closely entangled. Calculations that treat the cofactors of the PSII reaction center as a supermolecular complex allow energy and electron transfer reactions to be described in a unified way. This calculational approach is shown to be in good agreement with experimentally observed energy and electron transfer dynamics. This supermolecular view also correctly predicts the effect of changing the redox potentials of cofactors by site-directed mutagenesis, thus providing a unified and quantitative structure–function relationship for the PSII reaction center. PMID:12538865

Interfacial disorder drives charge separation in molecular semiconductors

NASA Astrophysics Data System (ADS)

Willard, Adam

One of the fundamental microscopic processes in photocurrent generation is the dissociation of neutral photo-excitations (i.e., Frenkel excitons) into free charge carriers (i.e., electrons and holes). This process requires the physical separation of oppositely charged electrons and holes, which are held to together by an attractive electrostatic binding energy. In traditional inorganic-based photovoltaic (PV) materials, this binding energy is generally small and easily overcome, however, in organic-based PVs (OPVs) the exciton binding energy can significantly exceed thermal energies. The inability of bound charges to overcome this large binding energy has been implicated as a primary source of efficiency loss in OPVs. Here I present results from our recent efforts to explore the role of static molecular disorder in mediating this process. Using a simple lattice model of exciton dynamics we demonstrate that random spatial variations in the energetic landscape can mitigate the attractive Coulomb interaction between electrons and holes. We show that this effect manifests as a reduction in the free energy barrier for exciton dissociation that grows more pronounced with increasing disorder. By considering the competition between this thermodynamic effect and the disorder-induced slowing of dissociation kinetics we demonstrate that exciton dissociation yields are expected to depend non-monotonically on the degree of static disorder.

Composite tin and zinc oxide nanocrystalline particles for enhanced charge separation in sensitized degradation of dyes.

PubMed

Bandara, J; Tennakone, K; Jayatilaka, P P B

2002-10-01

Composite ZnO/SnO2 catalyst has been studied for the sensitized degradation of dyes e.g. Eosin Y (2', 4', 5', 7'-tetrabromofluorescein disodium salt) in relation to efficient charge separation properties of the catalyst. Improved photocatalytic activity was observed in the case of ZnO/SnO2 composite catalyst compared to the catalytic activity of ZnO, SnO2 or TiO2 powder. The suppression of charge recombination in the composite ZnO/SnO2 catalyst led to higher catalytic activity for the degradation of Eosin Y. Degradation of Eosin follows concomitant formation of CO2 and formation of CO2 followed a pseudo-first-order rate. Photoelectrochemical cells constructed using SnO2, ZnO, ZnO/SnO2 sensitized with Eosin Y showed V(oc) of 175, 306, 512 mV/cm2 and I(sc) of 50, 70, 200 microA/cm2 respectively. A higher irreversible degradation of Eosin Y and higher V(oc) observed on composite ZnO/SnO2 than ZnO and SnO2 separately can be considered as a proof of enhanced charge separation of ZnO/SnO2 catalyst. Eosin Y showed a higher emission decreases on ZnO/SnO2 composite than on individual ZnO, SnO2 or TiO2 indicating dominance of the charge injection process. Photoinjected electrons are tunneled from ZnO to SnO2 particles accumulating injected electrons in the conduction bands allowing wider separation of excited carriers.

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%.

Electrospun nylon 6/zinc doped hydroxyapatite membrane for protein separation: Mechanism of fouling and blocking model.

PubMed

Esfahani, Hamid; Prabhakaran, Molamma P; Salahi, Esmaeil; Tayebifard, Ali; Rahimipour, Mohamad Reza; Keyanpour-Rad, Mansour; Ramakrishna, Seeram

2016-02-01

Development of composite nanofibrous membrane via electrospinning a polymer with ceramic nanoparticles (NPs) for application in protein separation systems is explored during this study. Positively charged zinc doped hydroxyapatite (xZH) NPs were prepared in three different compositions via chemical precipitation method. Herein, we created a positively charged surface containing nanoparticles on electrospun Nylon-6 nanofibers (NFs) to improve the separation and selectivity properties for adsorption of negatively charged protein, namely bovine serum albumin (BSA). The decline in permeate flux was analyzed using the framework of classical blocking models and fitting, demonstrated that the transition of fouling mechanisms was dominated during the filtration process. The standard blocking model provided the best fit of the experimental results during the mid-filtration period. The membrane decorated by NPs containing 4at.% zinc cations not only provided maximum BSA separation but also capable of separating higher amounts of BSA molecules (even after 1h filtration) than the pure Nylon membrane. Protein separation was achieved through this membrane with the incorporation of NPs that had high zeta potential (+5.9±0.2mV) and lower particle area (22,155nm(2)). The developed membrane has great potential to act as a high efficiency membrane for capturing BSA. Copyright © 2015 Elsevier B.V. All rights reserved.

Direct Observation of Photoinduced Charge Separation in Ruthenium Complex/Ni(OH) 2 Nanoparticle Hybrid

DOE PAGES

Tang, Yu; Pattengale, Brian A.; Ludwig, John M.; ...

2015-12-17

We report that Ni(OH) 2 have emerged as important functional materials for solar fuel conversion because of their potential as cost-effective bifunctional catalysts for both hydrogen and oxygen evolution reactions. However, their roles as photocatalysts in the photoinduced charge separation (CS) reactions remain unexplored. In this paper, we investigate the CS dynamics of a newly designed hybrid catalyst by integrating a Ru complex with Ni(OH) 2 nanoparticles (NPs). Using time resolved X-ray absorption spectroscopy (XTA), we directly observed the formation of the reduced Ni metal site (~60 ps), unambiguously demonstrating CS process in the hybrid through ultrafast electron transfer frommore » Ru complex to Ni(OH) 2 NPs. Compared to the ultrafast CS process, the charge recombination in the hybrid is ultraslow (>>50 ns). These results not only suggest the possibility of developing Ni(OH) 2 as solar fuel catalysts, but also represent the first time direct observation of efficient CS in a hybrid catalyst using XTA.« less

Single charging events on colloidal particles in a nonpolar liquid with surfactant

NASA Astrophysics Data System (ADS)

Schreuer, Caspar; Vandewiele, Stijn; Brans, Toon; Strubbe, Filip; Neyts, Kristiaan; Beunis, Filip

2018-01-01

Electrical charging of colloidal particles in nonpolar liquids due to surfactant additives is investigated intensively, motivated by its importance in a variety of applications. Most methods rely on average electrophoretic mobility measurements of many particles, which provide only indirect information on the charging mechanism. In the present work, we present a method that allows us to obtain direct information on the charging mechanism, by measuring the charge fluctuations on individual particles with a precision higher than the elementary charge using optical trapping electrophoresis. We demonstrate the capabilities of the method by studying the influence of added surfactant OLOA 11000 on the charging of single colloidal PMMA particles in dodecane. The particle charge and the frequency of charging events are investigated both below and above the critical micelle concentration (CMC) and with or without applying a DC offset voltage. It is found that at least two separate charging mechanisms are present below the critical micelle concentration. One mechanism is a process where the particle is stripped from negatively charged ionic molecules. An increase in the charging frequency with increased surfactant concentration suggests a second mechanism that involves single surfactant molecules. Above the CMC, neutral inverse micelles can also be involved in the charging process.

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

PubMed

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

2018-05-01

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

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.

Charge separation and carrier dynamics in donor-acceptor heterojunction photovoltaic systems.

PubMed

Teuscher, Joël; Brauer, Jan C; Stepanov, Andrey; Solano, Alicia; Boziki, Ariadni; Chergui, Majed; Wolf, Jean-Pierre; Rothlisberger, Ursula; Banerji, Natalie; Moser, Jacques-E

2017-11-01

Electron transfer and subsequent charge separation across donor-acceptor heterojunctions remain the most important areas of study in the field of third-generation photovoltaics. In this context, it is particularly important to unravel the dynamics of individual ultrafast processes (such as photoinduced electron transfer, carrier trapping and association, and energy transfer and relaxation), which prevail in materials and at their interfaces. In the frame of the National Center of Competence in Research "Molecular Ultrafast Science and Technology," a research instrument of the Swiss National Science Foundation, several groups active in the field of ultrafast science in Switzerland have applied a number of complementary experimental techniques and computational simulation tools to scrutinize these critical photophysical phenomena. Structural, electronic, and transport properties of the materials and the detailed mechanisms of photoinduced charge separation in dye-sensitized solar cells, conjugated polymer- and small molecule-based organic photovoltaics, and high-efficiency lead halide perovskite solar energy converters have been scrutinized. Results yielded more than thirty research articles, an overview of which is provided here.

New Techniques to Evaluate the Incendiary Behavior of Insulators

NASA Technical Reports Server (NTRS)

Buhler, Charles; Calle, Carlos; Clements, Sid; Trigwell, Steve; Ritz, Mindy

2008-01-01

New techniques for evaluating the incendiary behavior of insulators is presented. The onset of incendive brush discharges in air is evaluated using standard spark probe techniques for the case simulating approaches of an electrically grounded sphere to a charged insulator in the presence of a flammable atmosphere. However, this standard technique is unsuitable for the case of brush discharges that may occur during the charging-separation process for two insulator materials. We present experimental techniques to evaluate this hazard in the presence of a flammable atmosphere which is ideally suited to measure the incendiary nature of micro-discharges upon separation, a measurement never before performed. Other measurement techniques unique to this study include; surface potential measurements of insulators before, during and after contact and separation, as well as methods to verify fieldmeter calibrations using a charge insulator surface opposed to standard high voltage plates. Key words: Kapton polyimide film, incendiary discharges, brush discharges, contact and frictional electrification, ignition hazards, insulators, contact angle, surface potential measurements.

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.

METHOD OF SEPARATING ISOTOPES OF URANIUM IN A CALUTRON

DOEpatents

Jenkins, F.A.

1958-05-01

Mass separation devices of the calutron type and the use of uranium hexachloride as a charge material in the calutron ion source are described. The method for using this material in a mass separator includes heating the uranium hexachloride to a temperature in the range of 60 to 100 d C in a vacuum and thereby forming a vapor of the material. The vaporized uranium hexachloride is then ionized in a vapor ionizing device for subsequent mass separation processing.

A predictive theory of charge separation in organic photovoltaics interfaces

NASA Astrophysics Data System (ADS)

Troisi, Alessandro; Liu, Tao; Caruso, Domenico; Cheung, David L.; McMahon, David P.

2012-09-01

The key process in organic photovoltaics cells is the separation of an exciton, close to the donor/acceptor interface into a free hole (in the donor) and a free electron (in the acceptor). In an efficient solar cell, the majority of absorbed photons generate such hole-electron pairs but it is not clear why such a charge separation process is so efficient in some blends (for example in the blend formed by poly(3- hexylthiophene) (P3HT) and a C60 derivative (PCBM)) and how can one design better OPV materials. The electronic and geometric structure of the prototypical polymer:fullerene interface (P3HT:PCBM) is investigated theoretically using a combination of classical and quantum simulation methods. It is shown that the electronic structure of P3HT in contact with PCBM is significantly altered compared to bulk P3HT. Due to the additional free volume of the interface, P3HT chains close to PCBM are more disordered and, consequently, they are characterized by an increased band gap. Excitons and holes are therefore repelled by the interface. This provides a possible explanation of the low recombination efficiency and supports the direct formation of "quasi-free" charge separated species at the interface. This idea is further explored here by using a more general system-independent model Hamiltonian. The long range exciton dissociation rate is computed as a function of the exciton distance from the interface and the average dissociation distance is evaluated by comparing this rate with the exciton migration rate with a kinetic model. The phenomenological model shows that also in a generic interface the direct formation if quasi-free charges is extremely likely.

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

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.

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.

Use of cationic polymers to reduce pathogen levels during dairy manure separation.

PubMed

Liu, Zong; Carroll, Zachary S; Long, Sharon C; Gunasekaran, Sundaram; Runge, Troy

2016-01-15

Various separation technologies are used to deal with the enormous amounts of animal waste that large livestock operations generate. When the recycled waste stream is land applied, it is essential to lower the pathogen load to safeguard the health of livestock and humans. We investigated whether cationic polymers, used as a flocculent in the solid/liquid separation process, could reduce the pathogen indicator load in the animal waste stream. The effects of low charge density cationic polyacrylamide (CPAM) and high charge density cationic polydicyandiamide (PDCD) were investigated. Results demonstrated that CPAM was more effective than PDCD for manure coagulation and flocculation, while PDCD was more effective than CPAM in reducing the pathogen indicator loads. However, their combined use, CPAM followed by PDCD, resulted in both improved solids separation and pathogen indicator reduction. Copyright © 2015 The Authors. Published by Elsevier Ltd.. All rights reserved.

Early bacteriopheophytin reduction in charge separation in reaction centers of Rhodobacter sphaeroides.

PubMed

Zhu, Jingyi; van Stokkum, Ivo H M; Paparelli, Laura; Jones, Michael R; Groot, Marie Louise

2013-06-04

A question at the forefront of biophysical sciences is, to what extent do quantum effects and protein conformational changes play a role in processes such as biological sensing and energy conversion? At the heart of photosynthetic energy transduction lie processes involving ultrafast energy and electron transfers among a small number of tetrapyrrole pigments embedded in the interior of a protein. In the purple bacterial reaction center (RC), a highly efficient ultrafast charge separation takes place between a pair of bacteriochlorophylls: an accessory bacteriochlorophyll (B) and bacteriopheophytin (H). In this work, we applied ultrafast spectroscopy in the visible and near-infrared spectral region to Rhodobacter sphaeroides RCs to accurately track the timing of the electron on BA and HA via the appearance of the BA and HA anion bands. We observed an unexpectedly early rise of the HA⁻ band that challenges the accepted simple picture of stepwise electron transfer with 3 ps and 1 ps time constants. The implications for the mechanism of initial charge separation in bacterial RCs are discussed in terms of a possible adiabatic electron transfer step between BA and HA, and the effect of protein conformation on the electron transfer rate. Copyright © 2013 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Cyclic membrane separation process

DOEpatents

Bowser, John

2004-04-13

A cyclic process for controlling environmental emissions of volatile organic compounds (VOC) from vapor recovery in storage and dispensing operations of liquids maintains a vacuum in the storage tank ullage. In one of a two-part cyclic process ullage vapor is discharged through a vapor recovery system in which VOC are stripped from vented gas with a selectively gas permeable membrane. In the other part, the membrane is inoperative while gas pressure rises in the ullage. Ambient air is charged to the membrane separation unit during the latter part of the cycle.

ALCHEMIST (Anesthesia Log, Charge Entry, Medical Information, and Statistics)

PubMed Central

Covey, M. Carl

1979-01-01

This paper presents an automated system for the handling of charges and information processing within the Anesthesiology department of the University of Arkansas for the Medical Sciences (UAMS). The purpose of the system is to take the place of cumbersome, manual billing procedures and in the process of automated charge generation, to compile a data base of patient data for later use. ALCHEMIST has demonstrated its value by increasing both the speed and the accuracy of generation of patient charges as well as facilitating the compilation of valuable, informative reports containing statistical summaries of all aspects of the UAMS operating wing case load. ALCHEMIST allows for the entry of fifty different sets of information (multiple items in some sets) for a total of 107 separate data elements from the original anesthetic record. All this data is entered as part of the charge entry procedure.

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.

Acceptance as a Normative Aspect of the Process of Coming to Understand Emotionally Charged Concepts: Upper-Secondary School Students Make Meaning of Gender

ERIC Educational Resources Information Center

Trostek, Jonas R.

2016-01-01

Previous research on how students' acceptance of emotionally charged theories relates to their understanding is based on the measurement of acceptance and understanding as two separate variables. As an alternative, the present study takes a qualitative approach with the aim of exploring what 24 upper-secondary school students accept when they come…

Characterization of Boron Contamination in Fluorine Implantation using Boron Trifluoride as a Source Material

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

Schmeide, Matthias; Kondratenko, Serguei

2011-01-07

Fluorine implantation process purity was considered on different types of high current implanters. It was found that implanters equipped with an indirectly heated cathode ion source show an enhanced deep boron contamination compared to a high current implanter using a cold RF-driven multicusp ion source when boron trifluoride is used for fluorine implantations. This contamination is directly related to the source technology and thus, should be considered potentially for any implanter design using hot cathode/hot filament ion source, independently of the manufacturer.The boron contamination results from the generation of double charged boron ions in the arc chamber and the subsequentmore » charge exchange reaction to single charged boron ions taking place between the arc chamber and the extraction electrode. The generation of the double charged boron ions depends mostly on the source parameters, whereas the pressure in the region between the arc chamber and the extraction electrode is mostly responsible for the charge exchange from double charged to single charged ions. The apparent mass covers a wide range, starting at mass 11. A portion of boron ions with energies of (19/11) times higher than fluorine energy has the same magnetic rigidity as fluorine beam and cannot be separated by the analyzer magnet. The earlier described charge exchange effects between the extraction electrode and the entrance to the analyzer magnet, however, generates boron beam with a higher magnetic rigidity compared to fluorine beam and cannot cause boron contamination after mass-separation.The energetic boron contamination was studied as a function of the ion source parameters, such as gas flow, arc voltage, and source magnet settings, as well as analyzing magnet aperture resolution. This allows process optimization reducing boron contamination to the level acceptable for device performance.« less

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.

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.

Electrostatic Beneficiation of Lunar Simulant

NASA Technical Reports Server (NTRS)

Trigwell, Steve; Captain, James; Captain, Janine; Arens, Ellen; Quinn, Jacqueline; Calle, Carlos

2006-01-01

Electrostatic beneficiation of lunar regolith is a method allowing refinement of specific minerals in the material for processing on the moon. The use of tribocharging the regolith prior to separation was investigated on the lunar simulant MLS-I by passing the dust through static mixers constructed from different materials; aluminum, copper, stainless steel, and polytetrafluoroethylene (PTFE). The amount of charge acquired by the simulant was dependent upon the difference in the work function of the dust and the charging material. XPS and SEM were used to characterize the simulant after it was sieved into five size fractions (> 100 pm, 75-100 pm, 50- 75 pm, 50-25 pm, and < 25 pm), where very little difference in surface composition was observed between the sizes. Samples of the smallest (< 25 pm) and largest (> 100 pm) size fractions were beneficiated through a charge separator using the aluminum (charged the simulant negatively) and PTFE (charged positively) mixers. The mass fractions of the separated simulant revealed that for the larger particle size, significant unipolar charging was observed for both mixers, whereas for the smaller particle sizes, more bipolar charging was observed, probably due to the finer simulant adhering to the inside of the mixers shielding the dust from the charging material. Subsequent XPS analysis of the beneficiated fractions showed the larger particle size fraction having some species differentiation, but very little difference for the smaller.size. Although MLS-1 was made to have similar chemistry to actual lunar dust, its mineralogy is quite different. On-going experiments are using NASA JSC-1 lunar simulant. A vacuum chamber has been constructed, and future experiments are planned in a simulated lunar environment.

Separations in the STATS report

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

Choppin, G.R.

1996-12-31

The Separations Technology and Transmutation Systems (STATS) Committee formed a Subcommittee on Separations. This subcommittee was charged with evaluating the separations proposed for the several reactor and accelerator transmutation systems. It was also asked to review the processing options for the safe management of high-level waste generated by the defense programs, in particular, the special problems involved in dealing with the waste at the U.S. Department of Energy (DOE) facility in Hanford, Washington. Based on the evaluations from the Subcommittee on Separations, the STATS Committee concluded that for the reactor transmutation programs, aqueous separations involving a combination of PUREX andmore » TRUEX solvent extraction processes could be used. However, additional research and development (R&D) would be required before full plant-scale use of the TRUEX technology could be employed. Alternate separations technology for the reactor transmutation program involves pyroprocessing. This process would require a significant amount of R&D before its full-scale application can be evaluated.« less

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.

The Role of FRET in Non-Fullerene Organic Solar Cells: Implications for Molecular Design.

PubMed

Gautam, Bhoj R; Younts, Robert; Carpenter, Joshua; Ade, Harald; Gundogdu, Kenan

2018-04-19

Non-fullerene acceptors (NFAs) have been demonstrated to be promising candidates for highly efficient organic photovoltaic (OPV) devices. The tunability of absorption characteristics of NFAs can be used to make OPVs with complementary donor-acceptor absorption to cover a broad range of the solar spectrum. However, both charge transfer from donor to acceptor moieties and energy (energy) transfer from high-bandgap to low-bandgap materials are possible in such structures. Here, we show that when charge transfer and exciton transfer processes are both present, the coexistence of excitons in both domains can cause a loss mechanism. Charge separation of excitons in a low-bandgap material is hindered due to exciton population in the larger bandgap acceptor domains. Our results further show that excitons in low-bandgap material should have a relatively long lifetime compared to the transfer time of excitons from higher bandgap material in order to contribute to the charge separation. These observations provide significant guidance for design and development of new materials in OPV applications.

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

Simulation of isoelectro focusing processes. [stationary electrolysis of charged species

NASA Technical Reports Server (NTRS)

Palusinski, O. A.

1980-01-01

This paper presents the computer implementation of a model for the stationary electrolysis of two or more charged species. This has specific application to the technique of isoelectric focussing, in which the stationary electrolysis of ampholytes is used to generate a pH gradient useful for the separation of proteins, peptides and other biomolecules. The fundamental equations describing the process are given. These equations are transformed to a form suitable for digital computer implementation. Some results of computer simulation are described and compared to data obtained in the laboratory.

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.

Terahertz Emission from Hybrid Perovskites Driven by Ultrafast Charge Separation and Strong Electron-Phonon Coupling.

PubMed

Guzelturk, Burak; Belisle, Rebecca A; Smith, Matthew D; Bruening, Karsten; Prasanna, Rohit; Yuan, Yakun; Gopalan, Venkatraman; Tassone, Christopher J; Karunadasa, Hemamala I; McGehee, Michael D; Lindenberg, Aaron M

2018-03-01

Unusual photophysical properties of organic-inorganic hybrid perovskites have not only enabled exceptional performance in optoelectronic devices, but also led to debates on the nature of charge carriers in these materials. This study makes the first observation of intense terahertz (THz) emission from the hybrid perovskite methylammonium lead iodide (CH 3 NH 3 PbI 3 ) following photoexcitation, enabling an ultrafast probe of charge separation, hot-carrier transport, and carrier-lattice coupling under 1-sun-equivalent illumination conditions. Using this approach, the initial charge separation/transport in the hybrid perovskites is shown to be driven by diffusion and not by surface fields or intrinsic ferroelectricity. Diffusivities of the hot and band-edge carriers along the surface normal direction are calculated by analyzing the emitted THz transients, with direct implications for hot-carrier device applications. Furthermore, photogenerated carriers are found to drive coherent terahertz-frequency lattice distortions, associated with reorganizations of the lead-iodide octahedra as well as coupled vibrations of the organic and inorganic sublattices. This strong and coherent carrier-lattice coupling is resolved on femtosecond timescales and found to be important both for resonant and far-above-gap photoexcitation. This study indicates that ultrafast lattice distortions play a key role in the initial processes associated with charge transport. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Terahertz Emission from Hybrid Perovskites Driven by Ultrafast Charge Separation and Strong Electron-Phonon Coupling

DOE PAGES

Guzelturk, Burak; Belisle, Rebecca A.; Smith, Matthew D.; ...

2018-01-23

Unusual photophysical properties of organic–inorganic hybrid perovskites have not only enabled exceptional performance in optoelectronic devices, but also led to debates on the nature of charge carriers in these materials. This study makes the first observation of intense terahertz (THz) emission from the hybrid perovskite methylammonium lead iodide (CH 3NH 3PbI 3) following photoexcitation, enabling an ultrafast probe of charge separation, hot–carrier transport, and carrier–lattice coupling under 1–sun–equivalent illumination conditions. Using this approach, the initial charge separation/transport in the hybrid perovskites is shown to be driven by diffusion and not by surface fields or intrinsic ferroelectricity. Diffusivities of the hotmore » and band–edge carriers along the surface normal direction are calculated by analyzing the emitted THz transients, with direct implications for hot–carrier device applications. Furthermore, photogenerated carriers are found to drive coherent terahertz–frequency lattice distortions, associated with reorganizations of the lead–iodide octahedra as well as coupled vibrations of the organic and inorganic sublattices. This strong and coherent carrier–lattice coupling is resolved on femtosecond timescales and found to be important both for resonant and far–above–gap photoexcitation. As a result, this study indicates that ultrafast lattice distortions play a key role in the initial processes associated with charge transport.« less

Modeling the Electric Potential and Surface Charge Density Near Charged Thunderclouds

NASA Astrophysics Data System (ADS)

Neel, Matthew Stephen

2018-03-01

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 cloud-to-ground lightning. We wish to examine the latter form, in which upward leaders from Earth connect with downward leaders from the cloud to form a plasma channel and produce lightning. Much of the literature indicates that the lower part of a thundercloud becomes negatively charged while the upper part becomes positively charged via convective charging, although the opposite polarity can certainly exist along with various, complex intra-cloud currents. It is estimated that >90% of cloud-to-ground lightning is "negative lightning," or the flow of charges from the bottom of the cloud, while the remaining <10% of lightning strikes is "positive lightning," or the flow of charges from the top of the cloud. We wish to understand the electric potential surrounding charged thunderclouds as well as the resulting charge density on the surface of Earth below them. In this paper we construct a simple and adaptable model that captures the very basic features of the cloud/ground system and that exhibits conditions favorable for both forms of lightning. In this way, we provide a practical application of electrostatic dipole physics as well as the method of images that can serve as a starting point for further modeling and analysis by students.

Formation of Load Parameters of Destroyed Massife in Explosion of Multicharge Composition with Separation of its Parts by Profile Inert Interval

NASA Astrophysics Data System (ADS)

Paramonov, G. P.; Mysin, A. V.; Babkin, R. S.

2017-10-01

The paper introduces construction of multicharge composition with separation of parts by the profile inert interval. On the basis of the previous researches, the pulse-forming process at explosion of the borehole multicharge taking into account the offered design is considered. The physical model for definition of reflected wavelet taking into account an increment of radius of cross section of a charging cavity and the expiration of detonation products is offered. A technique is developed for numerical modeling of gas-dynamic processes in a borehole with a change in the axial channel of a profile inert interval caused by a high-temperature flow of gaseous products of an explosion. The authors obtained the dependence of the change in mean pressure on the borehole wall on time for each of the parts of the multicharge. To blast a series of charges of the proposed design, taking into account optimization of the stress fields of neighboring charges, the delay interval is determined for a short-delayed explosion.

Breaking the barriers of all-polymer solar cells: Solving electron transporter and morphology problems

NASA Astrophysics Data System (ADS)

Gavvalapalli, Nagarjuna

All-polymer solar cells (APSC) are a class of organic solar cells in which hole and electron transporting phases are made of conjugated polymers. Unlike polymer/fullerene solar cell, photoactive material of APSC can be designed to have hole and electron transporting polymers with complementary absorption range and proper frontier energy level offset. However, the highest reported PCE of APSC is 5 times less than that of polymer/fullerene solar cell. The low PCE of APSC is mainly due to: i) low charge separation efficiency; and ii) lack of optimal morphology to facilitate charge transfer and transport; and iii) lack of control over the exciton and charge transport in each phase. My research work is focused towards addressing these issues. The charge separation efficiency of APSC can be enhanced by designing novel electron transporting polymers with: i) broad absorption range; ii) high electron mobility; and iii) high dielectric constant. In addition to with the above parameters chemical and electronic structure of the repeating unit of conjugated polymer also plays a role in charge separation efficiency. So far only three classes of electron transporting polymers, CN substituted PPV, 2,1,3-benzothiadiazole derived polymers and rylene diimide derived polymers, are used in APSC. Thus to enhance the charge separation efficiency new classes of electron transporting polymers with the above characteristics need to be synthesized. I have developed a new straightforward synthetic strategy to rapidly generate new classes of electron transporting polymers with different chemical and electronic structure, broad absorption range, and high electron mobility from readily available electron deficient monomers. In APSCs due to low entropy of mixing, polymers tend to micro-phase segregate rather than forming the more useful nano-phase segregation. Optimizing the polymer blend morphology to obtain nano-phase segregation is specific to the system under study, time consuming, and not trivial. Thus to avoid micro-phase segregation, nanoparticles of hole and electron transporters are synthesized and blended. But the PCE of nanoparticle blends are far less than those of polymer blends. This is mainly due to the: i) lack of optimal assembly of nanoparticles to facilitate charge transfer and transport processes; and ii) lack of control over the exciton and charge transport properties within the nanoparticles. Polymer packing within the nanoparticle controls the optoelectronic and charge transport properties of the nanoparticle. In this work I have shown that the solvent used to synthesize nanoparticles plays a crucial role in determining the assembly of polymer chains inside the nanoparticle there by affecting its exciton and charge transport processes. To obtain the optimal morphology for better charge transfer and transport, we have also synthesized nanoparticles of different radius with surfactants of opposite charge. We propose that depending on the radius and/or Coulombic interactions these nanoparticles can be assembled into mineral structure-types that are useful for photovoltaic devices.

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.

Electrokinetic Response of Charge-Selective Nanostructured Polymeric Membranes

NASA Astrophysics Data System (ADS)

Schiffbauer, Jarrod; Li, Diya; Gao, Feng; Phillip, William; Chang, Hsueh-Chia

2017-11-01

Nanostructured polymeric membranes, with a tunable pore size and ease of surface molecular functionalization, are a promising material for separations, filtration, and sensing applications. Recently, such membranes have been fabricated wherein the ion selectivity is imparted by self-assembled functional groups through a two-step process. Amine groups are used to provide a positive surface charge and acid groups are used to yield a negative charge. The membranes can be fabricated as either singly-charged or patterned/mosaic membranes, where there are alternating regions of amine- lined or acid-lined pores. We demonstrate that such membranes, in addition to having many features in common with other charge selective membranes (i.e. AMX or Nafion), display a unique single-membrane rectification behavior. This is due to the asymmetric distribution of charged functional groups during the fabrication process. We demonstrate this rectification effect using both dc current-voltage characteristics as well as dc-biased electrical impedance spectroscopy. Furthermore, surface charge changes due to dc concentration polarization and generation of localized pH shifts are monitored using electrical impedance spectroscopy. (formerly at University of Notre Dame).

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.

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.

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.

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.

Charge separation and carrier dynamics in donor-acceptor heterojunction photovoltaic systems

PubMed Central

Teuscher, Joël; Brauer, Jan C.; Stepanov, Andrey; Solano, Alicia; Boziki, Ariadni; Chergui, Majed; Wolf, Jean-Pierre; Rothlisberger, Ursula; Banerji, Natalie; Moser, Jacques-E.

2017-01-01

Electron transfer and subsequent charge separation across donor-acceptor heterojunctions remain the most important areas of study in the field of third-generation photovoltaics. In this context, it is particularly important to unravel the dynamics of individual ultrafast processes (such as photoinduced electron transfer, carrier trapping and association, and energy transfer and relaxation), which prevail in materials and at their interfaces. In the frame of the National Center of Competence in Research “Molecular Ultrafast Science and Technology,” a research instrument of the Swiss National Science Foundation, several groups active in the field of ultrafast science in Switzerland have applied a number of complementary experimental techniques and computational simulation tools to scrutinize these critical photophysical phenomena. Structural, electronic, and transport properties of the materials and the detailed mechanisms of photoinduced charge separation in dye-sensitized solar cells, conjugated polymer- and small molecule-based organic photovoltaics, and high-efficiency lead halide perovskite solar energy converters have been scrutinized. Results yielded more than thirty research articles, an overview of which is provided here. PMID:29308415

Facile Synthesis of Ultrafine Hematite Nanowire Arrays in Mixed Water-Ethanol-Acetic Acid Solution for Enhanced Charge Transport and Separation.

PubMed

Wang, Jian; Wang, Menglong; Zhang, Tao; Wang, Zhiqiang; Guo, Penghui; Su, Jinzhan; Guo, Liejin

2018-04-18

Nanostructure engineering is of great significance for semiconductor electrode to achieve high photoelectrochemical performance. Herein, we report a novel strategy to fabricate ultrafine hematite (α-Fe 2 O 3 ) nanowire arrays in a mixed water-ethanol-acetic acid (WEA) solvent. To the best of our knowledge, this is the first report on direct growth of ultrafine (∼10 nm) α-Fe 2 O 3 nanowire arrays on fluorine-doped tin oxide substrates through solution-based fabrication process. The effect of WEA ratio on the morphology of nanowires has been systematically studied to understand the formation mechanism. Photoelectrochemical measurements were conducted on both Ti-treated α-Fe 2 O 3 nanowire and nanorod photoelectrodes. It reveals that α-Fe 2 O 3 nanowire electrode has higher photocurrent and charge separation efficiencies than nanorod electrode if the carrier concentration and space-charge carrier width are in the same order of magnitude. Normalized by electrochemically active surface area, the Ti-treated α-Fe 2 O 3 nanowire electrode obtains 6.4 times higher specific photocurrent density than nanorod electrode. This superiority of nanowires arises from the higher bulk and surface charge separation efficiencies, which could be partly attributed to reduced distance that holes must transfer to reach the semiconductor-liquid junction.

Light-induced charge separation across bio-inorganic interface.

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

Dimitrijevic, N. M.; Rajh, T.; De La Garza, L.

Rational design of hybrid biomolecule - nanoparticulate semiconductor conjugates enables coupling of functionality of biomolecules with the capability of semiconductors for solar energy capture, that can have potential application in energy conversion, sensing and catalysis. The particular challenge is to obtain efficient charge separation analogous to the natural photosynthesis process. The synthesis of axially anisotropic TiO{sub 2} nano-objects such as tubes, rods and bricks, as well as spherical and faceted nanoparticles has been developed in our laboratory. Depending on their size and shape, these nanostructures exhibit different domains of crystallinity, surface areas and aspect ratios. Moreover, in order to accommodatemore » for high curvature in nanoscale regime, the surfaces of TiO{sub 2} nano-objects reconstructs resulting in changes in the coordination of surface Ti atoms from octahedral (D{sub 2d}) to square pyramidal structures (C{sub 4v}). The formation of these coordinatively unsaturated Ti atoms, thus depends strongly on the size and shape of nanocrystallites and affects trapping and reactivity of photogenerated charges. We have exploited these coordinatively unsaturated Ti atoms to coupe electron-donating (such as dopamine) and electron-accepting (pyrroloquinoline quinone) conductive linkers that allow wiring of biomolecules and proteins resulting in enhanced charge separation which increases the yield of ensuing chemical transformations.« less

Charge Separation and Exciton Dynamics at Polymer/ZnO Interface from First-Principles Simulations.

PubMed

Wu, Guangfen; Li, Zi; Zhang, Xu; Lu, Gang

2014-08-07

Charge separation and exciton dynamics play a crucial role in determining the performance of excitonic photovoltaics. Using time-dependent density functional theory with a range-separated exchange-correlation functional as well as nonadiabatic ab initio molecular dynamics, we have studied the formation and dynamics of charge-transfer (CT) excitons at polymer/ZnO interface. The interfacial atomic structure, exciton density of states and conversions between exciton species are examined from first-principles. The exciton dynamics exhibits both adiabatic and nonadiabatic characters. While the adiabatic transitions are facilitated by C═C vibrations along the polymer (P3HT) backbone, the nonadiabatic transitions are realized by exciton hopping between the excited states. We find that the localized ZnO surface states lead to localized low-energy CT states and poor charge separation. In contrast, the surface states of crystalline C60 are indistinguishable from the bulk states, resulting in delocalized CT states and efficient charge separation in polymer/fullerene (P3HT/PCBM) heterojunctions. The hot CT states are found to cool down in an ultrafast time scale and may not play a major role in charge separation of P3HT/ZnO. Finally we suggest that the dimensions of nanostructured acceptors can be tuned to obtain both efficient charge separation and high open circuit voltages.

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

Possible origin and roles of nano-porosity in ZrO2 scales for hydrogen pick-up in Zr alloys

NASA Astrophysics Data System (ADS)

Lindgren, Mikaela; Geers, Christine; Panas, Itai

2017-08-01

A mechanistic understanding of Wagnerian build-up and subsequent non-Wagnerian break-down of barrier oxide upon oxidation of zirconium alloys by water is reiterated. Hydrogen assisted build-up of nano-porosity is addressed. Growth of sub-nanometer wide stalactitic pores owing to increasing aggregation of neutral oxygen vacancies offering a means to permeate hydrogen into the alloy is explored by density functional theory. The Wagnerian channel utilizes charge separation allowing charged oxygen vacancies and electrons to move separately from nominal anode to nominal cathode. This process becomes increasingly controlled by the charging of the barrier oxide resulting in sub-parabolic rate law for oxide growth. The break-down of the barrier oxide is understood to be preceded by avalanching hydrogen pick-up in the alloy. Pore mediated diffusion allows water to effectively short circuit the barrier oxide.

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.

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.

Aggregation of flexible polyelectrolytes: Phase diagram and dynamics.

PubMed

Tom, Anvy Moly; Rajesh, R; Vemparala, Satyavani

2017-10-14

Similarly charged polymers in solution, known as polyelectrolytes, are known to form aggregated structures in the presence of oppositely charged counterions. Understanding the dependence of the equilibrium phases and the dynamics of the process of aggregation on parameters such as backbone flexibility and charge density of such polymers is crucial for insights into various biological processes which involve biological polyelectrolytes such as protein, DNA, etc. Here, we use large-scale coarse-grained molecular dynamics simulations to obtain the phase diagram of the aggregated structures of flexible charged polymers and characterize the morphology of the aggregates as well as the aggregation dynamics, in the presence of trivalent counterions. Three different phases are observed depending on the charge density: no aggregation, a finite bundle phase where multiple small aggregates coexist with a large aggregate and a fully phase separated phase. We show that the flexibility of the polymer backbone causes strong entanglement between charged polymers leading to additional time scales in the aggregation process. Such slowing down of the aggregation dynamics results in the exponent, characterizing the power law decay of the number of aggregates with time, to be dependent on the charge density of the polymers. These results are contrary to those obtained for rigid polyelectrolytes, emphasizing the role of backbone flexibility.

Inactivation of Gating Currents of L-Type Calcium Channels

PubMed Central

Shirokov, Roman; Ferreira, Gonzalo; Yi, Jianxun; Ríos, Eduardo

1998-01-01

In studies of gating currents of rabbit cardiac Ca channels expressed as α1C/β2a or α1C/β2a/α2δ subunit combinations in tsA201 cells, we found that long-lasting depolarization shifted the distribution of mobile charge to very negative potentials. The phenomenon has been termed charge interconversion in native skeletal muscle (Brum, G., and E. Ríos. 1987. J. Physiol. (Camb.). 387:489–517) and cardiac Ca channels (Shirokov, R., R. Levis, N. Shirokova, and E. Ríos. 1992. J. Gen. Physiol. 99:863–895). Charge 1 (voltage of half-maximal transfer, V1/2 ≃ 0 mV) gates noninactivated channels, while charge 2 (V1/2 ≃ −90 mV) is generated in inactivated channels. In α1C/β2a cells, the available charge 1 decreased upon inactivating depolarization with a time constant τ ≃ 8, while the available charge 2 decreased upon recovery from inactivation (at −200 mV) with τ ≃ 0.3 s. These processes therefore are much slower than charge movement, which takes <50 ms. This separation between the time scale of measurable charge movement and that of changes in their availability, which was even wider in the presence of α2δ, implies that charges 1 and 2 originate from separate channel modes. Because clear modal separation characterizes slow (C-type) inactivation of Na and K channels, this observation establishes the nature of voltage-dependent inactivation of L-type Ca channels as slow or C-type. The presence of the α2δ subunit did not change the V1/2 of charge 2, but sped up the reduction of charge 1 upon inactivation at 40 mV (to τ ≃ 2 s), while slowing the reduction of charge 2 upon recovery (τ ≃ 2 s). The observations were well simulated with a model that describes activation as continuous electrodiffusion (Levitt, D. 1989. Biophys. J. 55:489–498) and inactivation as discrete modal change. The effects of α2δ are reproduced assuming that the subunit lowers the free energy of the inactivated mode. PMID:9607938

Domain Formation Induced by the Adsorption of Charged Proteins on Mixed Lipid Membranes

PubMed Central

Mbamala, Emmanuel C.; Ben-Shaul, Avinoam; May, Sylvio

2005-01-01

Peripheral proteins can trigger the formation of domains in mixed fluid-like lipid membranes. We analyze the mechanism underlying this process for proteins that bind electrostatically onto a flat two-component membrane, composed of charged and neutral lipid species. Of particular interest are membranes in which the hydrocarbon lipid tails tend to segregate owing to nonideal chain mixing, but the (protein-free) lipid membrane is nevertheless stable due to the electrostatic repulsion between the charged lipid headgroups. The adsorption of charged, say basic, proteins onto a membrane containing anionic lipids induces local lipid demixing, whereby charged lipids migrate toward (or away from) the adsorption site, so as to minimize the electrostatic binding free energy. Apart from reducing lipid headgroup repulsion, this process creates a gradient in lipid composition around the adsorption zone, and hence a line energy whose magnitude depends on the protein's size and charge and the extent of lipid chain nonideality. Above a certain critical lipid nonideality, the line energy is large enough to induce domain formation, i.e., protein aggregation and, concomitantly, macroscopic lipid phase separation. We quantitatively analyze the thermodynamic stability of the dressed membrane based on nonlinear Poisson-Boltzmann theory, accounting for both the microscopic characteristics of the proteins and lipid composition modulations at and around the adsorption zone. Spinodal surfaces and critical points of the dressed membranes are calculated for several different model proteins of spherical and disk-like shapes. Among the models studied we find the most substantial protein-induced membrane destabilization for disk-like proteins whose charges are concentrated in the membrane-facing surface. If additional charges reside on the side faces of the proteins, direct protein-protein repulsion diminishes considerably the propensity for domain formation. Generally, a highly charged flat face of a macroion appears most efficient in inducing large compositional gradients, hence a large and unfavorable line energy and consequently lateral macroion aggregation and, concomitantly, macroscopic lipid phase separation. PMID:15626713

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.

Interaction and Aggregation of Colloidal Biological Particles and Droplets in Electrically-Driven Flows

NASA Technical Reports Server (NTRS)

Davis, Robert H.; Loewenberg, Michael

1997-01-01

The primary objective of this research was to develop a fundamental understanding of aggregation and coalescence processes during electrically-driven migration of cells, particles and droplets. The process by which charged cells, particles, molecules, or drops migrate in a weak electric field is known as electrophoresis. If the migrating species have different charges or surface potentials, they will migrate at different speeds and thus may collide and aggregate or coalesce. Aggregation and coalescence are undesirable, if the goal is to separate the different species on the basis of their different electrophoretic mobilities.

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.

Recovery of Anthocyanins Using Membrane Technologies: A Review.

PubMed

Martín, Julia; Díaz-Montaña, Enrique Jacobo; Asuero, Agustin G

2018-05-04

Anthocyanins are naturally occurring polyphenolic compounds and give many flowers, fruits and vegetable their orange, red, purple and blue colors. Besides their color attributes, anthocyanins have received much attention in recent years due to the growing evidence of their antioxidant capacity and health benefits on humans. However, these compounds usually occur in low concentrations in mixtures of complex matrices, and therefore large-scale harvesting is needed to obtain sufficient amounts for their practical usage. Effective fractionation or separation technologies are therefore essential for the screening and production of these bioactive compounds. In this context, membrane technologies have become popular due to their operational simplicity, the capacity to achieve good simultaneous separation/pre-concentration and matrix reduction with lower temperature and lower operating cost in comparison to other sample preparation methods. Membrane fractionation is based on the molecular or particle sizes (pressure-driven processes), on their charge (electrically driven processes) or are dependent on both size and charge. Other non-pressure-driven membrane processes (osmotic pressure and vapor pressure-driven) have been developed in recent years and employed as alternatives for the separation or fractionation of bioactive compounds at ambient conditions without product deterioration. These technologies are applied either individually or in combination as an integrated membrane system to meet the different requirements for the separation of bioactive compounds. The first section of this review examines the basic principles of membrane processes, including the different types of membranes, their structure, morphology and geometry. The most frequently used techniques are also discussed. Last, the specific application of these technologies for the separation, purification and concentration of phenolic compounds, with special emphasis on anthocyanins, are also provided.

Reducing charging effects in scanning electron microscope images by Rayleigh contrast stretching method (RCS).

PubMed

Wan Ismail, W Z; Sim, K S; Tso, C P; Ting, H Y

2011-01-01

To reduce undesirable charging effects in scanning electron microscope images, Rayleigh contrast stretching is developed and employed. First, re-scaling is performed on the input image histograms with Rayleigh algorithm. Then, contrast stretching or contrast adjustment is implemented to improve the images while reducing the contrast charging artifacts. This technique has been compared to some existing histogram equalization (HE) extension techniques: recursive sub-image HE, contrast stretching dynamic HE, multipeak HE and recursive mean separate HE. Other post processing methods, such as wavelet approach, spatial filtering, and exponential contrast stretching, are compared as well. Overall, the proposed method produces better image compensation in reducing charging artifacts. Copyright © 2011 Wiley Periodicals, Inc.

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.

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.

Self-Assembly Strategies for Integrating Light Harvesting and Charge Separation in Artificial Photosynthetic Systems

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

Wasielewski, Michael R.

In natural photosynthesis, organisms optimize solar energy conversion through organized assemblies of photofunctional chromophores and catalysts within proteins that provide specifically tailored environments for chemical reactions. As with their natural counterparts, artificial photosynthetic systems for practical solar fuels production must collect light energy, separate charge, and transport charge to catalytic sites where multielectron redox processes will occur. While encouraging progress has been made on each aspect of this complex problem, researchers have not yet developed self-ordering and self-assembling components and the tailored environments necessary to realize a fully-functional artificial system. Previously researchers have used complex, covalent molecular systems comprised ofmore » chromophores, electron donors, and electron acceptors to mimic both the light-harvesting and the charge separation functions of photosynthetic proteins. These systems allow for study of the dependencies of electron transfer rate constants on donor?acceptor distance and orientation, electronic interaction, and the free energy of the reaction. The most useful and informative systems are those in which structural constraints control both the distance and the orientation between the electron donors and acceptors. Self-assembly provides a facile means for organizing large numbers of molecules into supramolecular structures that can bridge length scales from nanometers to macroscopic dimensions. The resulting structures must provide pathways for migration of light excitation energy among antenna chromophores, and from antennas to reaction centers. They also must incorporate charge conduits, that is, molecular 'wires' that can efficiently move electrons and holes between reaction centers and catalytic sites. The central scientific challenge is to develop small, functional building blocks with a minimum number of covalent linkages, which also have the appropriate molecular recognition properties to facilitate self-assembly of complete, functional artificial photosynthetic systems. In this Account, we explore how self-assembly strategies involving ?-stacking can be used to integrate light harvesting with charge separation and transport.« less

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

Organic phototransistors with nanoscale phase-separated polymer/polymer bulk heterojunction layers

NASA Astrophysics Data System (ADS)

Hwang, Hyemin; Kim, Hwajeong; Nam, Sungho; Bradley, Donal D. C.; Ha, Chang-Sik; Kim, Youngkyoo

2011-05-01

Low-cost detectors for sensing photons at a low light intensity are of crucial importance in modern science. Phototransistors can deliver better signals of low-intensity light by electrical amplification, but conventional inorganic phototransistors have a limitation owing to their high temperature processes in vacuum. In this work, we demonstrate organic phototransistors with polymer/polymer bulk heterojunction blend films (mixtures of p-type and n-type semiconducting polymers), which can be fabricated by inexpensive solution processes at room temperature. The key idea here is to effectively exploit hole charges (from p-type polymer) as major signaling carriers by employing p-type transistor geometry, while the n-type polymer helps efficient charge separation from excitons generated by incoming photons. Results showed that the present organic transistors exhibited proper functions as p-type phototransistors with ~4.3 A W-1 responsivity at a low light intensity (1 µW cm-2), which supports their encouraging potential to replace conventional cooled charge coupled devices (CCD) for low-intensity light detection applications.Low-cost detectors for sensing photons at a low light intensity are of crucial importance in modern science. Phototransistors can deliver better signals of low-intensity light by electrical amplification, but conventional inorganic phototransistors have a limitation owing to their high temperature processes in vacuum. In this work, we demonstrate organic phototransistors with polymer/polymer bulk heterojunction blend films (mixtures of p-type and n-type semiconducting polymers), which can be fabricated by inexpensive solution processes at room temperature. The key idea here is to effectively exploit hole charges (from p-type polymer) as major signaling carriers by employing p-type transistor geometry, while the n-type polymer helps efficient charge separation from excitons generated by incoming photons. Results showed that the present organic transistors exhibited proper functions as p-type phototransistors with ~4.3 A W-1 responsivity at a low light intensity (1 µW cm-2), which supports their encouraging potential to replace conventional cooled charge coupled devices (CCD) for low-intensity light detection applications. Electronic supplementary information (ESI) available: XPS spectra of P3HT:F8BT nanolayers and pristine P3HT and F8BT films, HRTEM images of P3HT:F8BT blend film detached from the substrate, and 1D GIXD profiles of P3HT:F8BT nanolayers and PI layer coated on the ITO-glass substrates. See DOI: 10.1039/c0nr00915f

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

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

A Model of the Turbulent Electric Dynamo in Multi-Phase Media

NASA Astrophysics Data System (ADS)

Dementyeva, Svetlana; Mareev, Evgeny

2016-04-01

Many terrestrial and astrophysical phenomena witness the conversion of kinetic energy into electric energy (the energy of the quasi-stationary electric field) in conducting media, which is natural to treat as manifestations of electric dynamo by analogy with well-known theory of magnetic dynamo. Such phenomena include thunderstorms and lightning in the Earth's atmosphere and atmospheres of other planets, electric activity caused by dust storms in terrestrial and Martian atmospheres, snow storms, electrical discharges occurring in technological setups, connected with intense mixing of aerosol particles like in the milling industry. We have developed a model of the large-scale turbulent electric dynamo in a weakly conducting medium, containing two heavy-particle components. We have distinguished two main classes of charging mechanisms (inductive and non-inductive) in accordance with the dependence or independence of the electric charge, transferred during a particle collision, on the electric field intensity and considered the simplified models which demonstrate the possibility of dynamo realization and its specific peculiarities for these mechanisms. Dynamo (the large-scale electric field growth) appears due to the charge separation between the colliding and rebounding particles. This process is may be greatly intensified by the turbulent mixing of particles with different masses and, consequently, different inertia. The particle charge fluctuations themselves (small-scale dynamo), however, do not automatically mean growth of the large-scale electric field without a large-scale asymmetry. Such an asymmetry arises due to the dependence of the transferred charge magnitude on the electric field intensity in the case of the inductive mechanism of charge separation, or due to the gravity and convection for non-inductive mechanisms. We have found that in the case of the inductive mechanism the large-scale dynamo occurs if the medium conductivity is small enough while the electrification process determined by the turbulence intensity and particles sizes is strong enough. The electric field strength grows exponentially. For the non-inductive mechanism we have found the conditions when the electric field strength grows but linearly in time. Our results show that turbulent electric dynamo could play a substantial role in the electrification processes for different mechanisms of charge generation and separation. Thunderstorms and lightning are the most frequent and spectacular manifestations of electric dynamo in the atmosphere, but turbulent electric dynamo may also be the reason of electric discharges occurring in dust and snow storms or even in technological setups with intense mixing of small particles.

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.

A Unified Model of Cloud-to-Ground Lightning Stroke

NASA Astrophysics Data System (ADS)

Nag, A.; Rakov, V. A.

2014-12-01

The first stroke in a cloud-to-ground lightning discharge is thought to follow (or be initiated by) the preliminary breakdown process which often produces a train of relatively large microsecond-scale electric field pulses. This process is poorly understood and rarely modeled. Each lightning stroke is composed of a downward leader process and an upward return-stroke process, which are usually modeled separately. We present a unified engineering model for computing the electric field produced by a sequence of preliminary breakdown, stepped leader, and return stroke processes, serving to transport negative charge to ground. We assume that a negatively-charged channel extends downward in a stepped fashion through the relatively-high-field region between the main negative and lower positive charge centers and then through the relatively-low-field region below the lower positive charge center. A relatively-high-field region is also assumed to exist near ground. The preliminary breakdown pulse train is assumed to be generated when the negatively-charged channel interacts with the lower positive charge region. At each step, an equivalent current source is activated at the lower extremity of the channel, resulting in a step current wave that propagates upward along the channel. The leader deposits net negative charge onto the channel. Once the stepped leader attaches to ground (upward connecting leader is presently neglected), an upward-propagating return stroke is initiated, which neutralizes the charge deposited by the leader along the channel. We examine the effect of various model parameters, such as step length and current propagation speed, on model-predicted electric fields. We also compare the computed fields with pertinent measurements available in the literature.

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).

Experimental design of a twin-column countercurrent gradient purification process.

PubMed

Steinebach, Fabian; Ulmer, Nicole; Decker, Lara; Aumann, Lars; Morbidelli, Massimo

2017-04-07

As typical for separation processes, single unit batch chromatography exhibits a trade-off between purity and yield. The twin-column MCSGP (multi-column countercurrent solvent gradient purification) process allows alleviating such trade-offs, particularly in the case of difficult separations. In this work an efficient and reliable procedure for the design of the twin-column MCSGP process is developed. This is based on a single batch chromatogram, which is selected as the design chromatogram. The derived MCSGP operation is not intended to provide optimal performance, but it provides the target product in the selected fraction of the batch chromatogram, but with higher yield. The design procedure is illustrated for the isolation of the main charge isoform of a monoclonal antibody from Protein A eluate with ion-exchange chromatography. The main charge isoform was obtained at a purity and yield larger than 90%. At the same time process related impurities such as HCP and leached Protein A as well as aggregates were at least equally well removed. Additionally, the impact of several design parameters on the process performance in terms of purity, yield, productivity and buffer consumption is discussed. The obtained results can be used for further fine-tuning of the process parameters so as to improve its performance. Copyright © 2017 Elsevier B.V. All rights reserved.

Dissecting protein function: an efficient protocol for identifying separation-of-function mutations that encode structurally stable proteins.

PubMed

Lubin, Johnathan W; Rao, Timsi; Mandell, Edward K; Wuttke, Deborah S; Lundblad, Victoria

2013-03-01

Mutations that confer the loss of a single biochemical property (separation-of-function mutations) can often uncover a previously unknown role for a protein in a particular biological process. However, most mutations are identified based on loss-of-function phenotypes, which cannot differentiate between separation-of-function alleles vs. mutations that encode unstable/unfolded proteins. An alternative approach is to use overexpression dominant-negative (ODN) phenotypes to identify mutant proteins that disrupt function in an otherwise wild-type strain when overexpressed. This is based on the assumption that such mutant proteins retain an overall structure that is comparable to that of the wild-type protein and are able to compete with the endogenous protein (Herskowitz 1987). To test this, the in vivo phenotypes of mutations in the Est3 telomerase subunit from Saccharomyces cerevisiae were compared with the in vitro secondary structure of these mutant proteins as analyzed by circular-dichroism spectroscopy, which demonstrates that ODN is a more sensitive assessment of protein stability than the commonly used method of monitoring protein levels from extracts. Reverse mutagenesis of EST3, which targeted different categories of amino acids, also showed that mutating highly conserved charged residues to the oppositely charged amino acid had an increased likelihood of generating a severely defective est3(-) mutation, which nevertheless encoded a structurally stable protein. These results suggest that charge-swap mutagenesis directed at a limited subset of highly conserved charged residues, combined with ODN screening to eliminate partially unfolded proteins, may provide a widely applicable and efficient strategy for generating separation-of-function mutations.

Unified superresolution experiments and stochastic theory provide mechanistic insight into protein ion-exchange adsorptive separations

PubMed Central

Kisley, Lydia; Chen, Jixin; Mansur, Andrea P.; Shuang, Bo; Kourentzi, Katerina; Poongavanam, Mohan-Vivekanandan; Chen, Wen-Hsiang; Dhamane, Sagar; Willson, Richard C.; Landes, Christy F.

2014-01-01

Chromatographic protein separations, immunoassays, and biosensing all typically involve the adsorption of proteins to surfaces decorated with charged, hydrophobic, or affinity ligands. Despite increasingly widespread use throughout the pharmaceutical industry, mechanistic detail about the interactions of proteins with individual chromatographic adsorbent sites is available only via inference from ensemble measurements such as binding isotherms, calorimetry, and chromatography. In this work, we present the direct superresolution mapping and kinetic characterization of functional sites on ion-exchange ligands based on agarose, a support matrix routinely used in protein chromatography. By quantifying the interactions of single proteins with individual charged ligands, we demonstrate that clusters of charges are necessary to create detectable adsorption sites and that even chemically identical ligands create adsorption sites of varying kinetic properties that depend on steric availability at the interface. Additionally, we relate experimental results to the stochastic theory of chromatography. Simulated elution profiles calculated from the molecular-scale data suggest that, if it were possible to engineer uniform optimal interactions into ion-exchange systems, separation efficiencies could be improved by as much as a factor of five by deliberately exploiting clustered interactions that currently dominate the ion-exchange process only accidentally. PMID:24459184

Unified superresolution experiments and stochastic theory provide mechanistic insight into protein ion-exchange adsorptive separations.

PubMed

Kisley, Lydia; Chen, Jixin; Mansur, Andrea P; Shuang, Bo; Kourentzi, Katerina; Poongavanam, Mohan-Vivekanandan; Chen, Wen-Hsiang; Dhamane, Sagar; Willson, Richard C; Landes, Christy F

2014-02-11

Chromatographic protein separations, immunoassays, and biosensing all typically involve the adsorption of proteins to surfaces decorated with charged, hydrophobic, or affinity ligands. Despite increasingly widespread use throughout the pharmaceutical industry, mechanistic detail about the interactions of proteins with individual chromatographic adsorbent sites is available only via inference from ensemble measurements such as binding isotherms, calorimetry, and chromatography. In this work, we present the direct superresolution mapping and kinetic characterization of functional sites on ion-exchange ligands based on agarose, a support matrix routinely used in protein chromatography. By quantifying the interactions of single proteins with individual charged ligands, we demonstrate that clusters of charges are necessary to create detectable adsorption sites and that even chemically identical ligands create adsorption sites of varying kinetic properties that depend on steric availability at the interface. Additionally, we relate experimental results to the stochastic theory of chromatography. Simulated elution profiles calculated from the molecular-scale data suggest that, if it were possible to engineer uniform optimal interactions into ion-exchange systems, separation efficiencies could be improved by as much as a factor of five by deliberately exploiting clustered interactions that currently dominate the ion-exchange process only accidentally.

Exploring what prompts ITIC to become a superior acceptor in organic solar cell by combining molecular dynamics simulation with quantum chemistry calculation.

PubMed

Pan, Qing-Qing; Li, Shuang-Bao; Duan, Ying-Chen; Wu, Yong; Zhang, Ji; Geng, Yun; Zhao, Liang; Su, Zhong-Min

2017-11-29

The interface characteristic is a crucial factor determining the power conversion efficiency of organic solar cells (OSCs). In this work, our aim is to conduct a comparative study on the interface characteristics between the very famous non-fullerene acceptor, ITIC, and a fullerene acceptor, PC71BM by combining molecular dynamics simulations with density functional theory. Based on some typical interface models of the acceptor ITIC or PC71BM and the donor PBDB-T selected from MD simulation, besides the evaluation of charge separation/recombination rates, the relative positions of Frenkel exciton (FE) states and the charge transfer states along with their oscillator strengths are also employed to estimate the charge separation abilities. The results show that, when compared with those for the PBDB-T/PC71BM interface, the CT states are more easily formed for the PBDB-T/ITIC interface by either the electron transfer from the FE state or direct excitation, indicating the better charge separation ability of the former. Moreover, the estimation of the charge separation efficiency manifests that although these two types of interfaces have similar charge recombination rates, the PBDB-T/ITIC interface possesses the larger charge separation rates than those of the PBDB-T/PC71BM interface. Therefore, the better match between PBDB-T and ITIC together with a larger charge separation efficiency at the interface are considered to be the reasons for the prominent performance of ITIC in OSCs.

Multi-chamber electroosmosis using textile reinforced agar membranes--A promising concept for the future of hemodialysis.

PubMed

Kofler, Markus; Lenninger, Margit; Mayer, Gert; Neuwirt, Hannes; Grimm, Michael; Bechtold, Thomas

2016-01-20

Renal replacement therapy options are limited to hemodialysis and peritoneal dialysis (70% of US patients) or renal transplantation. Diffusion processes are the main physico-chemical principle behind hemodialysis. An alternative way to achieve liquid flow through membranes bases on the electroosmotic flow which is observed as electrokinetic phenomenon in porous membranes which bear surface charges. Agar consists of the non-ionic agarose and the negatively charged agaropectine thus an electroosmotic flux is observed in analytical electrophoresis. In this study the potential electroosmosis on textile reinforced agar membranes as separation method was investigated. Using a five-chamber electrolysis cell and an agar membrane/cellulose fabric composite an intensive electroosmotic flow of 1-2 ml cm(2) h(-1) at 100 mA cell current could be observed. The movement of cations in the negatively charged agar structure led to an intensive electroosmotic flux, which also transported uncharged molecules such as urea, glucose through the membrane. Separation of uncharged low molecular weight molecules is determined by the membrane characteristic. The transport of ions (K(+), PO4(3-), creatinine) and uncharged molecules (urea, glucose) in electroosmotic separation experiments was monitored using a pH 5.5 phosphate electrolyte with the aim to assess the overall transport processes in the electrochemical cell. The results demonstrate the potential of the method for filtration of biological fluids in the absence of external pressure or high shear rates. Copyright © 2015 Elsevier Ltd. All rights reserved.

Antioxidants, mechanisms, and recovery by membrane processes.

PubMed

Bazinet, Laurent; Doyen, Alain

2017-03-04

Antioxidants molecules have a great interest for bio-food and nutraceutical industries since they play a vital role for their capacity to reduce oxidative processes. Consequently, these molecules, generally present in complex matrices, have to be fractionated and purified to characterize them and to test their antioxidant activity. However, as natural or synthetics antioxidant molecules differ in terms of structural composition and physico-chemical properties, appropriate separation technologies must be selected. Different fractionation technologies are available but the most commonly used are filtration processes. Indeed, these technologies allow fractionation according to molecular size (pressure-driven processes), charge, or both size and charge (electrically driven processes). In this context, and after summarizing the reaction mechanisms of the different classes and nature of antioxidants as well as membrane fractionation technologies, this manuscript presents the specific applications of these membranes processes for the recovery of antioxidant molecules.

Effect of charge ordering and phase separation on the electrical and magnetoresistive properties of polycrystalline La0.4Eu0.1Ca0.5MnO3

NASA Astrophysics Data System (ADS)

Krichene, A.; Boujelben, W.; Mukherjee, S.; Shah, N. A.; Solanki, P. S.

2018-03-01

We have investigated the effect of charge ordering and phase separation on the electrical and magnetotransport properties of La0.4Eu0.1Ca0.5MnO3 polycrystalline sample. Temperature dependence of resistivity shows a metal-insulator transition at transition temperature Tρ. A hysteretic behavior is observed for zero field resistivity curves with Tρ = 128 K on cooling process and Tρ = 136 K on warming process. Zero field resistivity curves follow Zener polynomial law in the metallic phase with unusual n exponent value ∼9. Presence of resistivity minimum at low temperatures has been ascribed to the coulombic electron-electron scattering process. Resistivity modification due to the magnetic field cycling testifies the presence of the training effect. Magnetization and resistivity appear to be highly correlated. Magnetoresistive study reveals colossal values of negative magnetoresistance reaching about 75% at 132 K under only 2T applied field. Colossal values of magnetoresistance suggest the possibility of using this sample for magnetic field sensing and spintronic applications.

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

Field-induced exciton dissociation in PTB7-based organic solar cells

NASA Astrophysics Data System (ADS)

Gerhard, Marina; Arndt, Andreas P.; Bilal, Mühenad; Lemmer, Uli; Koch, Martin; Howard, Ian A.

2017-05-01

The physics of charge separation in organic semiconductors is a topic of ongoing research of relevance to material and device engineering. Herein, we present experimental observations of the field and temperature dependence of charge separation from singlet excitons in PTB7 and PC71BM , and from charge-transfer states created across interfaces in PTB 7 /PC71BM bulk heterojunction solar cells. We obtain this experimental data by time-resolving the near infrared emission of the states from 10 K to room temperature and electric fields from 0 to 2.5 MVcm -1 . Examining how the luminescence is quenched by field and temperature gives direct insight into the underlying physics. We observe that singlet excitons can be split by high fields, and that disorder broadens the high threshold fields needed to split the excitons. Charge-transfer (CT) states, on the other hand, can be separated by both field and temperature. Also, the data imply a strong reduction of the activation barrier for charge splitting from the CT state relative to the exciton state. The observations provided herein of the field-dependent separation of CT states as a function of temperature offer a rich data set against which theoretical models of charge separation can be rigorously tested; it should be useful for developing the more advanced theoretical models of charge separation.

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

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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.

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.

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

Exceptionally Long-Lived Charge Separated State in Zeolitic Imidazolate Framework: Implication for Photocatalytic Applications

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

Pattengale, Brian; Yang, Sizhuo; Ludwig, John

2016-06-22

Zeolitic Imidazolate Frameworks (ZIFs) have emerged as a novel class of porous metal-organic frameworks (MOFs) for catalysis application because of their exceptional thermal and chemical stability. Inspired by the broad absorption of ZIF-67 in UV-visible-near IR region, we explored its excited state and charge separation dynamics, properties essential for photocatalytic applications, using optical (OTA) and X-ray transient absorption (XTA) spectroscopy. OTA results show that an exceptionally long-lived excited state is formed after photoexcitation. This long-lived excited state was confirmed to be the charge separated state with ligandto-metal charge transfer character using XTA. The surprisingly long-lived charge separated state, together withmore » its intrinsic hybrid nature, all point to its potential application in heterogeneous photocatalysis and energy conversion.« less

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.

Coagulation of dust particles in a plasma

NASA Technical Reports Server (NTRS)

Horanyi, M.; Goertz, C. K.

1990-01-01

The electrostatic charge of small dust grains in a plasma in which the temperature varies in time is discussed, pointing out that secondary electron emission might introduce charge separation. If the sign of the charge on small grains is opposite to that on big ones, enhanced coagulation can occur which will affect the size distribution of grains in a plasma. Two scenarios where this process might be relevant are considered: a hot plasma environment with temperature fluctuations and a cold plasma environment with transient heating events. The importance of the enhanced coagulation is uncertain, because the plasma parameters in grain-producing environments such as a molecular cloud or a protoplanetary disk are not known. It is possible, however, that this process is the most efficient mechanism for the growth of grains in the size range of 0.1-500 microns.

Strategies for Efficient Charge Separation and Transfer in Artificial Photosynthesis of Solar Fuels.

PubMed

Xu, Yuxing; Li, Ailong; Yao, Tingting; Ma, Changtong; Zhang, Xianwen; Shah, Jafar Hussain; Han, Hongxian

2017-11-23

Converting sunlight to solar fuels by artificial photosynthesis is an innovative science and technology for renewable energy. Light harvesting, photogenerated charge separation and transfer (CST), and catalytic reactions are the three primary steps in the processes involved in the conversion of solar energy to chemical energy (SE-CE). Among the processes, CST is the key "energy pump and delivery" step in determining the overall solar-energy conversion efficiency. Efficient CST is always high priority in designing and assembling artificial photosynthesis systems for solar-fuel production. This Review not only introduces the fundamental strategies for CST but also the combinatory application of these strategies to five types of the most-investigated semiconductor-based artificial photosynthesis systems: particulate, Z-scheme, hybrid, photoelectrochemical, and photovoltaics-assisted systems. We show that artificial photosynthesis systems with high SE-CE efficiency can be rationally designed and constructed through combinatory application of these strategies, setting a promising blueprint for the future of solar fuels. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photoinduced electron transfer in a ferrocene-distyryl BODIPY dyad and a ferrocene-distyryl BODIPY-C60 triad.

PubMed

Liu, Jian-Yong; El-Khouly, Mohamed E; Fukuzumi, Shunichi; Ng, Dennis K P

2012-06-04

A ferrocene-distyryl BODIPY dyad and a ferrocene-distyryl BODIPY-C(60) triad are synthesized and characterized. Upon photoexcitation at the distyryl BODIPY unit, these arrays undergo photoinduced electron transfer to form the corresponding charge-separated species. Based on their redox potentials, determined by cyclic voltammetry, the direction of the charge separation and the energies of these states are revealed. Femtosecond transient spectroscopic studies reveal that a fast charge separation (k(CS) =1.0×10(10) s(-1)) occurs for both the ferrocene-distyryl BODIPY dyad and the ferrocene-distyryl BODIPY-C(60) triad, but that a relatively slow charge recombination is observed only for the triad. The lifetime of the charge-separated state is 500 ps. Charge recombination of the dyad and triad leads to population of the triplet excited sate of ferrocene and the ground state, respectively. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanoimprinting-induced nanomorphological transition in polymer solar cells: enhanced electrical and optical performance.

PubMed

Jeong, Seonju; Cho, Changsoon; Kang, Hyunbum; Kim, Ki-Hyun; Yuk, Youngji; Park, Jeong Young; Kim, Bumjoon J; Lee, Jung-Yong

2015-03-24

We have investigated the effects of a directly nanopatterned active layer on the electrical and optical properties of inverted polymer solar cells (i-PSCs). The capillary force in confined molds plays a critical role in polymer crystallization and phase separation of the film. The nanoimprinting process induced improved crystallization and multidimensional chain alignment of polymers for more effective charge transfer and a fine phase-separation between polymers and [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) to favor exciton dissociation and increase the generation rate of charge transfer excitons. Consequently, the power conversion efficiency with a periodic nanostructure was enhanced from 7.40% to 8.50% and 7.17% to 9.15% in PTB7 and PTB7-Th based i-PSCs, respectively.

On-Line Ion Exchange Liquid Chromatography as a Process Analytical Technology for Monoclonal Antibody Characterization in Continuous Bioprocessing.

PubMed

Patel, Bhumit A; Pinto, Nuno D S; Gospodarek, Adrian; Kilgore, Bruce; Goswami, Kudrat; Napoli, William N; Desai, Jayesh; Heo, Jun H; Panzera, Dominick; Pollard, David; Richardson, Daisy; Brower, Mark; Richardson, Douglas D

2017-11-07

Combining process analytical technology (PAT) with continuous production provides a powerful tool to observe and control monoclonal antibody (mAb) fermentation and purification processes. This work demonstrates on-line liquid chromatography (on-line LC) as a PAT tool for monitoring a continuous biologics process and forced degradation studies. Specifically, this work focused on ion exchange chromatography (IEX), which is a critical separation technique to detect charge variants. Product-related impurities, including charge variants, that impact function are classified as critical quality attributes (CQAs). First, we confirmed no significant differences were observed in the charge heterogeneity profile of a mAb through both at-line and on-line sampling and that the on-line method has the ability to rapidly detect changes in protein quality over time. The robustness and versatility of the PAT methods were tested by sampling from two purification locations in a continuous mAb process. The PAT IEX methods used with on-line LC were a weak cation exchange (WCX) separation and a newly developed shorter strong cation exchange (SCX) assay. Both methods provided similar results with the distribution of percent acidic, main, and basic species remaining unchanged over a 2 week period. Second, a forced degradation study showed an increase in acidic species and a decrease in basic species when sampled on-line over 7 days. These applications further strengthen the use of on-line LC to monitor CQAs of a mAb continuously with various PAT IEX analytical methods. Implementation of on-line IEX will enable faster decision making during process development and could potentially be applied to control in biomanufacturing.

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).

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.

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.

Spray Formation from a Charged Liquid Jet of a Dielectric Fluid

NASA Astrophysics Data System (ADS)

Doak, William; de Bellis, Victor; Chiarot, Paul; Microfluidics; Multiphase Flow Laboratory Team

2017-11-01

Atomization of a dielectric micro-jet is achieved via an electrohydrodynamic charge injection process. The atomizer is comprised of a grounded nozzle housing (ground electrode) and an internal probe (high voltage electrode) that is concentric with the emitting orifice. The internal probe is held at electric potentials ranging from 1-10 kV. A pressurized reservoir drives a dielectric fluid at a desired flow rate through the 100-micrometer diameter orifice. The fluid fills the cavity between the electrodes as it passes through the atomizer, impeding the transport of electrons. This process injects charge into the flowing fluid. Upon exiting the orifice, the emitted jet is highly charged and it deforms via a bending instability that is qualitatively similar to the behavior observed in the electrospinning of fibers. We observed bulging regions, or nodes, of highly charged fluid forming along the bent, rotating jet. These nodes separate into highly charged droplets that emit satellite droplets. The remaining ligaments break up due to capillarity in a process that produces additional satellites. All of the droplets possess a normal (inertial) and radial (electrically-driven) momentum component. The radial component is responsible for the formation of a conical spray envelope. Our research focuses on the jet, its break up, and the droplet dynamics of this system. This research supported by the American Chemical Society.

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.

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).

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.

Continuum modeling of charging process and piezoelectricity of ferroelectrets

NASA Astrophysics Data System (ADS)

Xu, Bai-Xiang; von Seggern, Heinz; Zhukov, Sergey; Gross, Dietmar

2013-09-01

Ferroelectrets in the form of electrically charged micro-porous foams exhibit a very large longitudinal piezoelectric coefficient d33. The structure has hence received wide application interests as sensors particularly in acoustic devices. During charging process, electrical breakdown (Paschen breakdown) takes place in the air pores of the foam and introduces free charge pairs. These charges are separated by electrostatic forces and relocated at the interfaces between the polymer and the electrically broken-down medium, where they are trapped quasistatically. The development of this trapped charge density along the interfaces is key for enabling the piezoelectricity of ferroelectrets. In this article, an internal variable based continuum model is proposed to calculate the charge density development at the interfaces, whereas a Maxwell stress based electromechanical model is used for the bulk behavior, i.e., of the polymer and of the medium where the Paschen breakdown takes place. In the modeling, the electrostatic forces between the separated charge pairs are included, as well as the influence of deformation of the solid layers. The material models are implemented in a nonlinear finite element scheme, which allows a detailed analysis of different geometries. A ferroelectret unit with porous expanded polytetrafluoroethylene (ePTFE) surrounded by fluorinated ethylene propylene is studied first. The simulated hysteresis curves of charge density at the surfaces and the calculated longitudinal piezoelectric constant are in good agreement with experimental results. Simulations show a strong dependency of the interface charge development and thus the remnant charges on the thicknesses of the layers and the permittivity of the materials. According to the calculated relation between d33 and the Young's modulus of ePTFE, the value of the Young's modulus of ePTFE is identified to be around 0.75 MPa, which lies well in the predicted range of 0.45 to 0.80 MPa, determined from the dielectric resonance spectra in the work of Zhang et al. [X. Q. Zhang et al., J. Appl. Phys. 108, 064113 (2010)]. To show the potential of the models, it is also applied to simulation of ferroelectrets with a lens shape. The results indicate that the electrical breakdown happens in a sequential manner, and the local piezoelectric coefficient varies with position. Thereby, the middle point on the surface exhibits the maximum d33. The simulation results obtained by the proposed models will provide insight for device optimization.

Demonstration of a strategy for product purification by high-gradient magnetic fishing: recovery of superoxide dismutase from unconditioned whey.

PubMed

Meyer, Andrea; Hansen, Dennis B; Gomes, Cláudia S G; Hobley, Timothy J; Thomas, Owen R T; Franzreb, Matthias

2005-01-01

A systematic approach for the design of a bioproduct recovery process employing magnetic supports and the technique of high-gradient magnetic fishing (HGMF) is described. The approach is illustrated for the separation of superoxide dismutase (SOD), an antioxidant protein present in low concentrations (ca. 0.15-0.6 mg L(-1)) in whey. The first part of the process design consisted of ligand screening in which metal chelate supports charged with copper(II) ions were found to be the most suitable. The second stage involved systematic and sequential optimization of conditions for the following steps: product adsorption, support washing, and product elution. Next, the capacity of a novel high-gradient magnetic separator (designed for biotechnological applications) for trapping and holding magnetic supports was determined. Finally, all of the above elements were assembled to deliver a HGMF process for the isolation of SOD from crude sweet whey, which consisted of (i) binding SOD using Cu2+ -charged magnetic metal chelator particles in a batch reactor with whey; (ii) recovery of the "SOD-loaded" supports by high-gradient magnetic separation (HGMS); (iii) washing out loosely bound and entrained proteins and solids; (iv) elution of the target protein; and (v) recovery of the eluted supports from the HGMF rig. Efficient recovery of SOD was demonstrated at approximately 50-fold increased scale (cf magnetic rack studies) in three separate HGMF experiments, and in the best of these (run 3) an SOD yield of >85% and purification factor of approximately 21 were obtained.

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.

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

PubMed

Kamat, Prashant V

2012-11-20

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

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.

Method for producing dustless graphite spheres from waste graphite fines

DOEpatents

Pappano, Peter J [Oak Ridge, TN; Rogers, Michael R [Clinton, TN

2012-05-08

A method for producing graphite spheres from graphite fines by charging a quantity of spherical media into a rotatable cylindrical overcoater, charging a quantity of graphite fines into the overcoater thereby forming a first mixture of spherical media and graphite fines, rotating the overcoater at a speed such that the first mixture climbs the wall of the overcoater before rolling back down to the bottom thereby forming a second mixture of spherical media, graphite fines, and graphite spheres, removing the second mixture from the overcoater, sieving the second mixture to separate graphite spheres, charging the first mixture back into the overcoater, charging an additional quantity of graphite fines into the overcoater, adjusting processing parameters like overcoater dimensions, graphite fines charge, overcoater rotation speed, overcoater angle of rotation, and overcoater time of rotation, before repeating the steps until graphite fines are converted to graphite spheres.

Ion exchange polymers for anion separations

DOEpatents

Jarvinen, Gordon D.; Marsh, S. Fredric; Bartsch, Richard A.

1997-01-01

Anion exchange resins including at least two positively charged sites and a ell-defined spacing between the positive sites are provided together with a process of removing anions or anionic metal complexes from aqueous solutions by use of such resins. The resins can be substituted poly(vinylpyridine) and substituted polystyrene.

Ion exchange polymers for anion separations

DOEpatents

Jarvinen, G.D.; Marsh, S.F.; Bartsch, R.A.

1997-09-23

Anion exchange resins including at least two positively charged sites and a well-defined spacing between the positive sites are provided together with a process of removing anions or anionic metal complexes from aqueous solutions by use of such resins. The resins can be substituted poly(vinylpyridine) and substituted polystyrene.

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.

Energetic particle influences in Earth's atmosphere

NASA Astrophysics Data System (ADS)

Aplin, Karen; Harrison, R. Giles; Nicoll, Keri; Rycroft, Michael; Briggs, Aaron

2016-04-01

Energetic particles from outer space, known as galactic cosmic rays, constantly ionise the entire atmosphere. During strong solar storms, solar energetic particles can also reach the troposphere and enhance ionisation. Atmospheric ionisation generates cluster ions. These facilitate current flow in the global electric circuit, which arises from charge separation in thunderstorms driven by meteorological processes. Energetic particles, whether solar or galactic in origin, may influence the troposphere and stratosphere through a range of different mechanisms, each probably contributing a small amount. Some of the suggested processes potentially acting over a wide spatial area in the troposphere include enhanced scavenging of charged aerosol particles, modification of droplet or droplet-droplet behavior by charging, and the direct absorption of infra-red radiation by the bending and stretching of hydrogen bonds inside atmospheric cluster-ions. As well as reviewing the proposed mechanisms by which energetic particles modulate atmospheric properties, we will also discuss new instrumentation for measurement of energetic particles in the atmosphere.

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

Surface charge- and space-dependent transport of proteins in crowded environments of nanotailored posts.

PubMed

Choi, Chang Kyoung; Fowlkes, Jason D; Retterer, Scott T; Siuti, Piro; Iyer, Sukanya; Doktycz, Mitchel J

2010-06-22

The reaction and diffusion of molecules across barriers and through crowded environments is integral to biological system function and to separation technologies. Ordered, microfabricated post arrays are a promising route to creating synthetic barriers with controlled chemical and physical characteristics. They can be used to create crowded environments, to mimic aspects of cellular membranes, and to serve as engineered replacements of polymer-based separation media. Here, the translational diffusion of fluorescein isothiocyante and various forms of green fluorescent protein (GFP), including "supercharged" variants, are examined in a silicon-based post array environment. The technique of fluorescence recovery after photobleaching (FRAP) is combined with analytical approximations and numerical simulations to assess the relative effects of reaction and diffusion on molecular transport, respectively. FRAP experiments were conducted for 64 different cases where the molecular species, the density of the posts, and the chemical surface charge of the posts were varied. In all cases, the dense packing of the posts hindered the diffusive transport of the fluorescent species. The supercharged GFPs strongly interacted with oppositely charged surfaces. With similar molecular and surface charges, transport is primarily limited by hindered diffusion. For conventional, enhanced GFP in a positively charged surface environment, transport was limited by the coupled action of hindered diffusion and surface interaction with the posts. Quantification of the size-, space-, time-, and charge-dependent translational diffusion in the post array environments can provide insight into natural processes and guide the design and development of selective membrane systems.

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.

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.

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)].

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.

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

Synthesis of Ag{sub 9}(SiO{sub 4}){sub 2}NO{sub 3} through a reactive flux method and its visible-light photocatalytic performances

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

Zhu, Xianglin; Wang, Zeyan, E-mail: wangzeyan@sdu.edu.cn, E-mail: bbhuang@sdu.edu.cn; Huang, Baibiao, E-mail: wangzeyan@sdu.edu.cn, E-mail: bbhuang@sdu.edu.cn

2015-10-01

Ag{sub 9}(SiO{sub 4}){sub 2}NO{sub 3} was prepared by a reactive flux method. The structures, morphologies, and light absorption properties were investigated. Owing to the polar crystal structure, an internal electric field can be formed inside the material, which can facilitate the photogenerated charge separation during the photocatalytic process. Based on both the wide light absorption spectra and high charge separation efficiency originated from the polarized internal electric field, Ag{sub 9}(SiO{sub 4}){sub 2}NO{sub 3} exhibit higher efficiency over Ag{sub 3}PO{sub 4} during the degradation of organic dyes under visible light irradiation, which is expected to be a potential material for solarmore » energy harvest and conversion.« less

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.

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.

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.

Effects of Different Manufacturing Processes on TEMPO-Oxidized Carboxylated Cellulose Nanofiber Performance as Binder for Flexible Lithium-Ion Batteries.

PubMed

Lu, Huiran; Guccini, Valentina; Kim, Hyeyun; Salazar-Alvarez, German; Lindbergh, Göran; Cornell, Ann

2017-11-01

Carboxylated cellulose nanofibers (CNF) prepared using the TEMPO-route are good binders of electrode components in flexible lithium-ion batteries (LIB). However, the different parameters employed for the defibrillation of CNF such as charge density and degree of homogenization affect its properties when used as binder. This work presents a systematic study of CNF prepared with different surface charge densities and varying degrees of homogenization and their performance as binder for flexible LiFePO 4 electrodes. The results show that the CNF with high charge density had shorter fiber lengths compared with those of CNF with low charge density, as observed with atomic force microscopy. Also, CNF processed with a large number of passes in the homogenizer showed a better fiber dispersibility, as observed from rheological measurements. The electrodes fabricated with highly charged CNF exhibited the best mechanical and electrochemical properties. The CNF at the highest charge density (1550 μmol g -1 ) and lowest degree of homogenization (3 + 3 passes in the homogenizer) achieved the overall best performance, including a high Young's modulus of approximately 311 MPa and a good rate capability with a stable specific capacity of 116 mAh g -1 even up to 1 C. This work allows a better understanding of the influence of the processing parameters of CNF on their performance as binder for flexible electrodes. The results also contribute to the understanding of the optimal processing parameters of CNF to fabricate other materials, e.g., membranes or separators.

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 CE-Way of Thinking: "All Is Relative!".

PubMed

Schmitt-Kopplin, Philippe; Fekete, Agnes

2016-01-01

Over the last two decades the development of capillary electrophoresis instruments lead to systems with programmable sampler, separation column, separation buffer, and detection devices comparable visually in many aspects to the setup of classical chromatography.Two processes make capillary electrophoresis essentially different from chromatography and are the basis of the CE-way of thinking, namely, the injection type and the liquid flow within the capillary. (1) When the injection is made hydrodynamically (such as in most of the found applications in the literature), the injected volumes are directly dependent on the type and size of the separation capillary. (2) The buffer velocity is not pressure driven as in liquid chromatography but electrokinetically governed by the quality of the capillary surface (separation buffer dependant surface charge) inducing an electroosmotic flow (EOF). The EOF undergoes small variations and is not necessarily identical from one separation or day to the other. The direct consequence is an apparent nonreproducible migration time of the analytes, even though the own velocity of the ions is the same.The effective mobility (field strength normalized velocity) of the ions is a possible parameterization from acquired timescale to effective mobility-scale electropherograms leading to a reproducible visualization and better quantification with a direct relation to structural characters of the analytes (i.e., charge and size-see chapter on semiempirical modelization).

Hybrid supercapacitor-battery materials for fast electrochemical charge storage

PubMed Central

Vlad, A.; Singh, N.; Rolland, J.; Melinte, S.; Ajayan, P. M.; Gohy, J.-F.

2014-01-01

High energy and high power electrochemical energy storage devices rely on different fundamental working principles - bulk vs. surface ion diffusion and electron conduction. Meeting both characteristics within a single or a pair of materials has been under intense investigations yet, severely hindered by intrinsic materials limitations. Here, we provide a solution to this issue and present an approach to design high energy and high power battery electrodes by hybridizing a nitroxide-polymer redox supercapacitor (PTMA) with a Li-ion battery material (LiFePO4). The PTMA constituent dominates the hybrid battery charge process and postpones the LiFePO4 voltage rise by virtue of its ultra-fast electrochemical response and higher working potential. We detail on a unique sequential charging mechanism in the hybrid electrode: PTMA undergoes oxidation to form high-potential redox species, which subsequently relax and charge the LiFePO4 by an internal charge transfer process. A rate capability equivalent to full battery recharge in less than 5 minutes is demonstrated. As a result of hybrid's components synergy, enhanced power and energy density as well as superior cycling stability are obtained, otherwise difficult to achieve from separate constituents. PMID:24603843

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.

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

Interactions in hydrogen of relativistic neon to nickel projectiles: Total charge-changing cross sections

NASA Astrophysics Data System (ADS)

Chen, C.-X.; Albergo, S.; Caccia, Z.; Costa, S.; Crawford, H. J.; Cronqvist, M.; Engelage, J.; Ferrando, P.; Fonte, R.; Greiner, L.; Guzik, T. G.; Insolia, A.; Jones, F. C.; Knott, C. N.; Lindstrom, P. J.; Mitchell, J. W.; Potenza, R.; Romanski, J.; Russo, G. V.; Soutoul, A.; Testard, O.; Tull, C. E.; Tuvé, C.; Waddington, C. J.; Webber, W. R.; Wefel, J. P.; Zhang, X.

1994-06-01

A liquid hydrogen target was used to study the nuclear fragmentation of beams of relativistic heavy ions, 22Ne to 58Ni, over an energy range 400 to 900 MeV/nucleon. The experiments were carried out at the Lawrence Berkeley Laboratory Bevalac HISS facility, using the charge-velocity-rigidity method to identify the charged fragments. Here we describe the general concept of the experiment and present total charge-changing cross sections obtained from 17 separate runs. These new measured cross sections display an energy dependence which follows semiempirical model predictions. The mass dependence of the cross sections behaves as predicted by optical models, but within the experimental energy range, the optical model parameters display a clear energy dependence. The isospin of the projectile nuclei also appears to be an important factor in the interaction process.

Pi-Pi contacts are an overlooked protein feature relevant to phase separation

PubMed Central

Vernon, Robert McCoy; Chong, Paul Andrew; Tsang, Brian; Kim, Tae Hun; Bah, Alaji; Farber, Patrick; Lin, Hong

2018-01-01

Protein phase separation is implicated in formation of membraneless organelles, signaling puncta and the nuclear pore. Multivalent interactions of modular binding domains and their target motifs can drive phase separation. However, forces promoting the more common phase separation of intrinsically disordered regions are less understood, with suggested roles for multivalent cation-pi, pi-pi, and charge interactions and the hydrophobic effect. Known phase-separating proteins are enriched in pi-orbital containing residues and thus we analyzed pi-interactions in folded proteins. We found that pi-pi interactions involving non-aromatic groups are widespread, underestimated by force-fields used in structure calculations and correlated with solvation and lack of regular secondary structure, properties associated with disordered regions. We present a phase separation predictive algorithm based on pi interaction frequency, highlighting proteins involved in biomaterials and RNA processing. PMID:29424691

Experience of gastric cancer survivors and their spouses in Korea: secondary analysis.

PubMed

Yi, Myungsun; Kahn, David

2004-06-01

The purpose of this study was to explore the experiences of gastric cancer couples in Korea and to generate a substantive theory integrating the experiences of gastric cancer survivors and their spouses as a whole. The specific aims of this study were to explore major problems gastric cancer couples faced and how they resolved these problems, focusing on inter-relational dynamics within the couples and on similarities and differences between the couples. This was a secondary analysis study using grounded theory techniques. The study used the data of 11 married couples which was collected from in-depth interviews from two primary studies. The unit of analysis was dyads of gastric cancer survivors and their spouses. The basic social psychological process that emerged from the analysis was "taking charge of their health." Major categories involved in this process were identified as 1) adjusting to new diets, 2) reinforcing physical strength, 3) seeking information, 4) strengthening Ki, 5) lowering life-expectations, and 6) going their separate ways. These six categories represent major strategies in overcoming critical problems that occurred in day-to-day experiences. In terms of the process, the first five categories characterize the earlier stage of the process of "taking charge of their health," while "going their separate ways" indicates the later stage and also the beginning of their separate ways: "pursuing spiritual life" for the survivors, and "preparing for the future" for the spouses. The results of this study will help design family care for the people with gastric cancer by providing in-depth understanding and insight on the lives of gastric cancer couples.

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

Synthesis and Photophysical Characterization of an Artificial Photosynthetic Reaction Center Exhibiting Acid-Responsive Regulation of Charge Separation

NASA Astrophysics Data System (ADS)

Pahk, Ian

Non-photochemical quenching (NPQ) is a photoprotective regulatory mechanism essential to the robustness of the photosynthetic apparatus of green plants. Energy flow within the low-light adapted reaction centers is dynamically optimized to match the continuously fluctuating light conditions found in nature. Activated by compartmentalized decreases in pH resulting from photosynthetic activity during periods of elevated photon flux, NPQ induces rapid thermal dissipation of excess excitation energy that would otherwise overwhelm the apparatus's ability to consume it. Consequently, the frequency of charge separation decreases and the formation of potentially deleterious, high-energy intermediates slows, thereby reducing the threat of photodamage by disallowing their accumulation. Herein is described the synthesis and photophysical analysis of a molecular triad that mimics the effects of NPQ on charge separation within the photosynthetic reaction centers. Steady-state absorption and emission, time-resolved fluorescence, and transient absorption spectroscopies were used to demonstrate reversible quenching of the first singlet excited state affecting the quantum yield of charge separation by approximately one order of magnitude. As in the natural system, the populations of unquenched and quenched states and, therefore, the overall yields of charge separation were found to be dependent upon acid concentration.

A charge-stabilizing, multimodular, ferrocene-bis(triphenylamine)-zinc-porphyrin-fullerene polyad.

PubMed

Wijesinghe, Channa A; El-Khouly, Mohamed E; Zandler, Melvin E; Fukuzumi, Shunichi; D'Souza, Francis

2013-07-15

A novel multimodular donor-acceptor polyad featuring zinc porphyrin, fullerene, ferrocene, and triphenylamine entities was designed, synthesized, and studied as a charge-stabilizing, photosynthetic-antenna/reaction-center mimic. The ferrocene and fullerene entities, covalently linked to the porphyrin ring, were distantly separated to accomplish the charge-separation/hole-migration events leading to the creation of a long-lived charge-separated state. The geometry and electronic structures of the newly synthesized compound was deduced by B3LYP/3-21G(*) optimization, while the energy levels for different photochemical events was established using data from the optical absorption and emission, and electrochemical studies. Excitation of the triphenylamine entities revealed singlet-singlet energy transfer to the appended zinc porphyrin. As predicted from the energy levels, photoinduced electron transfer from both the singlet and triplet excited states of the zinc porphyrin to fullerene followed by subsequent hole migration involving ferrocene was witnessed from the transient absorption studies. The charge-separated state persisted for about 8.5 μs and was governed by the distance between the final charge-transfer product, that is, a species involving a ferrocenium cation and a fullerene radical anion, with additional influence from the charge-stabilizing triphenylamine entities located on the zinc-porphyrin macrocycle. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Phénomènes d'électrisation des matériaux isolants pour transformateurs de puissance

NASA Astrophysics Data System (ADS)

Peyraque, L.; Béroual, A.; Boisdon, C.; Buret, F.

1994-07-01

In power transformers, the oil flowed through the cooling ducts in coil assembly induces a static charge separation. The study of this static electrification phenomena is presented through a device allowing to investigate the charge separation generated by the rotating motion of a transformer pressboard in oil. This permits to show the influence of various parameters such as velocity, temperature, moisture and processing of oils and pressboards as well as their nature on this electrical charge. We also present another device allowing to classify oils according to their level of charge production. It appears from our results that a correlation exists between the density of these charges and the characteristics of oil such as conductivity, electric strength and water content. Dans les transformateurs de puissance, la circulation d'huile à travers les canaux de refroidissement en fibre cellulosique (carton isolant) est à l'origine d'une séparation de charges. L'étude de ce phénomène d'électrisation statique est présentée, tout d'abord à travers un dispositif permettant d'étudier la séparation de charges créées par le mouvement du carton dans l'huile. Celui-ci a permis de mettre en évidence l'influence de plusieurs paramètres comme la vitesse, la température, l'humidité et le traitement des huiles et cartons ainsi que la nature du carton sur cette charge. Le second dispositif présenté permet de classer les huiles selon leur niveau de création de charges. Une corrélation semble s'établir entre la densité de ces charges et les grandeurs caractéristiques de l'huile telles que la conductivité, la rigidité diélectrique et la teneur en eau.

Crystallization of Photosystem II for Time-Resolved Structural Studies Using an X-ray Free Electron Laser

PubMed Central

Coe, Jesse; Kupitz, Christopher; Basu, Shibom; Conrad, Chelsie E.; Roy-Chowdhury, Shatabdi; Fromme, Raimund; Fromme, Petra

2015-01-01

Photosystem II (PSII) is a membrane protein supercomplex that executes the initial reaction of photosynthesis in higher plants, algae, and cyanobacteria. It captures the light from the sun to catalyze a transmembrane charge separation. In a series of four charge separation events, utilizing the energy from four photons, PSII oxidizes two water molecules to obtain dioxygen, four protons, and four electrons. The light reactions of photosystems I and II (PSI and PSII) result in the formation of an electrochemical transmembrane proton gradient that is used for the production of ATP. Electrons that are subsequently transferred from PSI via the soluble protein ferredoxin to ferredoxin-NADP+ reductase that reduces NADP+ to NADPH. The products of photosynthesis and the elemental oxygen evolved sustain all higher life on Earth. All oxygen in the atmosphere is produced by the oxygen-evolving complex in PSII, a process that changed our planet from an anoxygenic to an oxygenic atmosphere 2.5 billion years ago. In this chapter, we provide recent insight into the mechanisms of this process and methods used in probing this question. PMID:25950978

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.

Downstream processing of biopharmaceutical proteins produced in plants: the pros and cons of flocculants.

PubMed

Buyel, Johannes Felix; Fischer, Rainer

2014-01-01

All biological platforms for the manufacture of biopharmaceutical proteins produce an initially turbid extract that must be clarified to avoid fouling sensitive media such as chromatography resins. Clarification is more challenging if the feed stream contains large amounts of dispersed particles, because these rapidly clog the filter media typically used to remove suspended solids. Charged polymers (flocculants) can increase the apparent size of the dispersed particles by aggregation, facilitating the separation of solids and liquids, and thus reducing process costs. However, many different factors can affect the behavior of flocculants, including the pH and conductivity of the medium, the size and charge distribution of the particulates, and the charge density and molecular mass of the polymer. Importantly, these properties can also affect the recovery of the target protein and the overall safety profile of the process. We therefore used a design of experiments approach to establish reliable predictive models that characterize the impact of flocculants during the downstream processing of biopharmaceutical proteins. We highlight strategies for the selection of flocculants during process optimization. These strategies will contribute to the quality by design aspects of process development and facilitate the development of safe and efficient downstream processes for plant-derived pharmaceutical proteins.

Simultaneous and selective decarboxylation of L-serine and deamination of L-phenylalanine in an amino acid mixture--a means of separating amino acids for synthesizing biobased chemicals.

PubMed

Teng, Yinglai; Scott, Elinor L; Witte-van Dijk, Susan C M; Sanders, Johan P M

2016-01-25

Amino acids (AAs) obtained from the hydrolysis of biomass-derived proteins are interesting feedstocks for the chemical industry. They can be prepared from the byproduct of biofuel production and agricultural wastes. They are rich in functionalities needed in petrochemicals, providing the opportunity to save energy, reagents, and process steps. However, their separation is required before they can be applied for further applications. Electrodialysis (ED) is a promising separation method, but its efficiency needs to be improved when separating AAs with similar isoelectric points. Thus, specific conversions are required to form product with different charges. Here we studied the enzymatic conversions which can be used as a means to aid the ED separation of neutral AAs. A model mixture containing L-serine, L-phenylalanine and L-methionine was used. The reactions of L-serine decarboxylase and L-phenylalanine ammonia-lyase were employed to specifically convert serine and phenylalanine into ethanolamine and trans-cinnamic acid. At the isoelectric point of methionine (pH 5.74), the charge of ethanolamine and trans-cinnamic acid are +1 and -1, therefore facilitating potential separation into three different streams by electrodialysis. Here the enzyme kinetics, specificity, inhibition and the operational stabilities were studied, showing that both enzymes can be applied simultaneously to aid the ED separation of neutral AAs. Copyright © 2015 Elsevier B.V. All rights reserved.

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.

Measuring charged particle multiplicity with early ATLAS public data

NASA Astrophysics Data System (ADS)

Üstün, G.; Barut, E.; Bektaş, E.; Özcan, V. E.

2017-07-01

We study 100 images of early LHC collisions that were recorded by the ATLAS experiment and made public for outreach purposes, and extract the charged particle multiplicity as a function of momentum for proton-proton collisions at a centre-of-mass energy of 7 TeV. As these collisions have already been pre-processed by the ATLAS Collaboration, the particle tracks are visible, but are available to the public only in the form of low-resolution bitmaps. We describe two separate image processing methods, one based on the industry-standard OpenCV library and C++, another based on self-developed algorithms in Python. We present our analysis of the transverse momentum and azimuthal angle distributions of the particles, in agreement with the literature.

Room-temperature current blockade in atomically defined single-cluster junctions

NASA Astrophysics Data System (ADS)

Lovat, Giacomo; Choi, Bonnie; Paley, Daniel W.; Steigerwald, Michael L.; Venkataraman, Latha; Roy, Xavier

2017-11-01

Fabricating nanoscopic devices capable of manipulating and processing single units of charge is an essential step towards creating functional devices where quantum effects dominate transport characteristics. The archetypal single-electron transistor comprises a small conducting or semiconducting island separated from two metallic reservoirs by insulating barriers. By enabling the transfer of a well-defined number of charge carriers between the island and the reservoirs, such a device may enable discrete single-electron operations. Here, we describe a single-molecule junction comprising a redox-active, atomically precise cobalt chalcogenide cluster wired between two nanoscopic electrodes. We observe current blockade at room temperature in thousands of single-cluster junctions. Below a threshold voltage, charge transfer across the junction is suppressed. The device is turned on when the temporary occupation of the core states by a transiting carrier is energetically enabled, resulting in a sequential tunnelling process and an increase in current by a factor of ∼600. We perform in situ and ex situ cyclic voltammetry as well as density functional theory calculations to unveil a two-step process mediated by an orbital localized on the core of the cluster in which charge carriers reside before tunnelling to the collector reservoir. As the bias window of the junction is opened wide enough to include one of the cluster frontier orbitals, the current blockade is lifted and charge carriers can tunnel sequentially across the junction.

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.

Highly efficient tandem organic light-emitting devices employing an easily fabricated charge generation unit

NASA Astrophysics Data System (ADS)

Yang, Huishan; Yu, Yaoyao; Wu, Lishuang; Qu, Biao; Lin, Wenyan; Yu, Ye; Wu, Zhijun; Xie, Wenfa

2018-02-01

We have realized highly efficient tandem organic light-emitting devices (OLEDs) employing an easily fabricated charge generation unit (CGU) combining 1,4,5,8,9,11-hexaazatriphenylene-hexacarbonitrile with ultrathin bilayers of CsN3 and Al. The charge generation and separation processes of the CGU have been demonstrated by studying the differences in the current density-voltage characteristics of external-carrier-excluding devices. At high luminances of 1000 and 10000 cd/m2, the current efficiencies of the phosphorescent tandem device are about 2.2- and 2.3-fold those of the corresponding single-unit device, respectively. Simultaneously, an efficient tandem white OLED exhibiting high color stability and warm white emission has also been fabricated.

Optimizing multi-step B-side charge separation in photosynthetic reaction centers from Rhodobacter capsulatus

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

Faries, Kaitlyn M.; Kressel, Lucas L.; Dylla, Nicholas P.

Using high-throughput methods for mutagenesis, protein isolation and charge-separation functionality, we have assayed 40 Rhodobacter capsulatus reaction center (RC) mutants for their P+ QB- yield (P is a dimer of bacteriochlorophylls and Q is a ubiquinone) as produced using the normally inactive B-side cofactors BB and HB (where B is a bacteriochlorophyll and H is a bacteriopheophytin). Two sets of mutants explore all possible residues at M131 (M polypeptide, native residue Val near HB) in tandem with either a fixed His or a fixed Asn at L181 (L polypeptide, native residue Phe near BB). A third set of mutants exploresmore » all possible residues at L181 with a fixed Glu at M131 that can form a hydrogen bond to HB. For each set of mutants, the results of a rapid millisecond screening assay that probes the yield of P+ QB- are compared among that set and to the other mutants reported here or previously. For a subset of eight mutants, the rate constants and yields of the individual B-side electron transfer processes are determined via transient absorption measurements spanning 100 fs to 50 μs. The resulting ranking of mutants for their yield of P+ QB- from ultrafast experiments is in good agreement with that obtained from the millisecond screening assay, further validating the efficient, high-throughput screen for B-side transmembrane charge separation. Results from mutants that individually show progress toward optimization of P+ HB- → P+ QB- electron transfer or initial P* → P+ HB- conversion highlight unmet challenges of optimizing both processes simultaneously.« less

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.

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

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.

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.

Study of the physicochemical effects on the separation of the non-metallic fraction from printed circuit boards by inverse flotation.

PubMed

Flores-Campos, R; Estrada-Ruiz, R H; Velarde-Sánchez, E J

2017-11-01

Recycling printed circuit boards using green technology is increasingly important due to the metals these contain and the environmental care that must be taken when separating the different materials. Inverse flotation is a process that can be considered a Green Technology, which separates metallic from non-metallic fractions. The degree of separation depends on how much material is adhered to air bubbles. The contact angle measurement allows to determine, in an easy way, whether the flotation process will occur or not and thus establish a material as hydrophobic or not. With the material directly obtained from the milling process, it was found that the contact angle of the non-metallic fraction-liquid-air system increases as temperature increases. In the same way, the increments in concentration of frother in the liquid increase the contact angle of the non-metallic fraction-liquid-air system. 10ppm of Methyl Isobutyl Carbinol provides the highest contact angle as well as the highest material charging in the bubble. Copyright © 2017 Elsevier Ltd. All rights reserved.

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.

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.

The pyroelectric behavior of lead free ferroelectric ceramics in thermally stimulated depolarization current measurements

NASA Astrophysics Data System (ADS)

González-Abreu, Y.; Peláiz-Barranco, A.; Garcia-Wong, A. C.; Guerra, J. D. S.

2012-06-01

The present paper shows a detailed analysis on the thermally stimulated processes in barium modified SrBi2Nb2O9 ferroelectric bi-layered perovskite, which is one of the most promising candidates for non-volatile random access memory applications because of its excellent fatigue-resistant properties. A numerical method is used to separate the real pyroelectric current from the other thermally stimulated processes. A discharge due to the space-charge injected during the poling process, the pyroelectric response, and a conductive process are discussed in a wide temperature range from ferroelectric to paraelectric phase. The pyroelectric response is separated from the other components to evaluate the polarization behavior and some pyroelectric parameters. The remanent polarization, the pyroelectric coefficient, and the merit figure are evaluated, which show good results.

The Charged Aerosol Release Experiment (CARE)

NASA Astrophysics Data System (ADS)

Bernhardt, P. A.; Ganguli, G.; Lampe, M.; Scales, W. A.

2005-12-01

The physics of radar scatter from charged particulates in the upper atmosphere will be studied with the Charged Aerosol Release Experiment (CARE). In 2008, two rocket payloads are being designed for launch North America. The purpose of the CARE program is to identify the mechanisms for radar scatter from polar mesospheric clouds. Polar mesospheric summer echoes (PMSE) are observed at high latitudes when small concentrations of electrons (one-thousand per cubic cm) become attached to sub-micron dust particles. Radar in the VHF (30-300 MHz) frequency range have seen 30 dB enhancements in radar echoes coincident with formation of ice near 85 km altitude. Radar echoes from electrons in the vicinity of charged dust have been observed for frequencies exceeding 1 GHz. Some fundamental questions that remain about the scatting process are: (1) What is the relative importance of turbulent scatter versus incoherent (i.e., Thompson) scatter from individual electrons? (2) What produces the inhomogeneous electron/dust plasma? (3) How is the radar scatter influenced by the density of background electrons, plasma instabilities and turbulence, and photo detachment of electrons from the particulates? These questions will be addressed when the CARE program releases 50 kg of dust particles in an expanding shell at about 300 km altitude. The dust will be manufactured by the chemical release payload to provide particulate sizes in the 10 to 1000 nm range. The expanding dust shell will collect electrons making dense, heavy particles the move the negative charges across magnetic field lines. Plasma turbulence and electron acceleration will be formed from the charge separation between the magnetized oxygen ions in the background ionosphere and the streaming negatively charged dust. Simulations of this process provide estimates of plasma structure which can scatter radar. As the particulates settle through the lower thermosphere into the mesosphere, artificial mesospheric clouds will be formed. Radar scatter form this artificial layer will be compared with natural PMSE observations. Along with the chemical release rocket, in situ probes with a separate instrumented payload will be used to measure dust density, electric fields, plasma density and velocity, and radio wave scattering.

Thermally stimulated processes in samarium-modified lead titanate ferroelectric ceramics

NASA Astrophysics Data System (ADS)

Peláiz-Barranco, A.; García-Wong, A. C.; González-Abreu, Y.; Gagou, Y.; Saint-Grégoire, P.

2013-08-01

The thermally stimulated processes in a samarium-modified lead titanate ferroelectric system are analyzed from the thermally stimulated depolarization discharge current. The discharge due to the space charge injected during the poling process, the pyroelectric response and a conduction process related to oxygen vacancies are evaluated considering a theoretical decomposition by using a numerical method. The pyroelectric response is separated from other components to evaluate the polarization behavior and some pyroelectric parameters. High remanent polarization, pyroelectric coefficient and merit figure values are obtained at room temperature.

Triboelectrostatic separation for granular plastic waste recycling: a review.

PubMed

Wu, Guiqing; Li, Jia; Xu, Zhenming

2013-03-01

The world's plastic consumption has increased incredibly in recent decades, generating more and more plastic waste, which makes it a great public concern. Recycling is the best treatment for plastic waste since it cannot only reduce the waste but also reduce the consumption of oil for producing new virgin plastic. Mechanical recycling is recommended for plastic waste to avoid the loss of its virgin value. As a mechanical separation technology, triboelectrostatic separation utilizes the difference between surface properties of different materials to get them oppositely charged, deflected in the electric field and separately collected. It has advantages such as high efficiency, low cost, no concern of water disposal or secondary pollution and a relatively wide processing range of particle size especially suitable for the granular plastic waste. The process of triboelectrostatic separation for plastic waste is reviewed in this paper. Different devices have been developed and proven to be effective for separation of plastic waste. The influence factors are also discussed. It can be concluded that the triboelectrostatic separation of plastic waste is a promising technology. However, more research is required before it can be widely applied in industry. Copyright © 2012 Elsevier Ltd. All rights reserved.

Local sensor based on nanowire field effect transistor from inhomogeneously doped silicon on insulator

NASA Astrophysics Data System (ADS)

Presnov, Denis E.; Bozhev, Ivan V.; Miakonkikh, Andrew V.; Simakin, Sergey G.; Trifonov, Artem S.; Krupenin, Vladimir A.

2018-02-01

We present the original method for fabricating a sensitive field/charge sensor based on field effect transistor (FET) with a nanowire channel that uses CMOS-compatible processes only. A FET with a kink-like silicon nanowire channel was fabricated from the inhomogeneously doped silicon on insulator wafer very close (˜100 nm) to the extremely sharp corner of a silicon chip forming local probe. The single e-beam lithographic process with a shadow deposition technique, followed by separate two reactive ion etching processes, was used to define the narrow semiconductor nanowire channel. The sensors charge sensitivity was evaluated to be in the range of 0.1-0.2 e /√{Hz } from the analysis of their transport and noise characteristics. The proposed method provides a good opportunity for the relatively simple manufacture of a local field sensor for measuring the electrical field distribution, potential profiles, and charge dynamics for a wide range of mesoscopic objects. Diagnostic systems and devices based on such sensors can be used in various fields of physics, chemistry, material science, biology, electronics, medicine, etc.

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.

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

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.

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.

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.

What can be Learned from X-Ray Spectroscopy Concerning Hot Gas in the Local Bubble and Charge Exchange Processes

NASA Technical Reports Server (NTRS)

Snowden, Steven L.

2007-01-01

Solar wind charge exchange produces diffuse X-ray emission with a variable surface brightness comparable to that of the cosmic background. While the temporal variation of the charge exchange emission allows some separation of the components, there remains a great deal of uncertainty as to the zero level of both. Because the production mechanisms of the two components are considerably different, their spectra would provide critical diagnostics to the understanding of both. However, current X-ray observatories are very limited in both spectral resolution and sensitivity in the critical soft X-ray (less than 1.0 keV) energy range. Non-dispersive high-resolution spectrometers, such as the calorimeter proposed for the Spectrum Roentgen Gamma mission, will be extremely useful in distinguishing the cascade emission of charge exchange from the spectra of thermal bremsstrahlung cosmic plasmas.

Pi-Pi contacts are an overlooked protein feature relevant to phase separation.

PubMed

Vernon, Robert McCoy; Chong, Paul Andrew; Tsang, Brian; Kim, Tae Hun; Bah, Alaji; Farber, Patrick; Lin, Hong; Forman-Kay, Julie Deborah

2018-02-09

Protein phase separation is implicated in formation of membraneless organelles, signaling puncta and the nuclear pore. Multivalent interactions of modular binding domains and their target motifs can drive phase separation. However, forces promoting the more common phase separation of intrinsically disordered regions are less understood, with suggested roles for multivalent cation-pi, pi-pi, and charge interactions and the hydrophobic effect. Known phase-separating proteins are enriched in pi-orbital containing residues and thus we analyzed pi-interactions in folded proteins. We found that pi-pi interactions involving non-aromatic groups are widespread, underestimated by force-fields used in structure calculations and correlated with solvation and lack of regular secondary structure, properties associated with disordered regions. We present a phase separation predictive algorithm based on pi interaction frequency, highlighting proteins involved in biomaterials and RNA processing. © 2018, Vernon et al.

Cast-to-shape electrokinetic trapping medium

DOEpatents

Shepodd, Timothy J.; Franklin, Elizabeth; Prickett, Zane T.; Artau, Alexander

2004-08-03

A three-dimensional microporous polymer network material, or monolith, cast-to-shape in a microchannel. The polymer monolith, produced by a phase separation process, is capable of trapping and retaining charged protein species from a mixture of charged and uncharged species under the influence of an applied electric field. The retained charged protein species are released from the porous polymer monolith by a pressure driven flow in the substantial absence of the electric field. The pressure driven flow is independent of direction and thus neither means to reverse fluid flow nor a multi-directional flow field is required, a single flow through the porous polymer monolith can be employed, in contrast to prior art systems. The monolithic polymer material produced by the invention can function as a chromatographic medium. Moreover, by virtue of its ability to retain charged protein species and quantitatively release the retained species the porous polymer monolith can serve as a means for concentrating charged protein species from, for example, a dilute solution.

Cast-to-shape electrokinetic trapping medium

DOEpatents

Shepodd, Timothy J [Livermore, CA; Franklin, Elizabeth [Rolla, MO; Prickett, Zane T [Golden, CO; Artau, Alexander [Pleasanton, CA

2006-05-30

A three-dimensional microporous polymer network material, or monolith, cast-to-shape in a microchannel. The polymer monolith, produced by a phase separation process, is capable of trapping and retaining charged protein species from a mixture of charged and uncharged species under the influence of an applied electric field. The retained charged protein species are released from the porous polymer monolith by a pressure driven flow in the substantial absence of the electric field. The pressure driven flow is independent of direction and thus neither means to reverse fluid flow nor a multi-directional flow field is required, a single flow through the porous polymer monolith can be employed, in contrast to prior art systems. The monolithic polymer material produced by the invention can function as a chromatographic medium. Moreover, by virtue of its ability to retain charged protein species and quantitatively release the retained species the porous polymer monolith can serve as a means for concentrating charged protein species from, for example, a dilute solution.

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.

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.

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.

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.

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.

Self-regenerating column chromatography

DOEpatents

Park, Woo K.

1995-05-30

The present invention provides a process for treating both cations and anions by using a self-regenerating, multi-ionic exchange resin column system which requires no separate regeneration steps. The process involves alternating ion-exchange chromatography for cations and anions in a multi-ionic exchange column packed with a mixture of cation and anion exchange resins. The multi-ionic mixed-charge resin column works as a multi-function column, capable of independently processing either cationic or anionic exchange, or simultaneously processing both cationic and anionic exchanges. The major advantage offered by the alternating multi-function ion exchange process is the self-regeneration of the resins.

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

Magnetic Separator Enhances Treatment Possibilities

NASA Technical Reports Server (NTRS)

2008-01-01

Since the earliest missions in space, NASA specialists have performed experiments in low gravity. Protein crystal growth, cell and tissue cultures, and separation technologies such as electrophoresis and magnetophoresis have been studied on Apollo 14, Apollo 16, STS-107, and many other missions. Electrophoresis and magnetophoresis, respectively, are processes that separate substances based on the electrical charge and magnetic field of a molecule or particle. Electrophoresis has been studied on over a dozen space shuttle flights, leading to developments in electrokinetics, which analyzes the effects of electric fields on mass transport (atoms, molecules, and particles) in fluids. Further studies in microgravity will continue to improve these techniques, which researchers use to extract cells for various medical treatments and research.

The synthesis and properties of linear A-π-D-π-A type organic small molecule containing diketopyrrolopyrrole terminal units.

PubMed

Zhang, Shanshan; Niu, Qingfen; Sun, Tao; Li, Yang; Li, Tianduo; Liu, Haixia

2017-08-05

A novel linear A-π-D-π-A-type organic small molecule Ph2(PDPP) 2 consisting diketopyrrolopyrrole (DPP) as acceptor unit, biphenylene as donor unit and acetylene unit as π-linkage has been successfully designed and synthesized. Its corresponding thermal, photophysical and electrochemical properties as well as the photoinduced charge-separation process were investigated. Ph2(PDPP) 2 exhibits high thermal stability and it can be soluble in common organic solvents such as chloroform and tetrahydrofuran. The photophysical properties show that DPP 2 Ph 2 harvests sunlight over the entire visible spectrum range in the thin-film state (300-800nm). DPP 2 Ph 2 has lower band gaps and appropriate energy levels to satisfy the requirement of solution-processable organic solar cells. The efficient photoinduced charge separation process was clearly observed between DPP 2 Ph 2 with PC 61 BM and the K sv value was found to be as high as 2.13×10 4 M -1 . Therefore, these excellent properties demonstrate that the designed A-π-D-π-A-type small molecule Ph2(PDPP) 2 is the prospective candidate as donor material for organic photovoltaic material. Copyright © 2017 Elsevier B.V. All rights reserved.

Noncovalent magnetic control and reversible recovery of graphene oxide using iron oxide and magnetic surfactants.

PubMed

McCoy, Thomas M; Brown, Paul; Eastoe, Julian; Tabor, Rico F

2015-01-28

The unique charging properties of graphene oxide (GO) are exploited in the preparation of a range of noncovalent magnetic GO materials, using microparticles, nanoparticles, and magnetic surfactants. Adsorption and desorption are controlled by modification of pH within a narrow window of <2 pH units. The benefit conferred by using charge-based adsorption is that the process is reversible, and the GO can be captured and separated from the magnetic nanomaterial, such that both components can be recycled. Iron oxide (Fe2O3) microparticles form a loosely flocculated gel network with GO, which is demonstrated to undergo magnetic compressional dewatering in the presence of an external magnetic field. For composites formed from GO and Fe2O3 nanoparticles, it is found that low Fe2O3:GO mass ratios (<5:1) favor flocculation of GO, whereas higher ratios (>5:1) cause overcharging of the surfaces resulting in restabilization. The effectiveness of the GO adsorption and magnetic capture process is demonstrated by separating traditionally difficult-to-recover gold nanoparticles (d ≈ 10 nm) from water. The fully recyclable nature of the assembly and capture process, combined with the vast adsorption capacity of GO, presents obvious and appealing advantages for applications in decontamination and water treatment.

Size and Temperature Dependence of Electron Transfer between CdSe Quantum Dots and a TiO 2 Nanobelt

DOE PAGES

Tafen, De Nyago; Prezhdo, Oleg V.

2015-02-24

Understanding charge transfer reactions between quantum dots (QD) and metal oxides is fundamental for improving photocatalytic, photovoltaic and electronic devices. The complexity of these processes makes it difficult to find an optimum QD size with rapid charge injection and low recombination. We combine time-domain density functional theory with nonadiabatic molecular dynamics to investigate the size and temperature dependence of the experimentally studied electron transfer and charge recombination at CdSe QD-TiO 2 nanobelt (NB) interfaces. The electron injection rate shows strong dependence on the QD size, increasing for small QDs. The rate exhibits Arrhenius temperature dependence, with the activation energy ofmore » the order of millielectronvolts. The charge recombination process occurs due to coupling of the electronic subsystem to vibrational modes of the TiO 2 NB. Inelastic electron-phonon scattering happens on a picosecond time scale, with strong dependence on the QD size. Our simulations demonstrate that the electron-hole recombination rate decreases significantly as the QD size increases, in excellent agreement with experiments. The temperature dependence of the charge recombination rates can be successfully modeled within the framework of the Marcus theory through optimization of the electronic coupling and the reorganization energy. Our simulations indicate that by varying the QD size, one can modulate the photoinduced charge separation and charge recombination, fundamental aspects of the design principles for high efficiency devices.« less

Mesons from Laser-Induced Processes in Ultra-Dense Hydrogen H(0)

PubMed Central

2017-01-01

Large signals of charged light mesons are observed in the laser-induced particle flux from ultra-dense hydrogen H(0) layers. The mesons are formed in such layers on metal surfaces using < 200 mJ laser pulse-energy. The time variation of the signal to metal foil collectors and the magnetic deflection to a movable pin collector are now studied. Relativistic charged particles with velocity up to 500 MeV u-1 thus 0.75 c are observed. Characteristic decay time constants for meson decay are observed, for charged and neutral kaons and also for charged pions. Magnetic deflections agree with charged pions and kaons. Theoretical predictions of the decay chains from kaons to muons in the particle beam agree with the results. Muons are detected separately by standard scintillation detectors in laser-induced processes in ultra-dense hydrogen H(0) as published previously. The muons formed do not decay appreciably within the flight distances used here. Most of the laser-ejected particle flux with MeV energy is not deflected by the magnetic fields and is thus neutral, either being neutral kaons or the ultra-dense HN(0) precursor clusters. Photons give only a minor part of the detected signals. PACS: 67.63.Gh, 14.40.-n, 79.20.Ds, 52.57.-z. PMID:28081199

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...

Moving towards sustainable resources: Recovery and fractionation of nutrients from dairy manure digestate using membranes.

PubMed

Gerardo, Michael L; Aljohani, Nasser H M; Oatley-Radcliffe, Darren L; Lovitt, Robert W

2015-09-01

The fractionation of nitrogen (as ammonia/ammonium) and phosphorus (as phosphate ions) present in the dairy manure digestate was investigated using a nanofiltration membrane NF270. The filtration and separation efficiencies were correlated to pH across the range 3 < pH < 11. Filtration at pH 11 enabled higher permeate flux of 125-150 LMH at 20 bar, however rejection of ammonia was high at 30-36% and phosphate was 96.4-97.2%. At pH 3 and pH 7, electrostatic charge effects led to higher permeation of ammonium and thus more efficient separation of nitrogen. The rejection of phosphorus was relatively constant at any given pH and determined as 83% at pH 3, 97% at pH 7 and 95% at pH 11. The fractionation of nitrogen and phosphorus from complex aqueous solutions was demonstrated to be highly dependent on the charge of the membrane and ionic speciation. Solutions rich in nitrogen (as ammonia/ammonium) were obtained with almost no phosphorus present (<1 ppm) whilst the purification of the PO4-P was achieved by series of diafiltration (DF) operations which further separated the nitrogen. The separation of nutrients benefited from an advantageous membrane process with potential added value for a wide range of industries. The analysis of the process economics for a membrane based plant illustrates that the recovery of nutrients, particularly NH3-N, may be commercially feasible when compared to manufactured anhydrous NH3. Copyright © 2015 Elsevier Ltd. All rights reserved.

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

Chen, C.; Albergo, S.; Caccia, Z.

A liquid hydrogen target was used to study the nuclear fragmentation of beams of relativistic heavy ions, [sup 22]Ne to [sup 58]Ni, over an energy range 400 to 900 MeV/nucleon. The experiments were carried out at the Lawrence Berkeley Laboratory Bevalac HISS facility, using the charge-velocity-rigidity method to identify the charged fragments. Here we describe the general concept of the experiment and present total charge-changing cross sections obtained from 17 separate runs. These new measured cross sections display an energy dependence which follows semiempirical model predictions. The mass dependence of the cross sections behaves as predicted by optical models, butmore » within the experimental energy range, the optical model parameters display a clear energy dependence. The isospin of the projectile nuclei also appears to be an important factor in the interaction process.« less

Molecular Structure and Sequence in Complex Coacervates

NASA Astrophysics Data System (ADS)

Sing, Charles; Lytle, Tyler; Madinya, Jason; Radhakrishna, Mithun

Oppositely-charged polyelectrolytes in aqueous solution can undergo associative phase separation, in a process known as complex coacervation. This results in a polyelectrolyte-dense phase (coacervate) and polyelectrolyte-dilute phase (supernatant). There remain challenges in understanding this process, despite a long history in polymer physics. We use Monte Carlo simulation to demonstrate that molecular features (charge spacing, size) play a crucial role in governing the equilibrium in coacervates. We show how these molecular features give rise to strong monomer sequence effects, due to a combination of counterion condensation and correlation effects. We distinguish between structural and sequence-based correlations, which can be designed to tune the phase diagram of coacervation. Sequence effects further inform the physical understanding of coacervation, and provide the basis for new coacervation models that take monomer-level features into account.

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

Mixed Metal Phosphonate- Phosphate Resins for Separation of Lanthanides from Actinides

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

Clearfield, Abraham

As indicated in the previous annual report the goals of this project are to develop procedures for efficient separation of lanthanides from actinides and curium from americium. These processes are required for the nuclear fuel cycle to minimize the waste and recover the valuable actinides. The basis for our study is that we have prepared a group of compounds that are porous and favor the uptake of ions with charges 3+ and 4+ over ions of lesser charge. The general formula for these materials is M(O 3PC 6H 4PO 3) 1-x/2(APO 4)x·nH 2O: where M=Zr 4+, Sn 4+, A=H, Na,more » or K and X=O, 0.5, 0.8, 1.0, 1.33 and 1.61-3. One of our tasks is to determine which members of this group of compounds are effective in carrying out the required separations. A difficulty in obtaining this required information is that the compounds are amorphous. That is they are not crystalline, therefore we need to resort to synchrotron data to obtain structural data which will be presented in detail. This information will be provided as a separate section.« less

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.

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.

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.

Time-resolved spectroscopic studies of photosynthetic reaction centers and tetrapyrrole chromophores for biomedical and solar-energy applications

NASA Astrophysics Data System (ADS)

Kee, Hooi Ling

2008-10-01

The photophysical properties of diverse tetrapyrrole chromophores as well as energy and electron transfer processes in tetrapyrrole dyads are investigated using static and time-resolved (femtoseconds to seconds) absorption and fluorescence spectroscopy. The goal of these studies is to elucidate the molecular design principals necessary to construct chromophores with the specific and tunable properties that will enhance applications in optical molecular imaging, photodynamic therapy, and solar-energy conversion. The kinetic properties of the transient intermediate P+H B- involving the bacteriopheophytin molecule HB on the normally inactive (B) cofactor branch of the bacterial photosynthetic reaction center are examined in Rhodobacter capsulatus mutants. Using nanosecond flash photolysis and F(L181)Y/Y(M208)F/L(M212)H mutant, the decay pathways and yields of P+HB- were measured, giving an overall yield of 13% for B-side charge separation P* → P+HB- → P+ QB- in this mutant. The goal of these studies is to understand the fundamental differences in the rates, yields, and mechanisms of charge separation and charge recombination along the two parallel electron-transport chains in the bacterial reaction center.

Spin-orbit coupling, electron transport and pairing instabilities in two-dimensional square structures

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

Kocharian, Armen N.; Fernando, Gayanath W.; Fang, Kun

Rashba spin-orbit effects and electron correlations in the two-dimensional cylindrical lattices of square geometries are assessed using mesoscopic two-, three- and four-leg ladder structures. Here the electron transport properties are systematically calculated by including the spin-orbit coupling in tight binding and Hubbard models threaded by a magnetic flux. These results highlight important aspects of possible symmetry breaking mechanisms in square ladder geometries driven by the combined effect of a magnetic gauge field spin-orbit interaction and temperature. The observed persistent current, spin and charge polarizations in the presence of spin-orbit coupling are driven by separation of electron and hole charges andmore » opposite spins in real-space. The modeled spin-flip processes on the pairing mechanism induced by the spin-orbit coupling in assembled nanostructures (as arrays of clusters) engineered in various two-dimensional multi-leg structures provide an ideal playground for understanding spatial charge and spin density inhomogeneities leading to electron pairing and spontaneous phase separation instabilities in unconventional superconductors. Such studies also fall under the scope of current challenging problems in superconductivity and magnetism, topological insulators and spin dependent transport associated with numerous interfaces and heterostructures.« less

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)

A metallic metal oxide (Ti5O9)-metal oxide (TiO2) nanocomposite as the heterojunction to enhance visible-light photocatalytic activity

NASA Astrophysics Data System (ADS)

Li, L. H.; Deng, Z. X.; Xiao, J. X.; Yang, G. W.

2015-06-01

Coupling titanium dioxide (TiO2) with other semiconductors is a popular method to extend the optical response range of TiO2 and improve its photon quantum efficiency, as coupled semiconductors can increase the separation rate of photoinduced charge carriers in photocatalysts. Differing from normal semiconductors, metallic oxides have no energy gap separating occupied and unoccupied levels, but they can excite electrons between bands to create a high carrier mobility to facilitate kinetic charge separation. Here, we propose the first metallic metal oxide-metal oxide (Ti5O9-TiO2) nanocomposite as a heterojunction for enhancing the visible-light photocatalytic activity of TiO2 nanoparticles and we demonstrate that this hybridized TiO2-Ti5O9 nanostructure possesses an excellent visible-light photocatalytic performance in the process of photodegrading dyes. The TiO2-Ti5O9 nanocomposites are synthesized in one step using laser ablation in liquid under ambient conditions. The as-synthesized nanocomposites show strong visible-light absorption in the range of 300-800 nm and high visible-light photocatalytic activity in the oxidation of rhodamine B. They also exhibit excellent cycling stability in the photodegrading process. A working mechanism for the metallic metal oxide-metal oxide nanocomposite in the visible-light photocatalytic process is proposed based on first-principle calculations of Ti5O9. This study suggests that metallic metal oxides can be regarded as partners for metal oxide photocatalysts in the construction of heterojunctions to improve photocatalytic activity.

A metallic metal oxide (Ti5O9)-metal oxide (TiO2) nanocomposite as the heterojunction to enhance visible-light photocatalytic activity.

PubMed

Li, L H; Deng, Z X; Xiao, J X; Yang, G W

2015-01-26

Coupling titanium dioxide (TiO2) with other semiconductors is a popular method to extend the optical response range of TiO2 and improve its photon quantum efficiency, as coupled semiconductors can increase the separation rate of photoinduced charge carriers in photocatalysts. Differing from normal semiconductors, metallic oxides have no energy gap separating occupied and unoccupied levels, but they can excite electrons between bands to create a high carrier mobility to facilitate kinetic charge separation. Here, we propose the first metallic metal oxide-metal oxide (Ti5O9-TiO2) nanocomposite as a heterojunction for enhancing the visible-light photocatalytic activity of TiO2 nanoparticles and we demonstrate that this hybridized TiO2-Ti5O9 nanostructure possesses an excellent visible-light photocatalytic performance in the process of photodegrading dyes. The TiO2-Ti5O9 nanocomposites are synthesized in one step using laser ablation in liquid under ambient conditions. The as-synthesized nanocomposites show strong visible-light absorption in the range of 300-800 nm and high visible-light photocatalytic activity in the oxidation of rhodamine B. They also exhibit excellent cycling stability in the photodegrading process. A working mechanism for the metallic metal oxide-metal oxide nanocomposite in the visible-light photocatalytic process is proposed based on first-principle calculations of Ti5O9. This study suggests that metallic metal oxides can be regarded as partners for metal oxide photocatalysts in the construction of heterojunctions to improve photocatalytic activity.

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.

Natural Limits for Currents in Charge Separated Pulsar Magnetospheres

NASA Astrophysics Data System (ADS)

Jessner, A.; Lesch, H.; Kunzl, T.

Rough estimates and upper limits on current and particle densities form the basis of most of the canonical pulsar models. Whereas the surface of the rotating neutron star is capable of supplying sufficient charges to provide a current that, given the polar cap potential, could easily fuel the observed energy loss processes, observational and theoretical constraints provide strict upper limits to the charge densities. The space charge of a current consisting solely of particles having only one sign creates a compensating potential that will make the maximum current dependent on potential and distance. In the non-relativistic case this fact is expressed in the familiar Child-Langmuir law. Its relativistic generalization and subsequent application to the inner pulsar magnetosphere provides clear limits on the strength and radial extension of charged currents originating on the polar cap. Violent Pierce-type oscillations set in, if one attempts to inject more current than the space charge limit into a given volume. These considerations apply wherever there is a significant amount of charged current flow, in particular in the gap regions. There they can be used to derive limits on the size of such gaps and their stability.

Qualification testing of general electric 50 Ah nickel-cadmium cells with new separator and new positive plate processing

NASA Astrophysics Data System (ADS)

Morrow, G. W.

1986-09-01

Forty-two 50 Ah aerospace nickel-cadmium cells were delivered to Goddard Space Flight Center (GSFC) by General Electric (GE) in February, 1985, for the purpose of evaluating and qualifying a new nylon separator material Pellon 2536, and the new GE Positive Plate Nickel Attack Control Passivation process. Testing began in May, 1985, at the Naval Weapons Support Center (NWSC) in Crane, Indiana with standard initial evaluation tests. Life cycling in both Low Earth Orbit (LEO) and Geosynchronous Orbit (GEO) began in July, 1985, with approximately 1200 LEO cycles complete at this writting. Early test results show that cells with positive plate passivation exhibit higher than normal charge voltage characteristics. Other aspects of performance were nominal.

Qualification Testing of General Electric 50 Ah Nickel-Cadmium Cells with New Separator and New Positive Plate Processing

NASA Technical Reports Server (NTRS)

Morrow, G. W.

1986-01-01

Forty-two 50 Ah aerospace nickel-cadmium cells were delivered to Goddard Space Flight Center (GSFC) by General Electric (GE) in February, 1985, for the purpose of evaluating and qualifying a new nylon separator material Pellon 2536, and the new GE Positive Plate Nickel Attack Control Passivation process. Testing began in May, 1985, at the Naval Weapons Support Center (NWSC) in Crane, Indiana with standard initial evaluation tests. Life cycling in both Low Earth Orbit (LEO) and Geosynchronous Orbit (GEO) began in July, 1985, with approximately 1200 LEO cycles complete at this writting. Early test results show that cells with positive plate passivation exhibit higher than normal charge voltage characteristics. Other aspects of performance were nominal.

Electric field measurements during the Condor critical velocity experiment

NASA Technical Reports Server (NTRS)

Kelley, M. C.; Pfaff, R. F.; Haerendel, G.

1986-01-01

The instrumentation of the Condor critical velocity Ba experiment (Wescott et al., 1986) for the measurements of the energetic particles and the electric field associated with a Ba explosion is described. The Ba explosion created a complex electric field pulse detected in situ by a single-axis double electric-field probe on a separate spacecraft. The measurements provide evidence of several important links in the critical-velocity chain, and are consistent with two hypotheses. The first hypothesis involves the creation of large polarization electric field due to charge separation; the second hypothesis implies a polarization of the beam by currents flowing across it. The chain of physical processes inferred from the observations is in agreement with most theories for the Alfven process.

Statistical patterns in the location of natural lightning

NASA Astrophysics Data System (ADS)

Zoghzoghy, F. G.; Cohen, M. B.; Said, R. K.; Inan, U. S.

2013-01-01

Lightning discharges are nature's way of neutralizing the electrical buildup in thunderclouds. Thus, if an individual discharge destroys a substantial fraction of the cloud charge, the probability of a subsequent flash is reduced until the cloud charge separation rebuilds. The temporal pattern of lightning activity in a localized region may thus inherently be a proxy measure of the corresponding timescales for charge separation and electric field buildup processes. We present a statistical technique to bring out this effect (as well as the subsequent recovery) using lightning geo-location data, in this case with data from the National Lightning Detection Network (NLDN) and from the GLD360 Network. We use this statistical method to show that a lightning flash can remove an appreciable fraction of the built up charge, affecting the neighboring lightning activity for tens of seconds within a ˜ 10 km radius. We find that our results correlate with timescales of electric field buildup in storms and suggest that the proposed statistical tool could be used to study the electrification of storms on a global scale. We find that this flash suppression effect is a strong function of flash type, flash polarity, cloud-to-ground flash multiplicity, the geographic location of lightning, and is proportional to NLDN model-derived peak stroke current. We characterize the spatial and temporal extent of the suppression effect as a function of these parameters and discuss various applications of our findings.

Continuous separation of copper ions from a mixture of heavy metal ions using a three-zone carousel process packed with metal ion-imprinted polymer.

PubMed

Jo, Se-Hee; Lee, See-Young; Park, Kyeong-Mok; Yi, Sung Chul; Kim, Dukjoon; Mun, Sungyong

2010-11-05

In this study, a three-zone carousel process based on a proper molecular imprinted polymer (MIP) resin was developed for continuous separation of Cu(2+) from Mn(2+) and Co(2+). For this task, the Cu (II)-imprinted polymer (Cu-MIP) resin was synthesized first and used to pack the chromatographic columns of a three-zone carousel process. Prior to the experiment of the carousel process based on the Cu-MIP resin (MIP-carousel process), a series of single-column experiments were performed to estimate the intrinsic parameters of the three heavy metal ions and to find out the appropriate conditions of regeneration and re-equilibration. The results from these single-column experiments and the additional computer simulations were then used for determination of the operating parameters of the MIP-carousel process under consideration. Based on the determined operating parameters, the MIP-carousel experiments were carried out. It was confirmed from the experimental results that the proposed MIP-carousel process was markedly effective in separating Cu(2+) from Mn(2+) and Co(2+) in a continuous mode with high purity and a relatively small loss. Thus, the MIP-carousel process developed in this study deserves sufficient attention in materials processing industries or metal-related industries, where the selective separation of heavy metal ions with the same charge has been a major concern. Copyright © 2010 Elsevier B.V. All rights reserved.

Long-Lived Photoinduced Charge Separation in a Trinuclear Iron-μ 3 -oxo-based Metal–Organic Framework

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

Hanna, Lauren; Kucheryavy, Pavel; Liu, Cunming

2017-06-14

The presence of long-lived charge-separated excited states in metal-organic frameworks (MOFs) can enhance their photocatalytic activity by decreasing the probability that photogenerated electrons and holes recombine before accessing adsorbed reactants. Detecting these charge separated states via optical transient absorption, however, can be challenging when they lack definitive optical signatures. Here, we investigate the long-lived excited state of a MOF with such vague optical properties, MIL-100(Fe), comprised of Fe3-μ3-oxo clusters and trimesic acid linkers using Fe K-edge X-ray transient absorption (XTA) spectroscopy, to unambiguously determine its ligand-to-metal charge transfer character. Spectra measured at time delays up to 3.6 μs confirm themore » long lived nature of the charge separated excited state. Several trinuclear iron μ3- oxo carboxylate complexes, which model the trinuclear cores of the MOF structure, are measured for comparison using both steady state XAS and XTA to further support this assignment and corresponding decay time. The MOF is prepared as a colloidal nanoparticle suspension for these measurements so both its fabrication and particle size analysis are presented, as well.« less

Charge separation and charge delocalization identified in long-living states of photoexcited DNA

PubMed Central

Bucher, Dominik B.; Pilles, Bert M.; Carell, Thomas; Zinth, Wolfgang

2014-01-01

Base stacking in DNA is related to long-living excited states whose molecular nature is still under debate. To elucidate the molecular background we study well-defined oligonucleotides with natural bases, which allow selective UV excitation of one single base in the strand. IR probing in the picosecond regime enables us to dissect the contribution of different single bases to the excited state. All investigated oligonucleotides show long-living states on the 100-ps time scale, which are not observable in a mixture of single bases. The fraction of these states is well correlated with the stacking probabilities and reaches values up to 0.4. The long-living states show characteristic absorbance bands that can be assigned to charge-transfer states by comparing them to marker bands of radical cation and anion spectra. The charge separation is directed by the redox potential of the involved bases and thus controlled by the sequence. The spatial dimension of this charge separation was investigated in longer oligonucleotides, where bridging sequences separate the excited base from a sensor base with a characteristic marker band. After excitation we observe a bleach of all involved bases. The contribution of the sensor base is observable even if the bridge is composed of several bases. This result can be explained by a charge delocalization along a well-stacked domain in the strand. The presence of charged radicals in DNA strands after light absorption may cause reactions—oxidative or reductive damage—currently not considered in DNA photochemistry. PMID:24616517

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.

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.

Left-right symmetry and the charged Higgs bosons at the LHC

NASA Astrophysics Data System (ADS)

Bambhaniya, G.; Chakrabortty, J.; Gluza, J.; Kordiaczynska, M.; Szafron, R.

2014-05-01

The charged Higgs boson sector of the Minimal Manifest Left-Right Symmetric model (MLRSM) is investigated in the context of LHC discovery search for new physics beyond Standard Model. We discuss and summarise the main processes within MLRSM where heavy charged Higgs bosons can be produced at the LHC. We explore the scenarios where the amplified signals due to relatively light charged scalars dominate against heavy neutral Z 2 and charged gauge W 2 as well as heavy neutral Higgs bosons signals which are dumped due to large vacuum expectation value v R of the right-handed scalar triplet. Consistency with FCNC effects implies masses of two neutral Higgs bosons to be at least of 10 TeV order, which in turn implies that in MLRSM only three of four charged Higgs bosons, namely and ,and can be simultaneously light. In particular, production processes with one and two doubly charged Higgs bosons are considered. We further incorporate the decays of those scalars leading to multi lepton signals at the LHC. Branching ratios for heavy neutrino N R , W 2 and Z 2 decay into charged Higgs bosons are calculated. These effects are substantial enough and cannot be neglected. The tri- and four-lepton final states for different benchmark points are analysed. Kinematic cuts are chosen in order to strength the leptonic signals and decrease the Standard Model (SM) background. The results are presented using di-lepton invariant mass and lepton-lepton separation distributions for the same sign (SSDL) and opposite sign (OSDL) di-leptons as well as the charge asymmetry are also discussed. We have found that for considered MLRSM processes tri-lepton and four-lepton signals are most important for their detection when compared to the SM background. Both of the signals can be detected at 14 TeV collisions at the LHC with integrated luminosity at the level of 300 fb-1 with doubly charged Higgs bosons up to approximately 600 GeV. Finally, possible extra contribution of the charged MLRSM scalar particles to the measured Higgs to di-photon ( → γγ) decay is computed and pointed out.

Effects of granular charge on flow and mixing

NASA Astrophysics Data System (ADS)

Shinbrot, T.; Herrmann, H. J.

2008-12-01

Sandstorms in the desert have long been reported to produce sparks and other electrical disturbances - indeed as long ago as 1850, Faraday commented on the peculiarities of granular charging during desert sandstorms. Similarly, lightning strikes within volcanic dust plumes have been repeatedly reported for over half a century, but remain unexplained. The problem of granular charging has applied, as well as natural, implications, for charged particle clouds frequently generate spectacularly devastating dust explosions in granular processing plants, and sand becomes strongly electrified by helicopters traveling in desert environments. The issue even has implications for missions to the Moon and to Mars, where charged dust degrades solar cells viability and clings to spacesuits, limiting the lifetime of their joints. Despite the wide-ranging importance of granular charging, even the simplest aspects of its causes remain elusive. To take one example, sand grains in the desert manage to charge one another despite having only similar materials to rub against over expanses of many miles - thus existing theories of charging due to material differences fail entirely to account for the observed charging of desert sands. In this talk, we describe recent progress made in identifying underlying causes of granular charging, both in desert-like environments and in industrial applications, and we examine effects of granular charging on flow, mixing and separation of common granular materials. We find that charging of identical grains can occur under simple laboratory conditions, and we make new predictions for the effects of this charging on granular behaviours.

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.

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.

Spectroscopy of Photovoltaic Materials: Charge-Transfer Complexes and Titanium Dioxide

NASA Astrophysics Data System (ADS)

Dillon, Robert John

The successful function of photovoltaic (PV) and photocatalytic (PC) systems centers primarily on the creation and photophysics of charge separated electron-hole pairs. The pathway leading to separate carriers varies by material; organic materials typically require multiple events to charge separate, whereas inorganic semiconductors can directly produce free carriers. In this study, time-resolved spectroscopy is used to provide insight into two such systems: 1) organic charge-transfer (CT) complexes, where electrons and holes are tightly bound to each other, and 2) Au-TiO2 core-shell nanostructures, where free carriers are directly generated. 1) CT complexes are structurally well defined systems consisting of donor molecules, characterized by having low ionization potentials, and acceptor molecules, characterized by having high electron affinities. Charge-transfer is the excitation of an electron from the HOMO of a donor material directly into the LUMO of the acceptor material, leading to an electron and hole separated across the donor:acceptor interface. The energy of the CT transition is often less than that of the bandgaps of donor and acceptor materials individually, sparking much interest if PV systems can utilize the CT band to generate free carriers from low energy photons. In this work we examine the complexes formed between acceptors tetracyanobenzene (TCNB) and tetracyanoquinodimethane (TCNQ) with several aromatic donors. We find excitation of the charge-transfer band of these systems leads to strongly bound electron-hole pairs that exclusively undergo recombination to the ground state. In the case of the TCNB complexes, our initial studies were flummoxed by the samples' generally low threshold for photo and mechanical damage. As our results conflicted with previous literature, a significant portion of this study was spent quantifying the photodegradation process. 2) Unlike the previous system, free carriers are directly photogenerated in TiO2, and the prime consideration is avoiding loss due to recombination of the electron and hole. In this study, four samples of core-shell Au-TiO 2 nanostructures are analyzed for their photocatalytic activity and spectroscopic properties. The samples were made with increasingly crystalline TiO2 shells. The more crystalline samples had higher photocatalytic activities, attributed to longer carrier lifetimes. The observed photophysics of these samples vary with excitation wavelength and detection method used. We find the time-resolved photoluminescence correlates with the samples' photocatalytic activities only when high energy, excitation wavelength less than or equal to 300 nm is used, while transient absorption experiments show no correlation regardless of excitation source. The results imply that photoexcitation with high energy photons can generate both reactive surface sites and photoluminescent surface sites in parallel. Both types of sites then undergo similar electron-hole recombination processes that depend on the crystallinity of the TiO2 shell. Surface sites created by low energy photons, as well as bulk TiO2 carrier dynamics that are probed by transient absorption, do not appear to be sensitive to the same dynamics that determine chemical reactivity.

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

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.

Automatic multiple-sample applicator and electrophoresis apparatus

NASA Technical Reports Server (NTRS)

Grunbaum, B. W. (Inventor)

1977-01-01

An apparatus for performing electrophoresis and a multiple-sample applicator is described. Electrophoresis is a physical process in which electrically charged molecules and colloidal particles, upon the application of a dc current, migrate along a gel or a membrane that is wetted with an electrolyte. A multiple-sample applicator is provided which coacts with a novel tank cover to permit an operator either to depress a single button, thus causing multiple samples to be deposited on the gel or on the membrane simultaneously, or to depress one or more sample applicators separately by means of a separate button for each applicator.

Simultaneously promoting charge separation and photoabsorption of BiOX (X = Cl, Br) for efficient visible-light photocatalysis and photosensitization by compositing low-cost biochar

NASA Astrophysics Data System (ADS)

Li, Min; Huang, Hongwei; Yu, Shixin; Tian, Na; Dong, Fan; Du, Xin; Zhang, Yihe

2016-11-01

Exploration of novel and efficient composite photocatalysts is of great significance for advancing the practical application of photocatalysis. BiOX (X = Cl, Br) is a kind of promising photocatalysts, but the charge separation efficiency and photoabsorption need to be ameliorated. In this work, we first employ a low-cost and easily accessable carbon material biochar to modify BiOX (X = Cl, Br) and develop biochar/BiOX (X = Cl, Br) composite photocatalysts via a facile in-situ deposition method. The as-prepared composites are detailedly characterized by SEM, SEM-mapping, TEM, XRD and XPS, and DRS result demonstrates that the visible-light absorption of BiOX (X = Cl, Br) catalysts can be exceedingly enhanced by biochar. The biochar/BiOX (X = Cl, Br) composites are found to unfold remarkably enhanced visible-light-driven photocatalytic activity toward degradation of MO and photocurrent generation. The strengthened photocatalytic performance mainly stems from the profoundly improved charge separation and delivery efficiency, as evidenced by the electrochemical impedance spectra (EIS), photoluminescence (PL), and time-resolved PL decay spectra. Additionally, the biochar exerts importance in enhancing the two different types of photochemical reactions of BiOBr and BiOCl, in which the photocatalytic mechanisms are found to be photocatalysis and photosensitization process, respectively. The present work may open up a new avenue for framing economic and efficient photocatalytic materials and new composite materials for photoelectric application.

3D-liquid chromatography as a complex mixture characterization tool for knowledge-based downstream process development.

PubMed

Hanke, Alexander T; Tsintavi, Eleni; Ramirez Vazquez, Maria Del Pilar; van der Wielen, Luuk A M; Verhaert, Peter D E M; Eppink, Michel H M; van de Sandt, Emile J A X; Ottens, Marcel

2016-09-01

Knowledge-based development of chromatographic separation processes requires efficient techniques to determine the physicochemical properties of the product and the impurities to be removed. These characterization techniques are usually divided into approaches that determine molecular properties, such as charge, hydrophobicity and size, or molecular interactions with auxiliary materials, commonly in the form of adsorption isotherms. In this study we demonstrate the application of a three-dimensional liquid chromatography approach to a clarified cell homogenate containing a therapeutic enzyme. Each separation dimension determines a molecular property relevant to the chromatographic behavior of each component. Matching of the peaks across the different separation dimensions and against a high-resolution reference chromatogram allows to assign the determined parameters to pseudo-components, allowing to determine the most promising technique for the removal of each impurity. More detailed process design using mechanistic models requires isotherm parameters. For this purpose, the second dimension consists of multiple linear gradient separations on columns in a high-throughput screening compatible format, that allow regression of isotherm parameters with an average standard error of 8%. © 2016 American Institute of Chemical Engineers Biotechnol. Prog., 32:1283-1291, 2016. © 2016 American Institute of Chemical Engineers.

Interfacial Engineering and Charge Carrier Dynamics in Extremely Thin Absorber Solar Cells

NASA Astrophysics Data System (ADS)

Edley, Michael

Photovoltaic energy is a clean and renewable source of electricity; however, it faces resistance to widespread use due to cost. Nanostructuring decouples constraints related to light absorption and charge separation, potentially reducing cost by allowing a wider variety of processing techniques and materials to be used. However, the large interfacial areas also cause an increased dark current which negatively affects cell efficiency. This work focuses on extremely thin absorber (ETA) solar cells that used a ZnO nanowire array as a scaffold for an extremely thin CdSe absorber layer. Photoexcited electrons generated in the CdSe absorber are transferred to the ZnO layer, while photogenerated holes are transferred to the liquid electrolyte. The transfer of photoexcited carriers to their transport layer competes with bulk recombination in the absorber layer. After charge separation, transport of charge carriers to their respective contacts must occur faster than interfacial recombination for efficient collection. Charge separation and collection depend sensitively on the dimensions of the materials as well as their interfaces. We demonstrated that an optimal absorber thickness can balance light absorption and charge separation. By treating the ZnO/CdSe interface with a CdS buffer layer, we were able to improve the Voc and fill factor, increasing the ETA cell's efficiency from 0.53% to 1.34%, which is higher than that achievable using planar films of the same material. We have gained additional insight into designing ETA cells through the use of dynamic measurements. Ultrafast transient absorption spectroscopy revealed that characteristic times for electron injection from CdSe to ZnO are less than 1 ps. Electron injection is rapid compared to the 2 ns bulk lifetime in CdSe. Optoelectronic measurements such as transient photocurrent/photovoltage and electrochemical impedance spectroscopy were applied to study the processes of charge transport and interfacial recombination. With these techniques, the extension of the depletion layer from CdSe into ZnO was determined to be vital to suppression of interfacial recombination. However, depletion of the ZnO also restricted the effective diffusion core for electrons and slowed their transport. Thus, materials and geometries should be chosen to allow for a depletion layer that suppresses interfacial recombination without impeding electron transport to the point that it is detrimental to cell performance. Thin film solar cells are another promising technology that can reduce costs by relaxing material processing requirements. CuInxGa (1-x)Se (CIGS) is a well studied thin film solar cell material that has achieved good efficiencies of 22.6%. However, use of rare elements raise concerns over the use of CIGS for global power production. CuSbS2 shares chemistry with CuInSe2 and also presents desirable properties for thin film absorbers such as optimal band gap (1.5 eV), high absorption coefficient, and Earth-abundant and non-toxic elements. Despite the promise of CuSbS2, direct characterization of the material for solar cell application is scarce in the literature. CuSbS2 nanoplates were synthesized by a colloidal hot-injection method at 220 °C in oleylamine. The CuSbS2 platelets synthesized for 30 minutes had dimensions of 300 nm by 400 nm with a thickness of 50 nm and were capped with the insulating oleylamine synthesis ligand. The oleylamine synthesis ligand provides control over nanocrystal growth but is detrimental to intercrystal charge transport that is necessary for optoelectronic device applications. Solid-state and solution phase ligand exchange of oleylamine with S2- were used to fabricate mesoporous films of CuSbS2 nanoplates for application in solar cells. Exchange of the synthesis ligand with S2- resulted in a two order of magnitude increase in 4-point probe conductivity. Photoexcited carrier lifetimes of 1.4 ns were measured by time-resolved terahertz spectroscopy, indicating potential for CuSbS2 as a solar cell absorber material.

Spontaneously formed high-performance charge-transport layers of organic single-crystal semiconductors on precisely synthesized insulating polymers

NASA Astrophysics Data System (ADS)

Makita, Tatsuyuki; Sasaki, Masayuki; Annaka, Tatsuro; Sasaki, Mari; Matsui, Hiroyuki; Mitsui, Chikahiko; Kumagai, Shohei; Watanabe, Shun; Hayakawa, Teruaki; Okamoto, Toshihiro; Takeya, Jun

2017-04-01

Charge-transporting semiconductor layers with high carrier mobility and low trap-density, desired for high-performance organic transistors, are spontaneously formed as a result of thermodynamic phase separation from a blend of π-conjugated small molecules and precisely synthesized insulating polymers dissolved in an aromatic solvent. A crystal film grows continuously to the size of centimeters, with the critical conditions of temperature, concentrations, and atmosphere. It turns out that the molecular weight of the insulating polymers plays an essential role in stable film growth and interfacial homogeneity at the phase separation boundary. Fabricating the transistor devices directly at the semiconductor-insulator boundaries, we demonstrate that the mixture of 3,11-didecyldinaphtho[2,3-d:2',3'-d']benzo[1,2-b:4,5-b']dithiophene and poly(methyl methacrylate) with the optimized weight-average molecular weight shows excellent device performances. The spontaneous phase separation with a one-step fabrication process leads to a high mobility up to 10 cm2 V-1 s-1 and a low subthreshold swing of 0.25 V dec-1 even without any surface treatment such as self-assembled monolayer modifications on oxide gate insulators.

Adsorbent for hydroquinone removal based on graphene oxide functionalized with magnetic cyclodextrin-chitosan.

PubMed

Li, Leilei; Fan, Lulu; Sun, Min; Qiu, Huamin; Li, Xiangjun; Duan, Huimin; Luo, Chuannan

2013-07-01

Magnetic cyclodextrin-chitosan/graphene oxide (CCGO) with high surface area was synthesized via a simple chemical bonding method. The characteristics results of FTIR, SEM, TEM and XRD showed that CCGO was prepared. The large saturation magnetization (22.35 emu/g) of the synthesized nanoparticles allows fast separation of the CCGO from liquid suspension. These composites could efficiently remove hydroquinone from simulated wastewater with a facile subsequent solid-liquid separation because of their large area, abundant hydroxyl and amino groups with handy operation, and hydrophobicity. The hydroquinone removal process was found to obey the Freundlich adsorption model and its kinetics followed pseudo-second-order rate equation. The hydroquinone removal mechanism of CCGO might be attributed to the electrostatic adsorption of hydroquinone in the form of negatively charged hydroquinone by positively charged chitosan, accompanying hydroquinone absorbed by cavities of the cyclodextrin, and forming hydrogen bonds between hydroquinone and the hydroxyl groups on the surface of CCGO. The used CCGO could be recovered with ethanol. This study provides a promising nanostructured adsorbent with easy separation property for heavy metal ions removal. Copyright © 2013 Elsevier B.V. All rights reserved.

A Mussel-Derived One-Component Adhesive Coacervate

PubMed Central

Wei, Wei; Tan, Yerpeng; Rodriguez, N. Martinez; Yu, Jing; Israelachvili, Jacob N.; Waite, J. Herbert

2013-01-01

Marine organisms process and deliver many of their underwater coatings and adhesives as complex fluids. In marine mussels, one such fluid, secreted during the formation of adhesive plaques, consists of a concentrated colloidal suspension of a mussel foot protein (mfp) known as Mfp-3S. Results of this study suggest that Mfp-3S becomes a complex fluid by a liquid-liquid phase separation from equilibrium solution at a pH and ionic strength reminiscent of conditions created by the mussel foot during plaque formation. The pH dependence of phase separation and its sensitivity indicate that inter/intra-molecular electrostatic interactions are partially responsible for driving the phase separation. Hydrophobic interactions between the nonpolar Mfp-3S proteins provide another important driving force for coacervation. As complex coacervation typically results from charge-charge interactions between polyanions and polycations, Mfp-3S is thus unique in being the only known protein that coacervates with itself. The Mfp-3S coacervate was shown to have an effective interfacial energy of ≤ 1 mJ/m2 which explains its tendency to spread over or engulf most surfaces. Of particular interest to biomedical applications is the extremely high adsorption capacity of coacervated Mfp-3S on hydroxyapatite. PMID:24060881

A unified engineering model of the first stroke in downward negative lightning

NASA Astrophysics Data System (ADS)

Nag, Amitabh; Rakov, Vladimir A.

2016-03-01

Each stroke in a negative cloud-to-ground lightning flash is composed of downward leader and upward return stroke processes, which are usually modeled individually. The first stroke leader is stepped and starts with preliminary breakdown (PB) which is often viewed as a separate process. We present the first unified engineering model for computing the electric field produced by a sequence of PB, stepped leader, and return stroke processes, serving to transport negative charge to ground. We assume that a negatively charged channel extends downward in a stepped fashion during both the PB and leader stages. Each step involves a current wave that propagates upward along the newly formed channel section. Once the leader attaches to ground, an upward propagating return stroke neutralizes the charge deposited along the channel. Model-predicted electric fields are in reasonably good agreement with simultaneous measurements at both near (hundreds of meters, electrostatic field component is dominant) and far (tens of kilometers, radiation field component is dominant) distances from the lightning channel. Relations between the features of computed electric field waveforms and model input parameters are examined. It appears that peak currents associated with PB pulses are similar to return stroke peak currents, and the observed variation of electric radiation field peaks produced by leader steps at different heights above ground is influenced by the ground corona space charge.

Organic solar cells: understanding the role of Förster resonance energy transfer.

PubMed

Feron, Krishna; Belcher, Warwick J; Fell, Christopher J; Dastoor, Paul C

2012-12-12

Organic solar cells have the potential to become a low-cost sustainable energy source. Understanding the photoconversion mechanism is key to the design of efficient organic solar cells. In this review, we discuss the processes involved in the photo-electron conversion mechanism, which may be subdivided into exciton harvesting, exciton transport, exciton dissociation, charge transport and extraction stages. In particular, we focus on the role of energy transfer as described by F¨orster resonance energy transfer (FRET) theory in the photoconversion mechanism. FRET plays a major role in exciton transport, harvesting and dissociation. The spectral absorption range of organic solar cells may be extended using sensitizers that efficiently transfer absorbed energy to the photoactive materials. The limitations of F¨orster theory to accurately calculate energy transfer rates are discussed. Energy transfer is the first step of an efficient two-step exciton dissociation process and may also be used to preferentially transport excitons to the heterointerface, where efficient exciton dissociation may occur. However, FRET also competes with charge transfer at the heterointerface turning it in a potential loss mechanism. An energy cascade comprising both energy transfer and charge transfer may aid in separating charges and is briefly discussed. Considering the extent to which the photo-electron conversion efficiency is governed by energy transfer, optimisation of this process offers the prospect of improved organic photovoltaic performance and thus aids in realising the potential of organic solar cells.

State of charge indicators for a battery

DOEpatents

Rouhani, S. Zia

1999-01-01

The present invention relates to state of charge indicators for a battery. One aspect of the present invention utilizes expansion and contraction displacements of an electrode plate of a battery to gauge the state of charge in the battery. One embodiment of a battery of the present invention includes an anodic plate; a cathodic plate; an electrolyte in contact with the anodic and cathodic plates; plural terminals individually coupled with one of the anodic and cathodic plates; a separator intermediate the anodic and cathodic plates; an indicator configured to indicate an energy level of the battery responsive to movement of the separator; and a casing configured to house the anodic and cathodic plates, electrolyte, and separator.

Selective, ultrathin membrane skins prepared by deposition of novel polymer films on porous alumina supports

NASA Astrophysics Data System (ADS)

Balachandra, Anagi Manjula

Membrane-based separations are attractive in industrial processes because of their low energy costs and simple operation. However, low permeabilities often make membrane processes uneconomical. Since flux is inversely proportional to membrane thickness, composite membranes consisting of ultrathin, selective skins on highly permeable supports are required to simultaneously achieve high throughput and high selectivity. However, the synthesis of defect-free skins with thicknesses less than 50 nm is difficult, and thus flux is often limited. Layer-by-layer deposition of oppositely charged polyelectrolytes on porous supports is an attractive method to synthesize ultrathin ion-separation membranes with high flux and high selectivity. The ion-transport selectivity of multilayer polyelectrolyte membranes (MPMs) is primarily due to Donnan exclusion; therefore increase in fixed charge density should yield high selectivity. However, control over charge density in MPMs is difficult because charges on polycations are electrostatically compensated by charges on polyanions, and the net charge in the bulk of these films is small. To overcome this problem, we introduced a templating method to create ion-exchange sites in the bulk of the membrane. This strategy involves alternating deposition of a Cu2+-poly(acrylic acid) complex and poly(allylamine hydrochloride) on a porous alumina support followed by removal of Cu2+ and deprotonation to yield free -COO- ion-exchange sites. Diffusion dialysis studies showed that the Cl-/SO42-. Selectivity of Cu2+-templated membranes is 4-fold higher than that of membranes prepared in the absence of Cu2+. Post-deposition cross-linking of these membranes by heat-induced amide bond formation further increased Cl-/SO42- selectivity to values as high as 600. Room-temperature, surface-initiated atom transfer radical polymerization (ATRP) provides another convenient method for formation of ultrathin polymer skins. This process involves attachment of polymerization initiators to a porous alumina support and subsequent polymerization from these initiators. Because ATRP is a controlled polymerization technique, it yields well-defined polymer films with low polydispersity indices (narrow molecular weight distributions). Additionally, this method is attractive because film thickness can be easily controlled by adjusting polymerization time. Gas-permeability data showed that grafted poly(ethylene glycol dimethacrylate) membranes have a CO 2/CH4 selectivity of 20, whereas poly(2-hydroxyethyl methacrylate) (PHEMA) films grown from a surface have negligible selectivity. However, derivatization of PHEMA with pentadecafluorooctanoyl chloride increases the solubility of CO2 in the membrane and results in a CO2/CH4 selectivity of 9. Although composite PHEMA membranes have no significant gas-transport selectivity, diffusion dialysis studies with PHEMA membranes showed moderate ion-transport selectivities. Cross-linking of PHEMA membranes by reaction with succinyl chloride greatly enhanced anion-transport selectivities while maintaining reasonable flux. The selectivities of these systems demonstrate that alternating polyelectrolyte deposition and surface-initiated ATRP are indeed capable of forming ultrathin, defect-free membrane skins that can potentially be modified for specific separations.

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.

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.

Molecular Effects on Coacervate-Driven Block Copolymer Self Assembly

NASA Astrophysics Data System (ADS)

Lytle, Tyer; Radhakrishna, Mithun; Sing, Charles

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

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

PubMed

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

2018-03-15

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

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.

Molecular approaches to solar energy conversion: the energetic cost of charge separation from molecular-excited states.

PubMed

Durrant, James R

2013-08-13

This review starts with a brief overview of the technological potential of molecular-based solar cell technologies. It then goes on to focus on the core scientific challenge associated with using molecular light-absorbing materials for solar energy conversion, namely the separation of short-lived, molecular-excited states into sufficiently long-lived, energetic, separated charges capable of generating an external photocurrent. Comparisons are made between different molecular-based solar cell technologies, with particular focus on the function of dye-sensitized photoelectrochemical solar cells as well as parallels with the function of photosynthetic reaction centres. The core theme of this review is that generating charge carriers with sufficient lifetime and a high quantum yield from molecular-excited states comes at a significant energetic cost-such that the energy stored in these charge-separated states is typically substantially less than the energy of the initially generated excited state. The role of this energetic loss in limiting the efficiency of solar energy conversion by such devices is emphasized, and strategies to minimize this energy loss are compared and contrasted.

Ion exchange separation of chromium from natural water matrix for stable isotope mass spectrometric analysis

USGS Publications Warehouse

Ball, J.W.; Bassett, R.L.

2000-01-01

A method has been developed for separating the Cr dissolved in natural water from matrix elements and determination of its stable isotope ratios using solid-source thermal-ionization mass spectrometry (TIMS). The separation method takes advantage of the existence of the oxidized form of Cr as an oxyanion to separate it from interfering cations using anion-exchange chromatography, and of the reduced form of Cr as a positively charged ion to separate it from interfering anions such as sulfate. Subsequent processing of the separated sample eliminates residual organic material for application to a solid source filament. Ratios for 53Cr/52Cr for National Institute of Standards and Technology Standard Reference Material 979 can be measured using the silica gel-boric acid technique with a filament-to-filament standard deviation in the mean 53Cr/52Cr ratio for 50 replicates of 0.00005 or less. (C) 2000 Elsevier Science B.V. All rights reserved.

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

Using factorial experimental design to evaluate the separation of plastics by froth flotation.

PubMed

Salerno, Davide; Jordão, Helga; La Marca, Floriana; Carvalho, M Teresa

2018-03-01

This paper proposes the use of factorial experimental design as a standard experimental method in the application of froth flotation to plastic separation instead of the commonly used OVAT method (manipulation of one variable at a time). Furthermore, as is common practice in minerals flotation, the parameters of the kinetic model were used as process responses rather than the recovery of plastics in the separation products. To explain and illustrate the proposed methodology, a set of 32 experimental tests was performed using mixtures of two polymers with approximately the same density, PVC and PS (with mineral charges), with particle size ranging from 2 to 4 mm. The manipulated variables were frother concentration, air flow rate and pH. A three-level full factorial design was conducted. The models establishing the relationships between the manipulated variables and their interactions with the responses (first order kinetic model parameters) were built. The Corrected Akaike Information Criterion was used to select the best fit model and an analysis of variance (ANOVA) was conducted to identify the statistically significant terms of the model. It was shown that froth flotation can be used to efficiently separate PVC from PS with mineral charges by reducing the floatability of PVC, which largely depends on the action of pH. Within the tested interval, this is the factor that most affects the flotation rate constants. The results obtained show that the pure error may be of the same magnitude as the sum of squares of the errors, suggesting that there is significant variability within the same experimental conditions. Thus, special care is needed when evaluating and generalizing the process. Copyright © 2017 Elsevier Ltd. All rights reserved.

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.

Understanding Solvent Manipulation of Morphology in Bulk-Heterojunction Organic Solar Cells.

PubMed

Chen, Yuxia; Zhan, Chuanlang; Yao, Jiannian

2016-10-06

Film morphology greatly influences the performance of bulk-heterojunction (BHJ)-structure-based solar cells. It is known that an interpenetrating bicontinuous network with nanoscale-separated donor and acceptor phases for charge transfer, an ordered molecular packing for exciton diffusion and charge transport, and a vertical compositionally graded structure for charge collection are prerequisites for achieving highly efficient BHJ organic solar cells (OSCs). Therefore, control of the morphology to obtain an ideal structure is a key problem. For this solution-processing BHJ system, the solvent participates fully in film processing. Its involvement is critical in modifying the nanostructure of BHJ films. In this review, we discuss the effects of solvent-related methods on the morphology of BHJ films, including selection of the casting solvent, solvent mixture, solvent vapor annealing, and solvent soaking. On the basis of a discussion on interaction strength and time between solvent and active materials, we believe that the solvent-morphology-performance relationship will be clearer and that solvent selection as a means to manipulate the morphology of BHJ films will be more rational. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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.

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.

Cationic flocculants carrying hydrophobic functionalities: applications for solid/liquid separation.

PubMed

Schwarz, S; Jaeger, W; Paulke, B-R; Bratskaya, S; Smolka, N; Bohrisch, J

2007-07-26

The flocculation behaviors of three series of polycations with narrow molecular weight distributions carrying hydrophobic substituents on their backbones [poly(N-vinylbenzyl-N,N,N-trimethylammonium chloride), poly(N-vinylbenzyl-N,N-dimethyl-N-butylammonium chloride), and poly(N-vinylbenzylpyridinium chloride)] were investigated in dispersions of monodisperse polystyrene latexes and kaolin. Apparently, the charge density of the polycations decreases with increasing substituent hydrophobicity and increasing molecular weight of the polyelectrolytes. The necessary amount of flocculant for phase separation in dispersions with high substrate surface charge densities increases with increasing hydrophobicity of the polyelectrolyte. Nevertheless, the introduction of hydrophobic functionalities is beneficial, resulting in a substantial broadening of the range between the minimum and maximum amounts of flocculant necessary for efficient flocculation (flocculation window). An increase in ionic strength supports this effect. When the substrate has a low charge density, the hydrophobic interactions play a much more significant role in the flocculation process. Here, the minimum efficient doses remained the same for all three polyelectrolytes investigated, but the width of the flocculation window increased as the polycation hydrophobicity and the molecular weight increased. The necessary amount of flocculant increased with an increase in particle size at constant solid content of the dispersion, as well as with a decreasing number of particles at a constant particle size.

Cross-section measurement for quasi-elastic production of charmed baryons in νN interactions

NASA Astrophysics Data System (ADS)

Kayis-Topaksu, A.; Onengüt, G.; van Dantzig, R.; de Jong, M.; Melzer, O.; Oldeman, R. G. C.; Pesen, E.; Spada, F. R.; Visschers, J. L.; Güler, M.; Köse, U.; Serin-Zeyrek, M.; Sever, R.; Tolun, P.; Zeyrek, M. T.; Catanesi, M. G.; de Serio, M.; Ieva, M.; Muciaccia, M. T.; Radicioni, E.; Simone, S.; Bülte, A.; Winter, K.; van de Vyver, B.; Vilain, P.; Wilquet, G.; Pittoni, G. L.; Saitta, B.; di Capua, E.; Ogawa, S.; Shibuya, H.; Artamonov, A.; Chizhov, M.; Doucet, M.; Hristova, I. R.; Kawamura, T.; Kolev, D.; Meinhard, H.; Panman, J.; Papadopoulos, I. M.; Ricciardi, S.; Rozanov, A.; Tsenov, R.; Uiterwijk, J. W. E.; Zucchelli, P.; Goldberg, J.; Chikawa, M.; Arik, E.; Song, J. S.; Yoon, C. S.; Kodama, K.; Ushida, N.; Aoki, S.; Hara, T.; Delbar, T.; Favart, D.; Grégoire, G.; Kalinin, S.; Maklioueva, I.; Gorbunov, P.; Khovansky, V.; Shamanov, V.; Tsukerman, I.; Bruski, N.; Frekers, D.; Hoshino, K.; Kawada, J.; Komatsu, M.; Miyanishi, M.; Nakamura, M.; Nakano, T.; Narita, K.; Niu, K.; Niwa, K.; Nonaka, N.; Sato, O.; Toshito, T.; Buontempo, S.; Cocco, A. G.; D'Ambrosio, N.; de Lellis, G.; De Rosa, G.; di Capua, F.; Ereditato, A.; Fiorillo, G.; Marotta, A.; Messina, M.; Migliozzi, P.; Pistillo, C.; Scotto Lavina, L.; Strolin, P.; Tioukov, V.; Nakamura, K.; Okusawa, T.; Dore, U.; Loverre, P. F.; Ludovici, L.; Righini, P.; Rosa, G.; Santacesaria, R.; Satta, A.; Barbuto, E.; Bozza, C.; Grella, G.; Romano, G.; Sirignano, C.; Sorrentino, S.; Sato, Y.; Tezuka, I.; CHORUS Collaboration

2003-11-01

A study of quasi-elastic production of charmed baryons in charged-current interactions of neutrinos with the nuclear emulsion target of CHORUS is presented. In a sample of about 46 000 interactions located in the emulsion, candidates for decays of short-lived particles were identified by using new automatic scanning systems and later confirmed through visual inspection. Criteria based both on the topological and kinematical characteristics of quasi-elastic charm production allowed a clear separation between events of this type and those in which charm is produced in deep inelastic processes. A final sample containing 13 candidates consistent with quasi-elastic production of a charmed baryon with an estimated background of 1.7 events was obtained. At the average neutrino energy of 27 GeV the cross-section for the total quasi-elastic production of charmed baryons relative to the νN charged-current cross-section was measured to be σ(QE)/σ(CC)=(0.23+0.12-0.06(stat)+0.02-0.03(syst))×10-2. Through an analysis of the topology at the production and decay vertices the relative cross-sections were measured separately for singly (Λc+,Σc+,Σc+∗) and doubly (Σc++,Σc++∗) charged baryons.

CdSe quantum dot-fullerene hybrid nanocomposite for solar energy conversion: electron transfer and photoelectrochemistry.

PubMed

Bang, Jin Ho; Kamat, Prashant V

2011-12-27

The development of organic/inorganic hybrid nanocomposite systems that enable efficient solar energy conversion has been important for applications in solar cell research. Nanostructured carbon-based systems, in particular C(60), offer attractive strategies to collect and transport electrons generated in a light harvesting assembly. We have assembled CdSe-C(60) nanocomposites by chemically linking CdSe quantum dots (QDs) with thiol-functionalized C(60). The photoinduced charge separation and collection of electrons in CdSe QD-C(60) nanocomposites have been evaluated using transient absorption spectroscopy and photoelectrochemical measurements. The rate constant for electron transfer between excited CdSe QD and C(60) increased with the decreasing size of the CdSe QD (7.9 × 10(9) s(-1) (4.5 nm), 1.7 × 10(10) s(-1) (3.2 nm), and 9.0 × 10(10) s(-1) (2.6 nm)). Slower hole transfer and faster charge recombination and transport events were found to dominate over the forward electron injection process, thus limiting the deliverance of maximum power in CdSe QD-C(60)-based solar cells. The photoinduced charge separation between CdSe QDs and C(60) opens up new design strategies for developing light harvesting assemblies.

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.

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.

Super NiCd Open-Circuit Storage and Low Earth Orbit (LEO) Life Test Evaluation

NASA Technical Reports Server (NTRS)

Baer, Jean Marie; Hwang, Warren C.; Ang, Valerie J.; Hayden, Jeff; Rao, Gopalakrishna; Day, John H. (Technical Monitor)

2002-01-01

This presentation discusses Air Force tests performed on super NiCd cells to measure their performance under conditions simulating Low Earth Orbit (LEO) conditions. Super NiCd cells offer potential advantages over existing NiCd cell designs including advanced cell design with improved separator material and electrode making processes, but handling and storage requires active charging. These tests conclude that the super NiCd cells support generic Air Force qualifications for conventional LEO missions (up to five years duration) and that handling and storage may not actually require active charging as previously assumed. Topics covered include: Test Plan, Initial Characterization Tests, Open-Circuit Storage Tests, and post storage capacities.

Electron beam influence on the carbon contamination of electron irradiated hydroxyapatite thin films

NASA Astrophysics Data System (ADS)

Hristu, Radu; Stanciu, Stefan G.; Tranca, Denis E.; Stanciu, George A.

2015-08-01

Electron beam irradiation which is considered a reliable method for tailoring the surface charge of hydroxyapatite is hindered by carbon contamination. Separating the effects of the carbon contamination from those of irradiation-induced trapped charge is important for a wide range of biological applications. In this work we focus on the understanding of the electron-beam-induced carbon contamination with special emphasis on the influence of the electron irradiation parameters on this phenomenon. Phase imaging in atomic force microscopy is used to evaluate the influence of electron energy, beam current and irradiation time on the shape and size of the resulted contamination patterns. Different processes involved in the carbon contamination of hydroxyapatite are discussed.

Double heterojunction nanowire photocatalysts for hydrogen generation

NASA Astrophysics Data System (ADS)

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

2014-03-01

Charge separation and charge transfer across interfaces are key aspects in the design of efficient photocatalysts for solar energy conversion. In this study, we investigate the hydrogen generating capabilities and underlying photophysics of nanostructured photocatalysts based on CdSe nanowires (NWs). Systems studied include CdSe, CdSe/CdS core/shell nanowires and their Pt nanoparticle-decorated counterparts. Femtosecond transient differential absorption measurements reveal how semiconductor/semiconductor and metal/semiconductor heterojunctions affect the charge separation and hydrogen generation efficiencies of these hybrid photocatalysts. In turn, we unravel the role of surface passivation, charge separation at semiconductor interfaces and charge transfer to metal co-catalysts in determining photocatalytic H2 generation efficiencies. This allows us to rationalize why Pt nanoparticle decorated CdSe/CdS NWs, a double heterojunction system, performs best with H2 generation rates of ~434.29 +/- 27.40 μmol h-1 g-1 under UV/Visible irradiation. In particular, we conclude that the CdS shell of this double heterojunction system serves two purposes. The first is to passivate CdSe NW surface defects, leading to long-lived charges at the CdSe/CdS interface capable of carrying out reduction chemistries. Upon photoexcitation, we also find that CdS selectively injects charges into Pt NPs, enabling simultaneous reduction chemistries at the Pt NP/solvent interface. Pt nanoparticle decorated CdSe/CdS NWs thus enable reduction chemistries at not one, but rather two interfaces, taking advantage of each junction's optimal catalytic activities.Charge separation and charge transfer across interfaces are key aspects in the design of efficient photocatalysts for solar energy conversion. In this study, we investigate the hydrogen generating capabilities and underlying photophysics of nanostructured photocatalysts based on CdSe nanowires (NWs). Systems studied include CdSe, CdSe/CdS core/shell nanowires and their Pt nanoparticle-decorated counterparts. Femtosecond transient differential absorption measurements reveal how semiconductor/semiconductor and metal/semiconductor heterojunctions affect the charge separation and hydrogen generation efficiencies of these hybrid photocatalysts. In turn, we unravel the role of surface passivation, charge separation at semiconductor interfaces and charge transfer to metal co-catalysts in determining photocatalytic H2 generation efficiencies. This allows us to rationalize why Pt nanoparticle decorated CdSe/CdS NWs, a double heterojunction system, performs best with H2 generation rates of ~434.29 +/- 27.40 μmol h-1 g-1 under UV/Visible irradiation. In particular, we conclude that the CdS shell of this double heterojunction system serves two purposes. The first is to passivate CdSe NW surface defects, leading to long-lived charges at the CdSe/CdS interface capable of carrying out reduction chemistries. Upon photoexcitation, we also find that CdS selectively injects charges into Pt NPs, enabling simultaneous reduction chemistries at the Pt NP/solvent interface. Pt nanoparticle decorated CdSe/CdS NWs thus enable reduction chemistries at not one, but rather two interfaces, taking advantage of each junction's optimal catalytic activities. Electronic supplementary information (ESI) available: Details of NW syntheses, processing and characterization. Additional TEM images of CdS, CdSe and CdSe/CdS core/shell NWs. NW concentration and cross section estimates. Details of the Pt NP decoration. Additional TEM images of Pt NP decorated CdS, CdSe and CdSe/CdS core/shell NWs. Size distribution of Pt NPs for CdSe/Pt NP and CdSe/CdS/Pt NP NWs. Xe arc lamp spectrum. Details of H2 generation experiments. Estimated photon absorption rate. Details of TDA measurements. TDA spectra and kinetics of CdS and CdS/Pt NP NWs. Plot illustrating CdSe NW band edge bleach kinetics. Comparison of CdSe band edge bleach kinetics in CdSe/CdS core/shell NWs when excited at λexc = 387 nm and λexc = 560 nm. Comparison of CdSe band edge bleach kinetics in CdSe/Pt NP NWs when excited at λexc = 387 nm and λexc = 560 nm. Bar graph showing H2 generation efficiencies of CdS and CdS/Pt NP NWs. Bleach kinetics of CdSe/CdS/Pt NP NWs at λexc = 387 nm and λexc = 560 nm. Comparison of CdS band edge bleach kinetics in CdS/Pt NP, and CdSe/CdS core/shell NWs when excited at λexc = 387 nm. See DOI: 10.1039/c4nr00298a

Solution-Processed Wide-Bandgap Organic Semiconductor Nanostructures Arrays for Nonvolatile Organic Field-Effect Transistor Memory.

PubMed

Li, Wen; Guo, Fengning; Ling, Haifeng; Liu, Hui; Yi, Mingdong; Zhang, Peng; Wang, Wenjun; Xie, Linghai; Huang, Wei

2018-01-01

In this paper, the development of organic field-effect transistor (OFET) memory device based on isolated and ordered nanostructures (NSs) arrays of wide-bandgap (WBG) small-molecule organic semiconductor material [2-(9-(4-(octyloxy)phenyl)-9H-fluoren-2-yl)thiophene]3 (WG 3 ) is reported. The WG 3 NSs are prepared from phase separation by spin-coating blend solutions of WG 3 /trimethylolpropane (TMP), and then introduced as charge storage elements for nonvolatile OFET memory devices. Compared to the OFET memory device with smooth WG 3 film, the device based on WG 3 NSs arrays exhibits significant improvements in memory performance including larger memory window (≈45 V), faster switching speed (≈1 s), stable retention capability (>10 4 s), and reliable switching properties. A quantitative study of the WG 3 NSs morphology reveals that enhanced memory performance is attributed to the improved charge trapping/charge-exciton annihilation efficiency induced by increased contact area between the WG 3 NSs and pentacene layer. This versatile solution-processing approach to preparing WG 3 NSs arrays as charge trapping sites allows for fabrication of high-performance nonvolatile OFET memory devices, which could be applicable to a wide range of WBG organic semiconductor materials. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hot Charge Carrier Transmission from Plasmonic Nanostructures

NASA Astrophysics Data System (ADS)

Christopher, Phillip; Moskovits, Martin

2017-05-01

Surface plasmons have recently been harnessed to carry out processes such as photovoltaic current generation, redox photochemistry, photocatalysis, and photodetection, all of which are enabled by separating energetic (hot) electrons and holes—processes that, previously, were the domain of semiconductor junctions. Currently, the power conversion efficiencies of systems using plasmon excitation are low. However, the very large electron/hole per photon quantum efficiencies observed for plasmonic devices fan the hope of future improvements through a deeper understanding of the processes involved and through better device engineering, especially of critical interfaces such as those between metallic and semiconducting nanophases (or adsorbed molecules). In this review, we focus on the physics and dynamics governing plasmon-derived hot charge carrier transfer across, and the electronic structure at, metal-semiconductor (molecule) interfaces, where we feel the barriers contributing to low efficiencies reside. We suggest some areas of opportunity that deserve early attention in the still-evolving field of hot carrier transmission from plasmonic nanostructures to neighboring phases.

Prevention of redox shuttle using electropolymerized polypyrrole film in a lithium-oxygen battery

NASA Astrophysics Data System (ADS)

Togasaki, Norihiro; Shibamura, Ryuji; Naruse, Takuya; Momma, Toshiyuki; Osaka, Tetsuya

2018-04-01

Among the recent advancements in lithium-oxygen (Li-O2) chemistries, redox mediators (RMs) have been revealed to play a significant role in decreasing overpotential on charging and in improving cycling performance. However, an intrinsic problem is redox shuttle of RMs, which leads to degraded RM utilization and induces the accumulation of discharge products on the cathode surface; this remains a significant issue in the current battery cell configuration (Li anode/separator/cathode). To address this detrimental problem, herein we propose a novel Li-O2 cell incorporating a freestanding electropolymerized polypyrrole (PPy) film for the restriction of the redox-shuttle phenomenon of lithium iodide (Li anode/separator/PPy film/cathode). In this study, a PPy film, which is prepared through oxidative electropolymerization using an ionic liquid of 1-methyl-1-butylpyrrolidinium mixed with pyrrole and lithium bis(trifluoromethanesulfonyl)imide, is introduced between the cathode and the separator. From the charge-discharge voltage profile, it is confirmed that the PPy film suppresses the diffusion of the oxidized I3- to the Li anode, while allowing Li ion transport. Secondary scanning electron microscope measurements confirm that the chemical reactions between I3- and Li2O2 are facilitated by the presence of the PPy film because I3- remains near the cathode surface during the charging process. As a result, the cycling performance in the Li-O2 cells with PPy film exhibits a cycling life four times as long as that of the Li-O2 cells without PPy film.

Angle-dependent strong-field molecular ionization rates with tuned range-separated time-dependent density functional theory.

PubMed

Sissay, Adonay; Abanador, Paul; Mauger, François; Gaarde, Mette; Schafer, Kenneth J; Lopata, Kenneth

2016-09-07

Strong-field ionization and the resulting electronic dynamics are important for a range of processes such as high harmonic generation, photodamage, charge resonance enhanced ionization, and ionization-triggered charge migration. Modeling ionization dynamics in molecular systems from first-principles can be challenging due to the large spatial extent of the wavefunction which stresses the accuracy of basis sets, and the intense fields which require non-perturbative time-dependent electronic structure methods. In this paper, we develop a time-dependent density functional theory approach which uses a Gaussian-type orbital (GTO) basis set to capture strong-field ionization rates and dynamics in atoms and small molecules. This involves propagating the electronic density matrix in time with a time-dependent laser potential and a spatial non-Hermitian complex absorbing potential which is projected onto an atom-centered basis set to remove ionized charge from the simulation. For the density functional theory (DFT) functional we use a tuned range-separated functional LC-PBE*, which has the correct asymptotic 1/r form of the potential and a reduced delocalization error compared to traditional DFT functionals. Ionization rates are computed for hydrogen, molecular nitrogen, and iodoacetylene under various field frequencies, intensities, and polarizations (angle-dependent ionization), and the results are shown to quantitatively agree with time-dependent Schrödinger equation and strong-field approximation calculations. This tuned DFT with GTO method opens the door to predictive all-electron time-dependent density functional theory simulations of ionization and ionization-triggered dynamics in molecular systems using tuned range-separated hybrid functionals.

Angle-dependent strong-field molecular ionization rates with tuned range-separated time-dependent density functional theory

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

Sissay, Adonay; Abanador, Paul; Mauger, François

2016-09-07

Strong-field ionization and the resulting electronic dynamics are important for a range of processes such as high harmonic generation, photodamage, charge resonance enhanced ionization, and ionization-triggered charge migration. Modeling ionization dynamics in molecular systems from first-principles can be challenging due to the large spatial extent of the wavefunction which stresses the accuracy of basis sets, and the intense fields which require non-perturbative time-dependent electronic structure methods. In this paper, we develop a time-dependent density functional theory approach which uses a Gaussian-type orbital (GTO) basis set to capture strong-field ionization rates and dynamics in atoms and small molecules. This involves propagatingmore » the electronic density matrix in time with a time-dependent laser potential and a spatial non-Hermitian complex absorbing potential which is projected onto an atom-centered basis set to remove ionized charge from the simulation. For the density functional theory (DFT) functional we use a tuned range-separated functional LC-PBE*, which has the correct asymptotic 1/r form of the potential and a reduced delocalization error compared to traditional DFT functionals. Ionization rates are computed for hydrogen, molecular nitrogen, and iodoacetylene under various field frequencies, intensities, and polarizations (angle-dependent ionization), and the results are shown to quantitatively agree with time-dependent Schrödinger equation and strong-field approximation calculations. This tuned DFT with GTO method opens the door to predictive all-electron time-dependent density functional theory simulations of ionization and ionization-triggered dynamics in molecular systems using tuned range-separated hybrid functionals.« less

Borophene as a Promising Material for Charge-Modulated Switchable CO2 Capture.

PubMed

Tan, Xin; Tahini, Hassan A; Smith, Sean C

2017-06-14

Ideal carbon dioxide (CO 2 ) capture materials for practical applications should bind CO 2 molecules neither too weakly to limit good loading kinetics nor too strongly to limit facile release. Although charge-modulated switchable CO 2 capture has been proposed to be a controllable, highly selective, and reversible CO 2 capture strategy, the development of a practical gas-adsorbent material remains a great challenge. In this study, by means of density functional theory (DFT) calculations, we have examined the possibility of conductive borophene nanosheets as promising sorbent materials for charge-modulated switchable CO 2 capture. Our results reveal that the binding strength of CO 2 molecules on negatively charged borophene can be significantly enhanced by injecting extra electrons into the adsorbent. At saturation CO 2 capture coverage, the negatively charged borophene achieves CO 2 capture capacities up to 6.73 × 10 14 cm -2 . In contrast to the other CO 2 capture methods, the CO 2 capture/release processes on negatively charged borophene are reversible with fast kinetics and can be easily controlled via switching on/off the charges carried by borophene nanosheets. Moreover, these negatively charged borophene nanosheets are highly selective for separating CO 2 from mixtures with CH 4 , H 2 , and/or N 2 . This theoretical exploration will provide helpful guidance for identifying experimentally feasible, controllable, highly selective, and high-capacity CO 2 capture materials with ideal thermodynamics and reversibility.

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

Enhanced Solar Cell Conversion Efficiency of InGaN/GaN Multiple Quantum Wells by Piezo-Phototronic Effect.

PubMed

Jiang, Chunyan; Jing, Liang; Huang, Xin; Liu, Mengmeng; Du, Chunhua; Liu, Ting; Pu, Xiong; Hu, Weiguo; Wang, Zhong Lin

2017-09-26

The piezo-phototronic effect is the tuning of piezoelectric polarization charges at the interface to largely enhance the efficiency of optoelectronic processes related to carrier separation or recombination. Here, we demonstrated the enhanced short-circuit current density and the conversion efficiency of InGaN/GaN multiple quantum well solar cells with an external stress applied on the device. The external-stress-induced piezoelectric charges generated at the interfaces of InGaN and GaN compensate the piezoelectric charges induced by lattice mismatch stress in the InGaN wells. The energy band realignment is calculated with a self-consistent numerical model to clarify the enhancement mechanism of optical-generated carriers. This research not only theoretically and experimentally proves the piezo-phototronic effect modulated the quantum photovoltaic device but also provides a great promise to maximize the use of solar energy in the current energy revolution.

A Nonmetal Plasmonic Z-Scheme Photocatalyst with UV- to NIR-Driven Photocatalytic Protons Reduction.

PubMed

Zhang, Zhenyi; Huang, Jindou; Fang, Yurui; Zhang, Mingyi; Liu, Kuichao; Dong, Bin

2017-05-01

Ultrabroad-spectrum absorption and highly efficient generation of available charge carriers are two essential requirements for promising semiconductor-based photocatalysts, towards achieving the ultimate goal of solar-to-fuel conversion. Here, a fascinating nonmetal plasmonic Z-scheme photocatalyst with the W 18 O 49 /g-C 3 N 4 heterostructure is reported, which can effectively harvest photon energies spanning from the UV to the nearinfrared region and simultaneously possesses improved charge-carrier dynamics to boost the generation of long-lived active electrons for the photocatalytic reduction of protons into H 2 . By combining with theoretical simulations, a unique synergistic photocatalysis effect between the semiconductive Z-scheme charge-carrier separation and metal-like localized-surface-plasmon-resonance-induced "hot electrons" injection process is demonstrated within this binary heterostructure. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrification of Shaken Granular Flows as a Model of Natural Storm Charging

NASA Astrophysics Data System (ADS)

Kara, O.; Nordsiek, F.; Lathrop, D. P.

2015-12-01

The charging of particulates in nature is widespread and observed in thunderstorms, volcanic ash clouds, thunder-snow, and dust storms. However the mechanism of charge separation at large (> 1km) scale is poorly understood. We perform simple laboratory experiments to better understand the collective phenomena involved in granular electrification. We confine granular particles in an oscillating cylindrical chamber which is enclosed and sealed by two conducting plates. The primary measurement is the voltage difference between the two plates. We find that collective effects occurring in the bulk of the material play a significant role in the electrification process. We extend that by addition of photodetection capabilities to the experimental chamber to detect electrical discharges between the particles and each other and the plates. We present measurements of electrical discharges in addition to the slower dynamics of voltage variation in the system.

Effects of Coulomb Repulsion on the Phase Diagram of the Asakura-Oosawa Model

NASA Astrophysics Data System (ADS)

Haaga, Jason; Pemberton, Elizabeth; Gunton, James; Rickman, Jeffrey

We investigate the effect of adding a screened Coulomb charge to a model colloidal system interacting via the Asakura-Oosawa depletion potential. This model has previously been used to study the early stages of amelogenin self-assembly, a crucial process in the formation of dental enamel, by Li et al (BiophysicalJournal 101, 2502 (2011). By employing Monte Carlo simulations, we explore the role of interaction strengths and ranges on phase behavior. We find that charge strength and range have a strong influence on the stable, in the case of long range depletion potential, or metastable, in the case of short range depletion, fluid-fluid phase separation. Coulomb repulsion narrows and flattens the coexistence curve with increasing charge. This talk will also discuss solid-solid transitions present for certain interaction ranges. This work is supported by the G. Harold and Leila Y. Mathers Foundation.

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.

Macroparticle separation and plasma collimation in positively biased ducts in filtered vacuum arc deposition systems

NASA Astrophysics Data System (ADS)

Beilis, I. I.; Keidar, M.; Boxman, R. L.; Goldsmith, S.

1999-02-01

The objective of the present work was to determine the influence of positive bias on plasma and macroparticle (MP) flow in curved magnetized plasma ducts. The plasma bulk and sheath regions were analyzed. In the plasma bulk, the current density and electrical field component normal to the wall were obtained and used as boundary conditions for the near wall sheath region. In the sheath, a nonstationary model for MP charging and motion was developed. The solution of the hydrodynamic equations in the plasma when a positive bias is applied to the wall result in a radial electrical current. The electric field in the plasma bulk is generated by the separation between the magnetically confined electrons, and the ions, which are thrown outwards by the centrifugal force. The field increases with increasing positive bias. It was shown that MPs traveling in the sheath accumulate a charge which depends on the potential distribution, in contrast to MP charging in the quasineutral plasma where the charge depends on plasma density and electron temperature. MP trapping in the near-wall sheath was found. MPs may move in the sheath region along the wall by a repetitive process of electrostatic attraction to the wall, mechanical reflection and neutralization, followed by MP charging and attraction, etc. For example, titanium MPs with a radius less than 0.4 μm and with a velocity component normal to the wall of about 20 m/s are trapped if the sheath potential drop exceeds 20 V. It was obtained that the MP transmission fraction through filter decreases by more than few orders of magnitude due to the trapping effect when a bias potential of +100 V is applied between the wall and the plasma.

Physical aspects of ferroelectric semiconductors for photovoltaic solar energy conversion

NASA Astrophysics Data System (ADS)

Lopez-Varo, Pilar; Bertoluzzi, Luca; Bisquert, Juan; Alexe, Marin; Coll, Mariona; Huang, Jinsong; Jimenez-Tejada, Juan Antonio; Kirchartz, Thomas; Nechache, Riad; Rosei, Federico; Yuan, Yongbo

2016-10-01

Solar energy conversion using semiconductors to fabricate photovoltaic devices relies on efficient light absorption, charge separation of electron-hole pair carriers or excitons, and fast transport and charge extraction to counter recombination processes. Ferroelectric materials are able to host a permanent electrical polarization which provides control over electrical field distribution in bulk and interfacial regions. In this review, we provide a critical overview of the physical principles and mechanisms of solar energy conversion using ferroelectric semiconductors and contact layers, as well as the main achievements reported so far. In a ferroelectric semiconductor film with ideal contacts, the polarization charge would be totally screened by the metal layers and no charge collection field would exist. However, real materials show a depolarization field, smooth termination of polarization, and interfacial energy barriers that do provide the control of interface and bulk electric field by switchable spontaneous polarization. We explore different phenomena as the polarization-modulated Schottky-like barriers at metal/ferroelectric interfaces, depolarization fields, vacancy migration, and the switchable rectifying behavior of ferroelectric thin films. Using a basic physical model of a solar cell, our analysis provides a general picture of the influence of ferroelectric effects on the actual power conversion efficiency of the solar cell device, and we are able to assess whether these effects or their combinations are beneficial or counterproductive. We describe in detail the bulk photovoltaic effect and the contact layers that modify the built-in field and the charge injection and separation in bulk heterojunction organic cells as well as in photocatalytic and water splitting devices. We also review the dominant families of ferroelectric materials that have been most extensively investigated and have provided the best photovoltaic performance.

Assessment and Control of Spacecraft Charging Risks on the International Space Station

NASA Technical Reports Server (NTRS)

Koontz, Steve; Edeen, Marybeth; Spetch, William; Dalton, Penni; Keening, Thomas

2003-01-01

Electrical interactions between the F2 region ionospheric plasma and the 160V photovoltaic (PV) electrical power system on the International Space Station (ISS) can produce floating potentials (FP) on the ISS conducting structure of greater magnitude than are usually observed on spacecraft in low-Earth orbit. Flight through the geomagnetic field also causes magnetic induction charging of ISS conducting structure. Charging processes resulting from interaction of ISS with auroral electrons may also contribute to charging albeit rarely. The magnitude and frequency of occurrence of possibly hazardous charging events depends on the ISS assembly stage (six more 160V PV arrays will be added to ISS), ISS flight configuration, ISS position (latitude and longitude), and the natural variability in the ionospheric flight environment. At present, ISS is equipped with two plasma contactors designed to control ISS FP to within 40 volts of the ambient F2 plasma. The negative-polarity grounding scheme utilized in the ISS 160V power system leads, naturally, to negative values of ISS FP. A negative ISS structural FP leads to application of electrostatic fields across the dielectrics that separate conducting structure from the ambient F2 plasma, thereby enabling dielectric breakdown and arcing. Degradation of some thermal control coatings and noise in electrical systems can result. Continued review and evaluation of the putative charging hazards, as required by the ISS Program Office, revealed that ISS charging could produce a risk of electric shock to the ISS crew during extra vehicular activity. ISS charging risks are being evaluated in ongoing ISS charging measurements and analysis campaigns. The results of ISS charging measurements are combined with a recently developed detailed model of the ISS charging process and an extensive analysis of historical ionospheric variability data, to assess ISS charging risks using Probabilistic Risk Assessment (PRA) methods. The PRA analysis (estimated frequency of occurrence and severity of the charging hazards) are then used to select the hazard control strategy that provides the best overall safety and mission success environment for ISS and the ISS crew. This paper presents: 1) a summary of ISS spacecraft charging analysis, measurements, observations made to date, 2) plans for future ISS spacecraft charging measurement campaigns, and 3) a detailed discussion of the PRA strategy used to assess ISS spacecraft charging risks and select charging hazard control strategies

Assessment and Control of International Space Station Spacecraft Charging Risks

NASA Astrophysics Data System (ADS)

Koontz, S.; Edeen, M.; Spetch, W.; Dalton, P.; Keeping, T.; Minow, J.

2003-12-01

Electrical interactions between the F2 region ionospheric plasma and the 160V photovoltaic (PV) electrical power system on the International Space Station (ISS) can produce floating potentials (FP) on ISS conducting structure of greater magnitude than are usually observed on spacecraft in low-Earth orbit. Flight through the geomagnetic field also causes magnetic induction charging of ISS conducting structure. Charging processes resulting from interaction of ISS with auroral electrons may also contribute to charging, albeit rarely. The magnitude and frequency of occurrence of possibly hazardous charging events depends on the ISS assembly stage (six more 160V PV arrays will be added to ISS), ISS flight configuration, ISS position (latitude and longitude), and the natural variability in the ionospheric flight environment. At present, ISS is equipped with two plasma contactors designed to control ISS FP to within 40 volts of the ambient F2 plasma. The negative-polarity grounding scheme utilized in the ISS 160V power system leads, naturally, to negative values of ISS FP. A negative ISS structural FP leads to application of electrostatic fields across the dielectrics that separate conducting structure from the ambient F2 plasma, thereby enabling dielectric breakdown and arcing. Degradation of some thermal control coatings and noise in electrical systems can result. Continued review and evaluation of the putative charging hazards, as required by the ISS Program Office, revealed that ISS charging could produce a risk of electric shock to the ISS crew during extra vehicular activity. ISS charging risks are being evaluated in ongoing ISS charging measurements and analysis campaigns. The results of ISS charging measurements are combined with a recently developed detailed model of the ISS charging process and an extensive analysis of historical ionospheric variability data, to assess ISS charging risks using Probabilistic Risk Assessment (PRA) methods. The PRA analysis (estimated frequency of occurrence and severity of the charging hazards) are then used to select the hazard control strategy that provides the best overall safety and mission success environment for ISS and the ISS crew. This paper presents: 1) a summary of ISS spacecraft charging analysis, measurements, observations made to date, 2) plans for future ISS spacecraft charging measurement campaigns, and 3) a detailed discussion of the PRA strategy used to assess ISS spacecraft charging risks and select charging hazard control strategies.

Defining Protein Electrostatic Recognition Processes

DTIC Science & Technology

1989-11-30

of the electrostatic potentiai on the molecular surface of negatively charged Asp-101 in the fifth residue of JH1. the hapten and the V regions of...making and aligning expanded molecular dot surfaces for each molecule and checking these surfaces for interpenetration. The program TURNIP used these...the molecular surfaces are separated by 6 and 12A. All orientations have the exposed heme edge of cytochrome c facing the acidic patch of plastocyanin

International Aerospace and Ground Conference on Lightning and Static Electricity Held in Dayton, Ohio on 24-26 June 1986

DTIC Science & Technology

1986-10-01

developed by the AEH Group has the advantages: of compactness which makes it easily transportable; computer controlled acquisi- tion, signal processing...be available to a negatively charged aircraft. The experimental arrangement attempts to simulate the streamer propagation and growth in a quasi ...separate foam configurations: the operational configuration of non - conductive foam and a second configuration which contained an experimental

CMOS serial link for fully duplexed data communication

NASA Astrophysics Data System (ADS)

Lee, Kyeongho; Kim, Sungjoon; Ahn, Gijung; Jeong, Deog-Kyoon

1995-04-01

This paper describes a CMOS serial link allowing fully duplexed 500 Mbaud serial data communication. The CMOS serial link is a robust and low-cost solution to high data rate requirements. A central charge pump PLL for generating multiphase clocks for oversampling is shared by several serial link channels. Fully duplexed serial data communication is realized in the bidirectional bridge by separating incoming data from the mixed signal on the cable end. The digital PLL accomplishes process-independent data recovery by using a low-ratio oversampling, a majority voting, and a parallel data recovery scheme. Mostly, digital approach could extend its bandwidth further with scaled CMOS technology. A single channel serial link and a charge pump PLL are integrated in a test chip using 1.2 micron CMOS process technology. The test chip confirms upto 500 Mbaud unidirectional mode operation and 320 Mbaud fully duplexed mode operation with pseudo random data patterns.

Polymeric efficiency in remove impurities during cottonseed biodiesel production

NASA Astrophysics Data System (ADS)

Lin, H. L.; Liang, Y. H.; Yan, J.; Lin, H. D.; Espinosa, A. R.

2016-07-01

This paper describes a new process for developing biodiesel by polymer from crude cottonseed oil. The study was conducted to examine the effectiveness of the alkali transesterification-flocculation-sedimentation process on fast glycerol and other impurities in the separation from biodiesel by using quaternary polyamine-based cationic polymers SL2700 and polyacylamide cationic polymer SAL1100. The settling velocity of glycerol and other impurities in biodiesel was investigated through settling test experiments; the quality of the biodiesel was investigated by evaluating the viscosity and density. The results revealed that SL2700, SAL1100 and their combination dramatically improved the settling velocity of glycerol and other impurities materials than traditional method. SL 2700 with molecular weight of 0.2 million Da and charge density of 50% then plus SAL1100 with molecular weight of 11 million Da and charge density of 10% induced observable particle aggregation with the best settling performance.

Fluorination-enabled optimal morphology leads to over 11% efficiency for inverted small-molecule organic solar cells

PubMed Central

Deng, Dan; Zhang, Yajie; Zhang, Jianqi; Wang, Zaiyu; Zhu, Lingyun; Fang, Jin; Xia, Benzheng; Wang, Zhen; Lu, Kun; Ma, Wei; Wei, Zhixiang

2016-01-01

Solution-processable small molecules for organic solar cells have attracted intense attention for their advantages of definite molecular structures compared with their polymer counterparts. However, the device efficiencies based on small molecules are still lower than those of polymers, especially for inverted devices, the highest efficiency of which is <9%. Here we report three novel solution-processable small molecules, which contain π-bridges with gradient-decreased electron density and end acceptors substituted with various fluorine atoms (0F, 1F and 2F, respectively). Fluorination leads to an optimal active layer morphology, including an enhanced domain purity, the formation of hierarchical domain size and a directional vertical phase gradation. The optimal morphology balances charge separation and transfer, and facilitates charge collection. As a consequence, fluorinated molecules exhibit excellent inverted device performance, and an average power conversion efficiency of 11.08% is achieved for a two-fluorine atom substituted molecule. PMID:27991486

Can the Dielectric Constant of Fullerene Derivatives Be Enhanced by Side-Chain Manipulation? A Predictive First-Principles Computational Study.

PubMed

Sami, Selim; Haase, Pi A B; Alessandri, Riccardo; Broer, Ria; Havenith, Remco W A

2018-04-19

The low efficiency of organic photovoltaic (OPV) devices has often been attributed to the strong Coulombic interactions between the electron and hole, impeding the charge separation process. Recently, it has been argued that by increasing the dielectric constant of materials used in OPVs, this strong interaction could be screened. In this work, we report the application of periodic density functional theory together with the coupled perturbed Kohn-Sham method to calculate the electronic contribution to the dielectric constant for fullerene C 60 derivatives, a ubiquitous class of molecules in the field of OPVs. The results show good agreement with experimental data when available and also reveal an important undesirable outcome when manipulating the side chain to maximize the static dielectric constant: in all cases, the electronic contribution to the dielectric constant decreases as the side chain increases in size. This information should encourage both theoreticians and experimentalists to further investigate the relevance of contributions to the dielectric constant from slower processes like vibrations and dipolar reorientations for facilitating the charge separation, because electronically, enlarging the side chain of conventional fullerene derivatives only lowers the dielectric constant, and consequently, their electronic dielectric constant is upper bound by the one of C 60 .

Can the Dielectric Constant of Fullerene Derivatives Be Enhanced by Side-Chain Manipulation? A Predictive First-Principles Computational Study

PubMed Central

2018-01-01

The low efficiency of organic photovoltaic (OPV) devices has often been attributed to the strong Coulombic interactions between the electron and hole, impeding the charge separation process. Recently, it has been argued that by increasing the dielectric constant of materials used in OPVs, this strong interaction could be screened. In this work, we report the application of periodic density functional theory together with the coupled perturbed Kohn–Sham method to calculate the electronic contribution to the dielectric constant for fullerene C60 derivatives, a ubiquitous class of molecules in the field of OPVs. The results show good agreement with experimental data when available and also reveal an important undesirable outcome when manipulating the side chain to maximize the static dielectric constant: in all cases, the electronic contribution to the dielectric constant decreases as the side chain increases in size. This information should encourage both theoreticians and experimentalists to further investigate the relevance of contributions to the dielectric constant from slower processes like vibrations and dipolar reorientations for facilitating the charge separation, because electronically, enlarging the side chain of conventional fullerene derivatives only lowers the dielectric constant, and consequently, their electronic dielectric constant is upper bound by the one of C60. PMID:29561616

Room-temperature preparation of trisilver-copper-sulfide/polymer based heterojunction thin film for solar cell application

NASA Astrophysics Data System (ADS)

Lei, Yan; Yang, Xiaogang; Gu, Longyan; Jia, Huimin; Ge, Suxiang; Xiao, Pin; Fan, Xiaoli; Zheng, Zhi

2015-04-01

Solar cells devices based on inorganic/polymer heterojunction can be a possible solution to harvest solar energy and convert to electric energy with high efficiency through a cost-effective fabrication. The solution-process method can be easily used to produce large area devices. Moreover, due to the intrinsic different charge separation, diffusion or recombination in various semiconductors, the interfaces between each component may strongly influence the inorganic/polymer heterojunction performance. Here we prepared a n-type Ag3CuS2 (Eg = 1.25 eV) nanostructured film through a room-temperature element reaction process, which was confirmed as direct bandgap semiconductor through density function theory simulation. This Ag3CuS2 film was spin-coated with an organic semiconducting poly(3-hexythiophene) (P3HT) or polythieno[3,4-b]-thiophene-co-benzodithiophene (PTB7) film, which formed an inorganic/polymer heterojunction. After constructing it to a solar cell device, the power conversion efficiencies of 0.79% and 0.31% were achieved with simulated solar illumination on Ag3CuS2/P3HT and Ag3CuS2/PTB7, respectively. A possible mechanism was discussed and we showed the charge separation at interface of inorganic and polymer semiconductors played an important role.

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

Novel Materials, Processing and Device Technologies for Space Exploration with Potential Dual-Use Applications

NASA Technical Reports Server (NTRS)

Hepp, A. F.; Bailey, S. G.; McNatt, J. S.; Chandrashekhar, M. V. S.; Harris, J. D.; Rusch, A. W.; Nogales, K. A.; Goettsche, K.V.; Hanson, W.; Amos, D.;

Novel Materials, Processing, and Device Technologies for Space Exploration with Potential Dual-Use Applications

NASA Technical Reports Server (NTRS)

Hepp, A. F.; Bailey, S. G.; McNatt, J. S.; Chandrashekhar, M. V. S.; Harris, J. D.; Rusch, A. W.; Nogales, K. A.; Goettsche, K. V.; Hanson, W.; Amos, D.;

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.

Capillary electrophoresis of covalently functionalized single-chirality carbon nanotubes.

PubMed

He, Pingli; Meany, Brendan; Wang, Chunyan; Piao, Yanmei; Kwon, Hyejin; Deng, Shunliu; Wang, YuHuang

2017-07-01

We demonstrate the separation of chirality-enriched single-walled carbon nanotubes (SWCNTs) by degree of surface functionalization using high-performance CE. Controlled amounts of negatively charged and positively charged functional groups were attached to the sidewall of chirality-enriched SWCNTs through covalent functionalization using 4-carboxybenzenediazonium tetrafluoroborate or 4-diazo-N,N-diethylaniline tetrafluoroborate, respectively. Surfactant- and pH-dependent studies confirmed that under conditions that minimized ionic screening effects, separation of these functionalized SWCNTs was strongly dependent on the surface charge density introduced through covalent surface chemistry. For both heterogeneous mixtures and single-chirality-enriched samples, covalently functionalized SWCNTs showed substantially increased peak width in electropherogram spectra compared to nonfunctionalized SWCNTs, which can be attributed to a distribution of surface charges along the functionalized nanotubes. Successful separation of functionalized single-chirality SWCNTs by functional density was confirmed with UV-Vis-NIR absorption and Raman scattering spectroscopies of fraction collected samples. These results suggest a high degree of structural heterogeneity in covalently functionalized SWCNTs, even for chirality-enriched samples, and show the feasibility of applying CE for high-performance separation of nanomaterials based on differences in surface functional density. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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)

Simultaneous measurement of triboelectrification and triboluminescence of crystalline materials

NASA Astrophysics Data System (ADS)

Collins, Adam L.; Camara, Carlos G.; Van Cleve, Eli; Putterman, Seth J.

2018-01-01

Triboelectrification has been studied for over 2500 years, yet there is still a lack of fundamental understanding as to its origin. Given its utility in areas such as xerography, powder spray painting, and energy harvesting, many devices have been made to investigate triboelectrification at many length-scales, though few seek to additionally make use of triboluminescence: the emission of electromagnetic radiation immediately following a charge separation event. As devices for measuring triboelectrification became smaller and smaller, now measuring down to the atomic scale with atomic force microscope based designs, an appreciation for the collective and multi-scale nature of triboelectrification has perhaps abated. Consider that the energy required to move a unit charge is very large compared to a van der Waals interaction, yet peeling Scotch tape (whose adhesion is derived from van der Waals forces) can provide strong enough energy-focusing to generate X-ray emission. This paper presents a device to press approximately cm-sized materials together in a vacuum, with in situ alignment. Residual surface charge, force, and position and X-ray, visible light, and RF emission are measured for single crystal samples. Charge is therefore tracked throughout the charging and discharging processes, resulting in a more complete picture of triboelectrification, with controllable and measurable environmental influence. Macroscale charging is directly measured, whilst triboluminescence, originating in atomic-scale processes, probes the microscale. The apparatus was built with the goal of obtaining an ab initio-level explanation of triboelectrification for well-defined materials, at the micro- and macro-scale, which has eluded scientists for millennia.

Invited review article: physics and Monte Carlo techniques as relevant to cryogenic, phonon, and ionization readout of Cryogenic Dark Matter Search radiation detectors.

PubMed

Leman, Steven W

2012-09-01

This review discusses detector physics and Monte Carlo techniques for cryogenic, radiation detectors that utilize combined phonon and ionization readout. A general review of cryogenic phonon and charge transport is provided along with specific details of the Cryogenic Dark Matter Search detector instrumentation. In particular, this review covers quasidiffusive phonon transport, which includes phonon focusing, anharmonic decay, and isotope scattering. The interaction of phonons in the detector surface is discussed along with the downconversion of phonons in superconducting films. The charge transport physics include a mass tensor which results from the crystal band structure and is modeled with a Herring-Vogt transformation. Charge scattering processes involve the creation of Neganov-Luke phonons. Transition-edge-sensor (TES) simulations include a full electric circuit description and all thermal processes including Joule heating, cooling to the substrate, and thermal diffusion within the TES, the latter of which is necessary to model normal-superconducting phase separation. Relevant numerical constants are provided for these physical processes in germanium, silicon, aluminum, and tungsten. Random number sampling methods including inverse cumulative distribution function (CDF) and rejection techniques are reviewed. To improve the efficiency of charge transport modeling, an additional second order inverse CDF method is developed here along with an efficient barycentric coordinate sampling method of electric fields. Results are provided in a manner that is convenient for use in Monte Carlo and references are provided for validation of these models.

Organic Solar Cells: Understanding the Role of Förster Resonance Energy Transfer

PubMed Central

Feron, Krishna; Belcher, Warwick J.; Fell, Christopher J.; Dastoor, Paul C.

2012-01-01

Organic solar cells have the potential to become a low-cost sustainable energy source. Understanding the photoconversion mechanism is key to the design of efficient organic solar cells. In this review, we discuss the processes involved in the photo-electron conversion mechanism, which may be subdivided into exciton harvesting, exciton transport, exciton dissociation, charge transport and extraction stages. In particular, we focus on the role of energy transfer as described by Förster resonance energy transfer (FRET) theory in the photoconversion mechanism. FRET plays a major role in exciton transport, harvesting and dissociation. The spectral absorption range of organic solar cells may be extended using sensitizers that efficiently transfer absorbed energy to the photoactive materials. The limitations of Förster theory to accurately calculate energy transfer rates are discussed. Energy transfer is the first step of an efficient two-step exciton dissociation process and may also be used to preferentially transport excitons to the heterointerface, where efficient exciton dissociation may occur. However, FRET also competes with charge transfer at the heterointerface turning it in a potential loss mechanism. An energy cascade comprising both energy transfer and charge transfer may aid in separating charges and is briefly discussed. Considering the extent to which the photo-electron conversion efficiency is governed by energy transfer, optimisation of this process offers the prospect of improved organic photovoltaic performance and thus aids in realising the potential of organic solar cells. PMID:23235328

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

Stevens, Mark J.; Saleh, Omar A.

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

Electrostatic attraction between overall neutral surfaces.

PubMed

Adar, Ram M; Andelman, David; Diamant, Haim

2016-08-01

Two overall neutral surfaces with positively and negatively charged domains ("patches") have been shown in recent experiments to exhibit long-range attraction when immersed in an ionic solution. Motivated by the experiments, we calculate analytically the osmotic pressure between such surfaces within the Poisson-Boltzmann framework, using a variational principle for the surface-averaged free energy. The electrostatic potential, calculated beyond the linear Debye-Hückel theory, yields an overall attraction at large intersurface separations, over a wide range of the system's controlled length scales. In particular, the attraction is stronger and occurs at smaller separations for surface patches of larger size and charge density. In this large patch limit, we find that the attraction-repulsion crossover separation is inversely proportional to the square of the patch-charge density and to the Debye screening length.

Boron Nitride Nanoporous Membranes with High Surface Charge by Atomic Layer Deposition.

PubMed

Weber, Matthieu; Koonkaew, Boonprakrong; Balme, Sebastien; Utke, Ivo; Picaud, Fabien; Iatsunskyi, Igor; Coy, Emerson; Miele, Philippe; Bechelany, Mikhael

2017-05-17

In this work, we report the design and the fine-tuning of boron nitride single nanopore and nanoporous membranes by atomic layer deposition (ALD). First, we developed an ALD process based on the use of BBr 3 and NH 3 as precursors in order to synthesize BN thin films. The deposited films were characterized in terms of thickness, composition, and microstructure. Next, we used the newly developed process to grow BN films on anodic aluminum oxide nanoporous templates, demonstrating the conformality benefit of BN prepared by ALD, and its scalability for the manufacturing of membranes. For the first time, the ALD process was then used to tune the diameter of fabricated single transmembrane nanopores by adjusting the BN thickness and to enable studies of the fundamental aspects of ionic transport on a single nanopore. At pH = 7, we estimated a surface charge density of 0.16 C·m -2 without slip and 0.07 C·m -2 considering a reasonable slip length of 3 nm. Molecular dynamics simulations performed with experimental conditions confirmed the conductivities and the sign of surface charges measured. The high ion transport results obtained and the ability to fine-tune nanoporous membranes by such a scalable method pave the way toward applications such as ionic separation, energy harvesting, and ultrafiltration devices.

Sequential energy and charge transfer processes in mixed host-guest complexes of subphthalocyanine, porphyrin and phthalocyanine chromophores.

PubMed

Menting, Roel; Ng, Dennis K P; Röder, Beate; Ermilov, Eugeny A

2012-11-14

Porphyrins, phthalocyanines and subphthalocyanines are three attractive classes of chromophores with intriguing properties making them suitable for the design of artificial photosynthetic systems. The assembly of these components by a supramolecular approach is of particular interest as it provides a facile means to build multi-chromophoric arrays with various architectures and tuneable photophysical properties. In this paper, we show the formation of mixed host-guest supramolecular complexes that consist of a β-cyclodextrin-conjugated subphthalocyanine, a tetrasulfonated porphyrin and a series of silicon(IV) phthalocyanines substituted axially with two β-cyclodextrins via different spacers. We found that the three components form supramolecular complexes held by host-guest interactions in aqueous solution. Upon excitation of the subphthalocyanine part of the complex, the excitation energy is delivered to the phthalocyanine unit via excitation energy transfer and the porphyrin chromophore acts as an energy transfer bridge enabling this process. It was shown that photo-induced charge transfer also takes place. A sequential electron transfer process from the porphyrin unit to the phthalocyanine moiety and subsequently from the subphthalocyanine moiety to the porphyrin unit takes place, and the probability of this process is controlled by the linker between β-cyclodextrin and phthalocyanine. The lifetime of the charge-separated state was found to be 1.7 ns by transient absorption spectroscopy.

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.

Encapsulating Bi2Ti2O7 (BTO) with reduced graphene oxide (RGO): an effective strategy to enhance photocatalytic and photoelectrocatalytic activity of BTO.

PubMed

Gupta, Satyajit; Subramanian, Vaidyanathan Ravi

2014-11-12

Multimetal oxides (AxByOz) offer a higher degree of freedom compared to single metal oxides (AOx) in that these oxides facilitate (i) designing nanomaterials with greater stability, (ii) tuning of the optical bandgap, and (iii) promoting visible light absorption. However, all AxByOz materials such as pyrochlores (A2B2O7)--referred to here as band-gap engineered composite oxide nanomaterials or BECONs--are traditionally prone to severe charge recombination at their surface. To alleviate the charge recombination, an effective strategy is to employ reduced graphene oxide (RGO) as a charge separator. The BECON and the RGO with oppositely charged functional groups attached to them can be integrated at the interface by employing a simple electrostatic self-assembly approach. As a case study, the approach is demonstrated using the Pt-free pyrochlore bismuth titanate (BTO) with RGO, and the application of the composite is investigated for the first time. When tested as a photocatalyst toward hydrogen production, an increase of ∼ 250% using BTO in the presence of RGO was observed. Further, photoelectrochemical measurements indicate an enhancement of ∼ 130% in the photocurrent with RGO inclusion. These two results firmly establish the viability of the electrostatic approach and the inclusion of RGO. The merits of the RGO addition is identified as (i) the RGO-assisted improvement in the separation of the photogenerated charges of BTO, (ii) the enhanced utilization of the charges in a photocatalytic process, and (iii) the maintenance of the BTO/RGO structural integrity after repeated use (established through reusability analysis). The success of the self-assembly strategy presented here lays the foundation for developing other forms of BECONs, belonging to perovskites (ABO3), sillenite (A12BO20), or delafossite (ABO2) groups, hitherto written off due to limited or no photoelectrochemicalactivity.

Effective Charge Carrier Utilization in Photocatalytic Conversions.

PubMed

Zhang, Peng; Wang, Tuo; Chang, Xiaoxia; Gong, Jinlong

2016-05-17

Continuous efforts have been devoted to searching for sustainable energy resources to alleviate the upcoming energy crises. Among various types of new energy resources, solar energy has been considered as one of the most promising choices, since it is clean, sustainable, and safe. Moreover, solar energy is the most abundant renewable energy, with a total power of 173 000 terawatts striking Earth continuously. Conversion of solar energy into chemical energy, which could potentially provide continuous and flexible energy supplies, has been investigated extensively. However, the conversion efficiency is still relatively low since complicated physical, electrical, and chemical processes are involved. Therefore, carefully designed photocatalysts with a wide absorption range of solar illumination, a high conductivity for charge carriers, a small number of recombination centers, and fast surface reaction kinetics are required to achieve a high activity. This Account describes our recent efforts to enhance the utilization of charge carriers for semiconductor photocatalysts toward efficient solar-to-chemical energy conversion. During photocatalytic reactions, photogenerated electrons and holes are involved in complex processes to convert solar energy into chemical energy. The initial step is the generation of charge carriers in semiconductor photocatalysts, which could be enhanced by extending the light absorption range. Integration of plasmonic materials and introduction of self-dopants have been proved to be effective methods to improve the light absorption ability of photocatalysts to produce larger amounts of photogenerated charge carriers. Subsequently, the photogenerated electrons and holes migrate to the surface. Therefore, acceleration of the transport process can result in enhanced solar energy conversion efficiency. Different strategies such as morphology control and conductivity improvement have been demonstrated to achieve this goal. Fine-tuning of the morphology of nanostructured photocatalysts can reduce the migration distance of charge carriers. Improving the conductivity of photocatalysts by using graphitic materials can also improve the transport of charge carriers. Upon charge carrier migration, electrons and holes also tend to recombine. The suppression of recombination can be achieved by constructing heterojunctions that enhance charge separation in the photocatalysts. Surface states acting as recombination centers should also be removed to improve the photocatalytic efficiency. Moreover, surface reactions, which are the core chemical processes during the solar energy conversion, can be enhanced by applying cocatalysts as well as suppressing side reactions. All of these strategies have been proved to be essential for enhancing the activities of semiconductor photocatalysts. It is hoped that delicate manipulation of photogenerated charge carriers in semiconductor photocatalysts will hold the key to effective solar-to-chemical energy conversion.

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.

Design rules for charge-transport efficient host materials for phosphorescent organic light-emitting diodes.

PubMed

May, Falk; Al-Helwi, Mustapha; Baumeier, Björn; Kowalsky, Wolfgang; Fuchs, Evelyn; Lennartz, Christian; Andrienko, Denis

2012-08-22

The use of blue phosphorescent emitters in organic light-emitting diodes (OLEDs) imposes demanding requirements on a host material. Among these are large triplet energies, the alignment of levels with respect to the emitter, the ability to form and sustain amorphous order, material processability, and an adequate charge carrier mobility. A possible design strategy is to choose a π-conjugated core with a high triplet level and to fulfill the other requirements by using suitable substituents. Bulky substituents, however, induce large spatial separations between conjugated cores, can substantially reduce intermolecular electronic couplings, and decrease the charge mobility of the host. In this work we analyze charge transport in amorphous 2,8-bis(triphenylsilyl)dibenzofuran, an electron-transporting material synthesized to serve as a host in deep-blue OLEDs. We show that mesomeric effects delocalize the frontier orbitals over the substituents recovering strong electronic couplings and lowering reorganization energies, especially for electrons, while keeping energetic disorder small. Admittance spectroscopy measurements reveal that the material has indeed a high electron mobility and a small Poole-Frenkel slope, supporting our conclusions. By linking electronic structure, molecular packing, and mobility, we provide a pathway to the rational design of hosts with high charge mobilities.

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.

Characterization and correction of charge-induced pixel shifts in DECam

DOE PAGES

Gruen, D.; Bernstein, G. M.; Jarvis, M.; ...

2015-05-28

Interaction of charges in CCDs with the already accumulated charge distribution causes both a flux dependence of the point-spread function (an increase of observed size with flux, also known as the brighter/fatter effect) and pixel-to-pixel correlations of the Poissonian noise in flat fields. We describe these effects in the Dark Energy Camera (DECam) with charge dependent shifts of effective pixel borders, i.e. the Antilogus et al. (2014) model, which we fit to measurements of flat-field Poissonian noise correlations. The latter fall off approximately as a power-law r -2.5 with pixel separation r, are isotropic except for an asymmetry in themore » direct neighbors along rows and columns, are stable in time, and are weakly dependent on wavelength. They show variations from chip to chip at the 20% level that correlate with the silicon resistivity. The charge shifts predicted by the model cause biased shape measurements, primarily due to their effect on bright stars, at levels exceeding weak lensing science requirements. We measure the flux dependence of star images and show that the effect can be mitigated by applying the reverse charge shifts at the pixel level during image processing. Differences in stellar size, however, remain significant due to residuals at larger distance from the centroid.« less

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.

Direct observation of metal nanoparticles as heterogeneous nuclei for the condensation of supersaturated organic vapors: nucleation of size-selected aluminum nanoparticles in acetonitrile and n-hexane vapors.

PubMed

Abdelsayed, Victor; El-Shall, M Samy

2014-08-07

This work reports the direct observation and separation of size-selected aluminum nanoparticles acting as heterogeneous nuclei for the condensation of supersaturated vapors of both polar and nonpolar molecules. In the experiment, we study the condensation of supersaturated acetonitrile and n-hexane vapors on charged and neutral Al nanoparticles by activation of the metal nanoparticles to act as heterogeneous nuclei for the condensation of the organic vapor. Aluminum seed nanoparticles with diameters of 1 and 2 nm are capable of acting as heterogeneous nuclei for the condensation of supersaturated acetonitrile and hexane vapors. The comparison between the Kelvin and Fletcher diameters indicates that for the heterogeneous nucleation of both acetonitrile and hexane vapors, particles are activated at significantly smaller sizes than predicted by the Kelvin equation. The activation of the Al nanoparticles occurs at nearly 40% and 65% of the onset of homogeneous nucleation of acetonitrile and hexane supersaturated vapors, respectively. The lower activation of the charged Al nanoparticles in acetonitrile vapor is due to the charge-dipole interaction which results in rapid condensation of the highly polar acetonitrile molecules on the charged Al nanoparticles. The charge-dipole interaction decreases with increasing the size of the Al nanoparticles and therefore at low supersaturations, most of the heterogeneous nucleation events are occurring on neutral nanoparticles. No sign effect has been observed for the condensation of the organic vapors on the positively and negatively charged Al nanoparticles. The present approach of generating metal nanoparticles by pulsed laser vaporization within a supersaturated organic vapor allows for efficient separation between nucleation and growth of the metal nanoparticles and, consequently controls the average particle size, particle density, and particle size distribution within the liquid droplets of the condensing vapor. Strong correlation is found between the seed nanoparticle's size and the degree of the supersaturation of the condensing vapor. This result and the agreement among the calculated Kelvin diameters and the size of the nucleating Al nanoparticles determined by transmission electron microscopy provide strong proof for the development of a new approach for the separation and characterization of heterogeneous nuclei formed in organic vapors. These processes can take place in the atmosphere by a combination of several organic species including polar compounds which could be very efficient in activating charged nanoparticles and cluster ions of atmospheric relevance.

Direct observation of metal nanoparticles as heterogeneous nuclei for the condensation of supersaturated organic vapors: Nucleation of size-selected aluminum nanoparticles in acetonitrile and n-hexane vapors

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

Abdelsayed, Victor; Samy El-Shall, M., E-mail: mselshal@vcu.edu

This work reports the direct observation and separation of size-selected aluminum nanoparticles acting as heterogeneous nuclei for the condensation of supersaturated vapors of both polar and nonpolar molecules. In the experiment, we study the condensation of supersaturated acetonitrile and n-hexane vapors on charged and neutral Al nanoparticles by activation of the metal nanoparticles to act as heterogeneous nuclei for the condensation of the organic vapor. Aluminum seed nanoparticles with diameters of 1 and 2 nm are capable of acting as heterogeneous nuclei for the condensation of supersaturated acetonitrile and hexane vapors. The comparison between the Kelvin and Fletcher diameters indicatesmore » that for the heterogeneous nucleation of both acetonitrile and hexane vapors, particles are activated at significantly smaller sizes than predicted by the Kelvin equation. The activation of the Al nanoparticles occurs at nearly 40% and 65% of the onset of homogeneous nucleation of acetonitrile and hexane supersaturated vapors, respectively. The lower activation of the charged Al nanoparticles in acetonitrile vapor is due to the charge-dipole interaction which results in rapid condensation of the highly polar acetonitrile molecules on the charged Al nanoparticles. The charge-dipole interaction decreases with increasing the size of the Al nanoparticles and therefore at low supersaturations, most of the heterogeneous nucleation events are occurring on neutral nanoparticles. No sign effect has been observed for the condensation of the organic vapors on the positively and negatively charged Al nanoparticles. The present approach of generating metal nanoparticles by pulsed laser vaporization within a supersaturated organic vapor allows for efficient separation between nucleation and growth of the metal nanoparticles and, consequently controls the average particle size, particle density, and particle size distribution within the liquid droplets of the condensing vapor. Strong correlation is found between the seed nanoparticle's size and the degree of the supersaturation of the condensing vapor. This result and the agreement among the calculated Kelvin diameters and the size of the nucleating Al nanoparticles determined by transmission electron microscopy provide strong proof for the development of a new approach for the separation and characterization of heterogeneous nuclei formed in organic vapors. These processes can take place in the atmosphere by a combination of several organic species including polar compounds which could be very efficient in activating charged nanoparticles and cluster ions of atmospheric relevance.« less

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.

Therapeutic Antibody Engineering To Improve Viscosity and Phase Separation Guided by Crystal Structure.

PubMed

Chow, Chi-Kin; Allan, Barrett W; Chai, Qing; Atwell, Shane; Lu, Jirong

2016-03-07

Antibodies at high concentrations often reveal unanticipated biophysical properties suboptimal for therapeutic development. The purpose of this work was to explore the use of point mutations based on crystal structure information to improve antibody physical properties such as viscosity and phase separation (LLPS) at high concentrations. An IgG4 monoclonal antibody (Mab4) that exhibited high viscosity and phase separation at high concentration was used as a model system. Guided by the crystal structure, four CDR point mutants were made to evaluate the role of hydrophobic and charge interactions on solution behavior. Surprisingly and unpredictably, two of the charge mutants, R33G and N35E, showed a reduction in viscosity and a lower propensity to form LLPS at high concentration compared to the wild-type (WT), while a third charge mutant S28K showed an increased propensity to form LLPS compared to the WT. A fourth mutant, F102H, had reduced hydrophobicity, but unchanged viscosity and phase separation behavior. We further evaluated the correlation of various biophysical measurements including second virial coefficient (A2), interaction parameter (kD), weight-average molecular weight (WAMW), and hydrodynamic diameters (DH), at relatively low protein concentration (4 to 15 mg/mL) to physical properties, such as viscosity and liquid-liquid phase separation (LLPS), at high concentration. Surprisingly, kD measured using dynamic light scattering (DLS) at low antibody concentration correlated better with viscosity and phase separation than did A2 for Mab4. Our results suggest that the high viscosity and phase separation observed at high concentration for Mab4 are mainly driven by charge and not hydrophobicity.

The role of algal organic matter in the separation of algae and cyanobacteria using the novel "Posi" - Dissolved air flotation process.

PubMed

Hanumanth Rao, Narasinga Rao; Yap, Russell; Whittaker, Michael; Stuetz, Richard M; Jefferson, Bruce; Peirson, William L; Granville, Anthony M; Henderson, Rita K

2018-03-01

Algae and cyanobacteria frequently require separation from liquid media in both water treatment and algae culturing for biotechnology applications. The effectiveness of cell separation using a novel dissolved air flotation process that incorporates positively charged bubbles (PosiDAF) has recently been of interest but has been shown to be dependent on the algae or cyanobacteria species tested. Previously, it was hypothesised that algal organic matter (AOM) could be impacting the separation efficiency. Hence, this study investigates the influence of AOM on cell separation using PosiDAF, in which bubbles are modified using a commercially available cationic polyelectrolyte poly(N, N-diallyl-N,N-dimethylammonium chloride) (PDADMAC). The separation of Chlorella vulgaris CS-42/7, Mychonastes homosphaera CS-556/01 and two strains of Microcystis aeruginosa (CS-564/01 and CS-555/1), all of which have similar cell morphology but different AOM character, was investigated. By testing the cell separation in the presence and absence of AOM, it was determined that AOM enhanced cell separation for all the strains but to different extents depending on the quantity and composition of carbohydrates and proteins in the AOM. By extracting AOM from the strain for which optimal separation was observed and adding it to the others, cell separation improved from <55% to >90%. This was attributed to elevated levels of acidic carbohydrates as well as glycoprotein-carbohydrate conjugations, which in turn were related to the nature and quantity of proteins and carbohydrates present in the AOM. Therefore, it was concluded that process optimisation requires an in-depth understanding of the AOM and its components. If culturing algae for biotechnology applications, this indicates that strain selection is not only important with respect to high value product content, but also for cell separation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Charge carrier concentration dependence of encounter-limited bimolecular recombination in phase-separated organic semiconductor blends

NASA Astrophysics Data System (ADS)

Heiber, Michael C.; Nguyen, Thuc-Quyen; Deibel, Carsten

2016-05-01

Understanding how the complex intermolecular configurations and nanostructure present in organic semiconductor donor-acceptor blends impacts charge carrier motion, interactions, and recombination behavior is a critical fundamental issue with a particularly major impact on organic photovoltaic applications. In this study, kinetic Monte Carlo (KMC) simulations are used to numerically quantify the complex bimolecular charge carrier recombination behavior in idealized phase-separated blends. Recent KMC simulations have identified how the encounter-limited bimolecular recombination rate in these blends deviates from the often used Langevin model and have been used to construct the new power mean mobility model. Here, we make a challenging but crucial expansion to this work by determining the charge carrier concentration dependence of the encounter-limited bimolecular recombination coefficient. In doing so, we find that an accurate treatment of the long-range electrostatic interactions between charge carriers is critical, and we further argue that many previous KMC simulation studies have used a Coulomb cutoff radius that is too small, which causes a significant overestimation of the recombination rate. To shed more light on this issue, we determine the minimum cutoff radius required to reach an accuracy of less than ±10 % as a function of the domain size and the charge carrier concentration and then use this knowledge to accurately quantify the charge carrier concentration dependence of the recombination rate. Using these rigorous methods, we finally show that the parameters of the power mean mobility model are determined by a newly identified dimensionless ratio of the domain size to the average charge carrier separation distance.

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.

Double heterojunction nanowire photocatalysts for hydrogen generation.

PubMed

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

2014-04-21

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

Evaluation of newly synthesized and commercially available charged cyclomaltooligosaccharides (cyclodextrins) for capillary electrokinetic chromatography.

PubMed

Culha, Mustafa; Schell, Fred M; Fox, Shannon; Green, Thomas; Betts, Thomas; Sepaniak, Michael J

2004-01-22

A highly new charged cyclodextrin (CD) derivatives, (6-O-carboxymethyl-2,3-di-O-methyl)cyclomaltoheptaoses (CDM-beta-CDs), was synthesized and characterized as anionic reagents for capillary electrophoresis (CE) in an electrokinetic chromatography mode of separation. Substitution with dimethyl groups at the secondary hydroxyl sites of the CD is aimed at influencing the magnitude and selectivity of analyte-CD interactions, while substitution by carboxymethyl groups at the primary hydroxyl sites provides for high charge and electrophoretic mobility. Full regioselective methylation at the secondary hydroxyl sites was achieved in this work, while substitution at the primary hydroxyl sites generated a mixture of multiply charged products. The separation performance of CDM-beta-CD was evaluated using a variety of analyte mixtures. The results obtained from commercially available negatively charged cyclodextrins, heptakis(2,3-di-O-methyl-6-O-sulfo)cyclomaltoheptaose (HDMS-beta-CD) and O-(carboxymethyl)cyclomaltoheptaose (CM-beta-CD) with an average degree of substitution one (DS 1), were compared to CDM-beta-CD using a sample composed of eight positional isomers of dihydroxynaphthalene. Four hydroxylated polychlorobiphenyl derivatives, a group of chiral and isomeric catchecins, and chiral binaphthyl compounds were also separated with CDM-beta-CD. The effect of adding neutral beta-cyclodextrin (beta-CD) into the running buffer containing charged cyclodextrins was investigated and provided evidence of significant inter-CD interactions. Under certain running buffer conditions, the charged cyclodextrins also appear to adsorb to the capillary walls to various degrees.

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

Tsoupas, Nicholaos

The acceleration process of charged particle beam often required the use of few acceleration stages to provide the beam with the desired energy. The extraction of the beam from one acceleration stage and the injection to the next, both require a special type of magnet which comes under the name septum magnet. Such a magnet generates a strong field in one region of space an a very low field in another region with two regions separated by a very thin material (septum).

Selective Adsorption and Separation of Organic Dyes with Spherical Polyelectrolyte Brushes and Compressed Carbon Dioxide.

PubMed

Zhang, Rui; Yu, Zhenchuan; Wang, Lei; Shen, Qizhe; Hou, Xiaoyan; Guo, Xuhong; Wang, Junwei; Zhu, Xuedong; Yao, Yuan

2017-10-04

Dye-containing wastewater has caused serious environmental pollution. Herein, rationally designed spherical polyelectrolyte brushes (SPBs) with cationic charges, polystyrene-poly(2-aminoethylmethacrylate hydrochloride) (PS-PAEMH) as the absorbent, and compressed carbon dioxide as the antisolvent are proposed for the separation of the anionic dye eosin Y (EY) from a solution of mixed dyes. The adsorption behavior of EY onto PS-PAEMH was highly dependent on CO 2 pressure, contact time, and initial concentration. The maximum adsorption capacity of PS-PAEMH was 335.20 mg g -1 . FTIR and UV/Vis measurements proved that the electrostatic interactions between EY and PS-PAEMH played an important role in the absorbance process. The adsorption process fitted the pseudo-second-order kinetic model and Freundlich isotherm model very well. The combined dye and polymer brush could be easily separated through ion exchange by adding an aqueous solution of NaCl. Recovered PS-PAEMH retained a high adsorption capacity even after ten cycles of regeneration. This method provides a simple and effective way to separate ionic materials for environmental engineering. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Separation of porcine parvovirus from bovine serum albumin using PEG-salt aqueous two-phase system.

PubMed

Vijayaragavan, K Saagar; Zahid, Amna; Young, Jonathan W; Heldt, Caryn L

2014-09-15

Vaccine production faces a challenge in adopting conventional downstream processing steps that can efficiently purify large viral particles. Some major issues that plague vaccine purification are purity, potency, and quality. The industry currently considers 30% as an acceptable virus recovery for a vaccine purification process, including all downstream processes, whereas antibody recovery from CHO cell culture is generally around 80-85%. A platform technology with an improved virus recovery would revolutionize vaccine production. In a quest to fulfill this goal, we have been exploring aqueous two-phase systems (ATPSs) as an optional mechanism to purify virus. ATPS has been unable to gain wide implementation mainly due to loss of virus infectivity, co-purification of proteins, and difficulty of polymer recycling. Non-enveloped viruses are chemically resistant enough to withstand the high polymer and salt concentrations that are required for effective ATPS separations. We used infectious porcine parvovirus (PPV), a non-enveloped, DNA virus as a model virus to test and develop an ATPS separation method. We successfully tackled two of the three main disadvantages of ATPS previously stated; we achieved a high infectious yield of 64% in a PEG-citrate ATPS process while separating out the main contaminate protein, bovine serum albumin (BSA). The most dominant forces in the separation were biomolecule charge, virus surface hydrophobicity, and the ATPS surface tension. Highly hydrophobic viruses are likely to benefit from the discovered ATPS for high-purity vaccine production and ease of implementation. Copyright © 2014 Elsevier B.V. All rights reserved.

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 Use of Tribocharging in the Electrostatic Beneficiation of Lunar Simulant

NASA Technical Reports Server (NTRS)

Trigwell, S.; Captain, J. G.; Arens, E. E.; Captain, J. E.; Quinn, J. W.; Calle, C. I.

2007-01-01

Any future lunar base and habitat must be constructed from strong dense materials in order to provide for thermal and radiation protection. Lunar soil may meet this need. Lunar regolith has high concentrations of aluminum, silicon, calcium, iron, sodium, and titanium oxides. Refinement or enrichment of specific minerals in the soil before it is chemically processed may be more desirable as it would reduce the size and energy requirements required to produce the virgin material and it may significantly reduce the process' complexity. Also, investigations into the potential production of breathable oxygen from oxidized mineral components are a major research initiative by NASA. In this study. the objective was to investigate the use of tribocharging to charge lunar simulants and pass them through a parallel plate separator to enrich different mineral fractions. This technique takes advantage of the high Lunar vacuum in which much higher voltages can be used on the separation plates than in air. Additionally, the Lunar g1avity, only being 1/6 that of Earth, allows the particles more separation time between the plates and therefore enhances separation. For the separation studies, two lunar stimulants were used. The first simulant was created in-house, labeled KSC-1. using commercially supplied (sieved to 325 mesh) materials, and was composed of 40 wt. % feldspar ((Na,K,Ca)AlSi3O8;SiO2), 40 wt. % olivine ((Mg,Fe)2SiO4), 10 wt. % ilmenite (FeTiO3). and 10 wt. % spodumene (LiAlSi2O6) (pyroxene). The advantage of the in-house mixture is that the composition can he varied to simulate different soil compositions from different areas on the moon. This simulant was used to show proof-of-concept using the designed separator in air. The second stimulant was JSC-1. used for the vacuum experiments. JSC-1 is principally basalts, containing phases of plagioclase. pyroxene. olivine, and ilmenite. The JSC-1 was sieved to provide a 50-75 micron size range to correlate with the mean grain size found on the moon's surface [1]. Four different materials were investigated for the triboelectrification process; aluminum, copper. stainless steel, and PTFE. These materials were selected because they offer a wide variation in work functions (aluminum 4.28 eV, copper 4.65 eV. stainless steel 5.04 eV, and PTFE 5.75 eV). The difference between the work function of each material and the simulant influences the charge obtained by the grains. Each simulant was analyzed before and after separation using X-ray Photoelectron Spectroscopy (XPS) to determine mineral surface composition. In addition. Raman spectroscopy was performed on the JSC-1 before and after separation in vacuum to determine the mineral composition. Charge-to-mass (Q/M) measurements were performed using a fluidizing bed in air and passing the simulant through a static mixer of a particular material and collecting it in a Faraday pail grounded through an electrometer. To measure the Q/M in vacuum, a special device was constructed consisting of a heater/shaker cup that fed into a solid block of material (either PTFE, copper, or aluminum) in which a channel composed of a "zig-zag" series of inclines greater than 50 degrees has been cut. The voltage to the vibrating motor can be varied to control the amount of simulant passing through the channel. Figure I shows the Q/M measurements for JSC-1 tribocharged using the static mixers and the incline plane chargers in air, and the incline plane chargers in vacuum.

The effect of charged quantum dots on the mobility of a two-dimensional electron gas: How important is the Coulomb scattering?

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

Kurzmann, A., E-mail: annika.kurzmann@uni-due.de; Beckel, A.; Lorke, A.

2015-02-07

We have investigated the influence of a layer of charged self-assembled quantum dots (QDs) on the mobility of a nearby two-dimensional electron gas (2DEG). Time-resolved transconductance spectroscopy was used to separate the two contributions of the change in mobility, which are: (i) The electrons in the QDs act as Coulomb scatterers for the electrons in the 2DEG. (ii) The screening ability and, hence, the mobility of the 2DEG decreases when the charge carrier density is reduced by the charged QDs, i.e., the mobility itself depends on the charge carrier concentration. Surprisingly, we find a negligible influence of the Coulomb scatteringmore » on the mobility for a 2DEG, separated by a 30 nm tunneling barrier to the layer of QDs. This means that the mobility change is completely caused by depletion, i.e., reduction of the charge carrier density in the 2DEG, which indirectly influences the mobility.« less

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.

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.

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 .

Is it Possible to Conserve Electric Charge Without Separately Conserving Baryonic Number and Leptonic Number?

NASA Astrophysics Data System (ADS)

Tsan, Ung Chan

Charges that are sources of fields must be universally conserved. Any quantity which is proved to be violated in certain circumstance cannot be a source of field. To account for the asymmetry of our Universe baryon number A has to be violated; thus A cannot be a charge. We postulate a new interaction, matter creation, with (A-L) as charge and Z* as messenger. Conservation of (A-L) instead of (3A-L) suggested by Sakharov is deduced on the one hand from observational facts (our Universe is both material and neutral) and on the other hand from the generalized Gell-Mann and Nishijima formula. Conservation of (A-L) forbids neutrinoless double beta decay and neutron antineutron oscillations. The union of four interactions — electromagnetism, the MC interaction, the weak interaction and the strong interaction — considered as the product U(1) × U(1) × SU(2) × SU(3) would account for available experimental and observational data. Observation of processes violating baryon number conservation would be of great interest in falsifying this suggestion.

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

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.

Electronic Structure and Stability of [B 12 X 12 ] 2– (X = F–At): A Combined Photoelectron Spectroscopic and Theoretical Study

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

Warneke, Jonas; Hou, Gao-Lei; Aprà, Edoardo

2017-10-09

The relative stability and electron loss process of Multiply Charged Anions have been traditionally explained in terms of the classical Coulomb interaction between spatially separated charges. In this study we report the surprising properties of [B12X12]2-, X = F – At, that are counterintuitive compared to the prevailing classical description and justify their classification into a new class of MCAs. In this new class of MCAs, comprising of a “Boron core” surrounded by a “Halogen shell”, the sign of the total charge in these two regions changes along the halogen series from F to At. With the aid of photoelectronmore » spectroscopy and electronic structure calculations we demonstrate that the behavior of these MCAs is largely determined by quantum effects rather than classical electrostatics. The second excess electron is always taken from the most positively charged region, viz. the “Boron core” for F – Br and the surrounding “Halogen shell” for I, At.« less

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.

Charged-pion cross sections and double-helicity asymmetries in polarized p + p collisions at √s = 200 GeV

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

Adare, A.; Aidala, C.; Ajitanand, N. N.

2015-02-02

We present midrapidity charged-pion invariant cross sections, the ratio of the π⁻ to π⁺ cross sections and the charge-separated double-spin asymmetries in polarized p+p collisions at √s = 200 GeV. While the cross section measurements are consistent within the errors of next-to-leadingorder (NLO) perturbative quantum chromodynamics predictions (pQCD), the same calculations over estimate the ratio of the charged-pion cross sections. This discrepancy arises from the cancellation of the substantial systematic errors associated with the NLO-pQCD predictions in the ratio and highlights the constraints these data will place on flavor dependent pion fragmentation functions. Thus, the charge-separated pion asymmetries presented heremore » sample an x range of ~0.03–0.16 and provide unique information on the sign of the gluon-helicity distribution.« less

Charged-pion cross sections and double-helicity asymmetries in polarized p +p collisions at √{s }=200 GeV

NASA Astrophysics Data System (ADS)

Adare, A.; Aidala, C.; Ajitanand, N. N.; Akiba, Y.; Akimoto, R.; Al-Ta'Ani, H.; Alexander, J.; Andrews, K. R.; Angerami, A.; Aoki, K.; Apadula, N.; Appelt, E.; Aramaki, Y.; Armendariz, R.; Aschenauer, E. C.; Atomssa, E. T.; Awes, T. C.; Azmoun, B.; Babintsev, V.; Bai, M.; Bannier, B.; Barish, K. N.; Bassalleck, B.; Basye, A. T.; Bathe, S.; Baublis, V.; Baumann, C.; Bazilevsky, A.; Belmont, R.; Ben-Benjamin, J.; Bennett, R.; Blau, D. S.; Bok, J. S.; Boyle, K.; Brooks, M. L.; Broxmeyer, D.; Buesching, H.; Bumazhnov, V.; Bunce, G.; Butsyk, S.; Campbell, S.; Castera, P.; Chen, C.-H.; Chi, C. Y.; Chiu, M.; Choi, I. J.; Choi, J. B.; Choudhury, R. K.; Christiansen, P.; Chujo, T.; Chvala, O.; Cianciolo, V.; Citron, Z.; Cole, B. A.; Conesa Del Valle, Z.; Connors, M.; Csanád, M.; Csörgő, T.; Dairaku, S.; Datta, A.; David, G.; Dayananda, M. K.; Denisov, A.; Deshpande, A.; Desmond, E. J.; Dharmawardane, K. V.; Dietzsch, O.; Dion, A.; Donadelli, M.; Drapier, O.; Drees, A.; Drees, K. A.; Durham, J. M.; Durum, A.; D'Orazio, L.; Efremenko, Y. V.; Engelmore, T.; Enokizono, A.; En'yo, H.; Esumi, S.; Fadem, B.; Fields, D. E.; Finger, M.; Finger, M.; Fleuret, F.; Fokin, S. L.; Frantz, J. E.; Franz, A.; Frawley, A. D.; Fukao, Y.; Fusayasu, T.; Gal, C.; Garishvili, I.; Giordano, F.; Glenn, A.; Gong, X.; Gonin, M.; Goto, Y.; Granier de Cassagnac, R.; Grau, N.; Greene, S. V.; Grosse Perdekamp, M.; Gunji, T.; Guo, L.; Gustafsson, H.-Å.; Haggerty, J. S.; Hahn, K. I.; Hamagaki, H.; Hamblen, J.; Han, R.; Hanks, J.; Harper, C.; Hashimoto, K.; Haslum, E.; Hayano, R.; He, X.; Hemmick, T. K.; Hester, T.; Hill, J. C.; Hollis, R. S.; Holzmann, W.; Homma, K.; Hong, B.; Horaguchi, T.; Hori, Y.; Hornback, D.; Huang, S.; Ichihara, T.; Ichimiya, R.; Iinuma, H.; Ikeda, Y.; Imai, K.; Inaba, M.; Iordanova, A.; Isenhower, D.; Ishihara, M.; Issah, M.; Ivanischev, D.; Iwanaga, Y.; Jacak, B. V.; Jia, J.; Jiang, X.; John, D.; Johnson, B. M.; Jones, T.; Joo, K. S.; Jouan, D.; Kamin, J.; Kaneti, S.; Kang, B. H.; Kang, J. H.; Kang, J. S.; Kapustinsky, J.; Karatsu, K.; Kasai, M.; Kawall, D.; Kazantsev, A. V.; Kempel, T.; Khanzadeev, A.; Kijima, K. M.; Kim, B. I.; Kim, D. J.; Kim, E.-J.; Kim, Y.-J.; Kim, Y. K.; Kinney, E.; Kiss, Á.; Kistenev, E.; Kleinjan, D.; Kline, P.; Kochenda, L.; Komkov, B.; Konno, M.; Koster, J.; Kotov, D.; Král, A.; Kunde, G. J.; Kurita, K.; Kurosawa, M.; Kwon, Y.; Kyle, G. S.; Lacey, R.; Lai, Y. S.; Lajoie, J. G.; Lebedev, A.; Lee, D. M.; Lee, J.; Lee, K. B.; Lee, K. S.; Lee, S. H.; Lee, S. R.; Leitch, M. J.; Leite, M. A. L.; Li, X.; Lim, S. H.; Linden Levy, L. A.; Liu, H.; Liu, M. X.; Love, B.; Lynch, D.; Maguire, C. F.; Makdisi, Y. I.; Manion, A.; Manko, V. I.; Mannel, E.; Mao, Y.; Masui, H.; McCumber, M.; McGaughey, P. L.; McGlinchey, D.; McKinney, C.; Means, N.; Mendoza, M.; Meredith, B.; Miake, Y.; Mibe, T.; Mignerey, A. C.; Miki, K.; Milov, A.; Mitchell, J. T.; Miyachi, Y.; Mohanty, A. K.; Moon, H. J.; Morino, Y.; Morreale, A.; Morrison, D. P.; Motschwiller, S.; Moukhanova, T. V.; Murakami, T.; Murata, J.; Nagamiya, S.; Nagle, J. L.; Naglis, M.; Nagy, M. I.; Nakagawa, I.; Nakamiya, Y.; Nakamura, K. R.; Nakamura, T.; Nakano, K.; Newby, J.; Nguyen, M.; Nihashi, M.; Nouicer, R.; Nyanin, A. S.; Oakley, C.; O'Brien, E.; Ogilvie, C. A.; Oka, M.; Okada, K.; Oskarsson, A.; Ouchida, M.; Ozawa, K.; Pak, R.; Pantuev, V.; Papavassiliou, V.; Park, B. H.; Park, I. H.; Park, S. K.; Pate, S. F.; Patel, L.; Pei, H.; Peng, J.-C.; Pereira, H.; Peressounko, D. Yu.; Petti, R.; Pinkenburg, C.; Pisani, R. P.; Proissl, M.; Purschke, M. L.; Qu, H.; Rak, J.; Ravinovich, I.; Read, K. F.; Reygers, K.; Riabov, V.; Riabov, Y.; Richardson, E.; Roach, D.; Roche, G.; Rolnick, S. D.; Rosati, M.; Rosendahl, S. S. E.; Rubin, J. G.; Sahlmueller, B.; Saito, N.; Sakaguchi, T.; Samsonov, V.; Sano, S.; Sarsour, M.; Sato, T.; Savastio, M.; Sawada, S.; Sedgwick, K.; Seidl, R.; Seto, R.; Sharma, D.; Shein, I.; Shibata, T.-A.; Shigaki, K.; Shim, H. H.; Shimomura, M.; Shoji, K.; Shukla, P.; Sickles, A.; Silva, C. L.; Silvermyr, D.; Silvestre, C.; Sim, K. S.; Singh, B. K.; Singh, C. P.; Singh, V.; Slunečka, M.; Sodre, T.; Soltz, R. A.; Sondheim, W. E.; Sorensen, S. P.; Sourikova, I. V.; Stankus, P. W.; Stenlund, E.; Stoll, S. P.; Sugitate, T.; Sukhanov, A.; Sun, J.; Sziklai, J.; Takagui, E. M.; Takahara, A.; Taketani, A.; Tanabe, R.; Tanaka, Y.; Taneja, S.; Tanida, K.; Tannenbaum, M. J.; Tarafdar, S.; Taranenko, A.; Tennant, E.; Themann, H.; Thomas, D.; Togawa, M.; Tomášek, L.; Tomášek, M.; Torii, H.; Towell, R. S.; Tserruya, I.; Tsuchimoto, Y.; Utsunomiya, K.; Vale, C.; van Hecke, H. W.; Vazquez-Zambrano, E.; Veicht, A.; Velkovska, J.; Vértesi, R.; Virius, M.; Vossen, A.; Vrba, V.; Vznuzdaev, E.; Wang, X. R.; Watanabe, D.; Watanabe, K.; Watanabe, Y.; Watanabe, Y. S.; Wei, F.; Wei, R.; Wessels, J.; White, S. N.; Winter, D.; Woody, C. L.; Wright, R. M.; Wysocki, M.; Yamaguchi, Y. L.; Yang, R.; Yanovich, A.; Ying, J.; Yokkaichi, S.; Yoo, J. S.; You, Z.; Young, G. R.; Younus, I.; Yushmanov, I. E.; Zajc, W. A.; Zelenski, A.; Zhou, S.; Phenix Collaboration

2015-02-01

We present midrapidity charged-pion invariant cross sections, the ratio of the π- to π+ cross sections and the charge-separated double-spin asymmetries in polarized p +p collisions at √{s }=200 GeV . While the cross section measurements are consistent within the errors of next-to-leading-order (NLO) perturbative quantum chromodynamics predictions (pQCD), the same calculations overestimate the ratio of the charged-pion cross sections. This discrepancy arises from the cancellation of the substantial systematic errors associated with the NLO-pQCD predictions in the ratio and highlights the constraints these data will place on flavor-dependent pion fragmentation functions. The charge-separated pion asymmetries presented here sample an x range of ˜0.03 - 0.16 and provide unique information on the sign of the gluon-helicity distribution.

Microencapsulation and Electrostatic Processing Device

NASA Technical Reports Server (NTRS)

Morrison, Dennis R. (Inventor); Mosier, Benjamin (Inventor); Cassanto, John M. (Inventor)

2001-01-01

A microencapsulation and electrostatic processing (MEP) device is provided for forming microcapsules. In one embodiment, the device comprises a chamber having a filter which separates a first region in the chamber from a second region in the chamber. An aqueous solution is introduced into the first region through an inlet port, and a hydrocarbon/ polymer solution is introduced into the second region through another inlet port. The filter acts to stabilize the interface and suppress mixing between the two immiscible solutions as they are being introduced into their respective regions. After the solutions have been introduced and have become quiescent, the interface is gently separated from the filter. At this point, spontaneous formation of microcapsules at the interface may begin to occur, or some fluid motion may be provided to induce microcapsule formation. In any case, the fluid shear force at the interface is limited to less than 100 dynes/sq cm. This low-shear approach to microcapsule formation yields microcapsules with good sphericity and desirable size distribution. The MEP device is also capable of downstream processing of microcapsules, including rinsing, re-suspension in tertiary fluids, electrostatic deposition of ancillary coatings, and free-fluid electrophoretic separation of charged microcapsules.

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.

Control of gel swelling and phase separation of weakly charged thermoreversible gels by salt addition

PubMed Central

Solis, Francisco J.; Vernon, Brent

2009-01-01

Doping of thermoreversible polymer gels with charged monomers provides a way to control phase separation and gelation conditions by coupling the properties of the gel with a tunable ionic environment. We analyze the dependence of the gelation and phase separation conditions on the amount of salt present using a mean field model of weakly charged associative polymers. The ions and co-ions present are explicitly considered at the mean field level, and we determine their concentrations in the different equilibrium phases when the system undergoes phase separation. For weak polymer charge, the entropic contributions of the ions to the free energy of the system play a central role in the determination of the location of phase equilibrium. In the simplest case, when the associative interaction responsible for gel formation is independent of the electrostatic interaction, the addition of salt changes the polymer equilibrium concentrations and indirectly changes the measurable swelling of the gel. We construct phase diagrams of these systems showing the location of the coexistence region, the gel-sol boundary and the location of the tie-lines. We determine the swelling of the gel within the co-existence region. Our main result is that the description of the effect of the salt on the properties of the weakly charged gel can be described through an extra contribution to the effective immiscibility parameter χ proportional to the square of the doping degree f2 and to the inverse square of the added salt concentration s−2. PMID:19759854

A Novel, In-solution Separation of Endogenous Cardiac Sarcomeric Proteins and Identification of Distinct Charged Variants of Regulatory Light Chain*

PubMed Central

Scruggs, Sarah B.; Reisdorph, Rick; Armstrong, Mike L.; Warren, Chad M.; Reisdorph, Nichole; Solaro, R. John; Buttrick, Peter M.

2010-01-01

The molecular conformation of the cardiac myosin motor is modulated by intermolecular interactions among the heavy chain, the light chains, myosin binding protein-C, and titin and is governed by post-translational modifications (PTMs). In-gel digestion followed by LC/MS/MS has classically been applied to identify cardiac sarcomeric PTMs; however, this approach is limited by protein size, pI, and difficulties in peptide extraction. We report a solution-based work flow for global separation of endogenous cardiac sarcomeric proteins with a focus on the regulatory light chain (RLC) in which specific sites of phosphorylation have been unclear. Subcellular fractionation followed by OFFGEL electrophoresis resulted in isolation of endogenous charge variants of sarcomeric proteins, including regulatory and essential light chains, myosin heavy chain, and myosin-binding protein-C of the thick filament. Further purification of RLC using reverse-phase HPLC separation and UV detection enriched for RLC PTMs at the intact protein level and provided a stoichiometric and quantitative assessment of endogenous RLC charge variants. Digestion and subsequent LC/MS/MS unequivocally identified that the endogenous charge variants of cardiac RLC focused in unique OFFGEL electrophoresis fractions were unphosphorylated (78.8%), singly phosphorylated (18.1%), and doubly phosphorylated (3.1%) RLC. The novel aspects of this study are that 1) milligram amounts of endogenous cardiac sarcomeric subproteome were focused with resolution comparable with two-dimensional electrophoresis, 2) separation and quantification of post-translationally modified variants were achieved at the intact protein level, 3) separation of intact high molecular weight thick filament proteins was achieved in solution, and 4) endogenous charge variants of RLC were separated; a novel doubly phosphorylated form was identified in mouse, and singly phosphorylated, singly deamidated, and deamidated/phosphorylated forms were identified and quantified in human non-failing and failing heart samples, thus demonstrating the clinical utility of the method. PMID:20445002

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

Reduced Carrier Recombination in PbS - CuInS2 Quantum Dot Solar Cells

PubMed Central

Sun, Zhenhua; Sitbon, Gary; Pons, Thomas; Bakulin, Artem A.; Chen, Zhuoying

2015-01-01

Energy loss due to carrier recombination is among the major factors limiting the performance of TiO2/PbS colloidal quantum dot (QD) heterojunction solar cells. In this work, enhanced photocurrent is achieved by incorporating another type of hole-transporting QDs, Zn-doped CuInS2 (Zn-CIS) QDs into the PbS QD matrix. Binary QD solar cells exhibit a reduced charge recombination associated with the spatial charge separation between these two types of QDs. A ~30% increase in short-circuit current density and a ~20% increase in power conversion efficiency are observed in binary QD solar cells compared to cells built from PbS QDs only. In agreement with the charge transfer process identified through ultrafast pump/probe spectroscopy between these two QD components, transient photovoltage characteristics of single-component and binary QDs solar cells reveal longer carrier recombination time constants associated with the incorporation of Zn-CIS QDs. This work presents a straightforward, solution-processed method based on the incorporation of another QDs in the PbS QD matrix to control the carrier dynamics in colloidal QD materials and enhance solar cell performance. PMID:26024021

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.

A comparative study of the reduction of silver and gold salts in water by a cathodic microplasma electrode

NASA Astrophysics Data System (ADS)

De Vos, Caroline; Baneton, Joffrey; Witzke, Megan; Dille, Jean; Godet, Stéphane; Gordon, Michael J.; Mohan Sankaran, R.; Reniers, François

2017-03-01

A comparative study of the reduction of aqueous silver (Ag) and gold (Au) salts to colloidal Ag and Au nanoparticles, respectively, by a gaseous, cathodic, atmospheric-pressure microplasma electrode is presented. The resulting nanoparticles (NPs) were characterized by ultraviolet-visible (UV-vis) absorption spectroscopy and transmission electron microscopy (TEM), and the aqueous solution composition before and after experiments was determined by ionic conductivity, electrochemical potential, and/or UV-vis absorption measurements. TEM showed that Ag and Au NPs were spherical and non-agglomerated when synthesized in the presence of a stabilizer, polyvinyl alcohol. The charge injected by the plasma was correlated to the maximum intensity in the absorbance spectra which in turn depends on the nanoparticle concentration. Separately, the charge injected was correlated to the metal cation concentration. Ag and Au reduction rates were found to be directly proportional to the charge injected, independent of plasma current and process time. Differences in the mechanism for Ag and Au reduction were also observed, and solution species generated by the plasma and their role in the reduction process (e.g. H2O2, electrons) is discussed.

Imaging the Anomalous Charge Distribution Inside CsPbBr3 Perovskite Quantum Dots Sensitized Solar Cells.

PubMed

Panigrahi, Shrabani; Jana, Santanu; Calmeiro, Tomás; Nunes, Daniela; Martins, Rodrigo; Fortunato, Elvira

2017-10-24

Highly luminescent CsPbBr 3 perovskite quantum dots (QDs) have gained huge attention in research due to their various applications in optoelectronics, including as a light absorber in photovoltaic solar cells. To improve the performances of such devices, it requires a deeper knowledge on the charge transport dynamics inside the solar cell, which are related to its power-conversion efficiency. Here, we report the successful fabrication of an all-inorganic CsPbBr 3 perovskite QD sensitized solar cell and the imaging of anomalous electrical potential distribution across the layers of the cell under different illuminations using Kelvin probe force microscopy. Carrier generation, separation, and transport capacity inside the cells are dependent on the light illumination. Large differences in surface potential between electron and hole transport layers with unbalanced carrier separation at the junction have been observed under white light (full solar spectrum) illumination. However, under monochromatic light (single wavelength of solar spectrum) illumination, poor charge transport occurred across the junction as a consequence of less difference in surface potential between the active layers. The outcome of this study provides a clear idea on the carrier dynamic processes inside the cells and corresponding surface potential across the layers under the illumination of different wavelengths of light to understand the functioning of the solar cells and ultimately for the improvement of their photovoltaic performances.

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

Color-selective photodetection from intermediate colloidal quantum dots buried in amorphous-oxide semiconductors.

PubMed

Cho, Kyung-Sang; Heo, Keun; Baik, Chan-Wook; Choi, Jun Young; Jeong, Heejeong; Hwang, Sungwoo; Lee, Sang Yeol

2017-10-10

We report color-selective photodetection from intermediate, monolayered, quantum dots buried in between amorphous-oxide semiconductors. The proposed active channel in phototransistors is a hybrid configuration of oxide-quantum dot-oxide layers, where the gate-tunable electrical property of silicon-doped, indium-zinc-oxide layers is incorporated with the color-selective properties of quantum dots. A remarkably high detectivity (8.1 × 10 13 Jones) is obtained, along with three major findings: fast charge separation in monolayered quantum dots; efficient charge transport through high-mobility oxide layers (20 cm 2  V -1  s -1 ); and gate-tunable drain-current modulation. Particularly, the fast charge separation rate of 3.3 ns -1 measured with time-resolved photoluminescence is attributed to the intermediate quantum dots buried in oxide layers. These results facilitate the realization of efficient color-selective detection exhibiting a photoconductive gain of 10 7 , obtained using a room-temperature deposition of oxide layers and a solution process of quantum dots. This work offers promising opportunities in emerging applications for color detection with sensitivity, transparency, and flexibility.The development of highly sensitive photodetectors is important for image sensing and optical communication applications. Cho et al., report ultra-sensitive photodetectors based on monolayered quantum dots buried in between amorphous-oxide semiconductors and demonstrate color-detecting logic gates.

Simultaneous separation and analysis of water- and fat-soluble vitamins on multi-modal reversed-phase weak anion exchange material by HPLC-UV.

PubMed

Dabre, Romain; Azad, Nazanin; Schwämmle, Achim; Lämmerhofer, Michael; Lindner, Wolfgang

2011-04-01

Several methods for the separation of vitamins on HPLC columns were already validated in the last 20 years. However, most of the techniques focus on separating either fat- or water-soluble vitamins and only few methods are intended to separate lipophilic and hydrophilic vitamins simultaneously. A mixed-mode reversed-phase weak anion exchange (RP-WAX) stationary phase was developed in our laboratory in order to address such mixture of analytes with different chemical characteristics, which are difficult to separate on standard columns. The high versatility in usage of the RP-WAX chromatographic material allowed a baseline separation of ten vitamins within a single run, seven water-soluble and three fat-soluble, using three different chromatographic modes: some positively charged vitamins are eluted in ion exclusion and ion repulsion modes whereas the negatively charged molecules are eluted in the ion exchange mechanism. The non-charged molecules are eluted in a classical reversed-phase mode, regarding their polarities. The method was validated for the vitamin analysis in tablets, evaluating selectivity, robustness, linearity, accuracy, and precision. The validated method was finally employed for the analysis of the vitamin content of some commercially available supplement tablets. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

First tests of a novel radiation hard CMOS sensor process for Depleted Monolithic Active Pixel Sensors

NASA Astrophysics Data System (ADS)

Pernegger, H.; Bates, R.; Buttar, C.; Dalla, M.; van Hoorne, J. W.; Kugathasan, T.; Maneuski, D.; Musa, L.; Riedler, P.; Riegel, C.; Sbarra, C.; Schaefer, D.; Schioppa, E. J.; Snoeys, W.

2017-06-01

The upgrade of the ATLAS [1] tracking detector for the High-Luminosity Large Hadron Collider (LHC) at CERN requires novel radiation hard silicon sensor technologies. Significant effort has been put into the development of monolithic CMOS sensors but it has been a challenge to combine a low capacitance of the sensing node with full depletion of the sensitive layer. Low capacitance brings low analog power. Depletion of the sensitive layer causes the signal charge to be collected by drift sufficiently fast to separate hits from consecutive bunch crossings (25 ns at the LHC) and to avoid losing the charge by trapping. This paper focuses on the characterization of charge collection properties and detection efficiency of prototype sensors originally designed in the framework of the ALICE Inner Tracking System (ITS) upgrade [2]. The prototypes are fabricated both in the standard TowerJazz 180nm CMOS imager process [3] and in an innovative modification of this process developed in collaboration with the foundry, aimed to fully deplete the sensitive epitaxial layer and enhance the tolerance to non-ionizing energy loss. Sensors fabricated in standard and modified process variants were characterized using radioactive sources, focused X-ray beam and test beams before and after irradiation. Contrary to sensors manufactured in the standard process, sensors from the modified process remain fully functional even after a dose of 1015neq/cm2, which is the the expected NIEL radiation fluence for the outer pixel layers in the future ATLAS Inner Tracker (ITk) [4].

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.

Greatly Increasing Trapped Ion Populations for Mobility Separations Using Traveling Waves in Structures for Lossless Ion Manipulations

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

Deng, Liulin; Ibrahim, Yehia M.; Garimella, Sandilya V. B.

The initial use of traveling waves (TW) for ion mobility (IM) separations using a structures for lossless ion manipulations (SLIM) employed an ion funnel trap (IFT) to accumulate ions from a continuous electrospray ionization source, and limited to injected ion populations of ~106 charges due to the onset of space charge effects in the trapping region. Additional limitations arise due to the loss of resolution for the injection of ions over longer periods (e.g. in extended pulses). In this work a new SLIM ‘flat funnel’ (FF) module has been developed and demonstrated to enable the accumulation of much larger ionmore » populations and their injection for IM separations. Ion current measurements indicate a capacity of ~3.2×108 charges for the extended trapping volume, over an order of magnitude greater than the IFT. The orthogonal ion injection into a funnel shaped separation region can greatly reduce space charge effects during the initial IM separation stage, and the gradually reduced width of the path allows the ion packet to be increasingly compressed in the lateral dimension as the separation progresses, allowing e.g. efficient transmission through conductance limits or compatibility with subsequent ion manipulations. This work examined the TW, RF, and DC confining field SLIM parameters involved in ion accumulation, injection, transmission and separation in the FF IM module using both direct ion current and MS measurements. Wide m/z range ion transmission is demonstrated, along with significant increases in signal to noise (S/N) ratios due to the larger ion populations injected. Additionally, we observed a reduction in the chemical background, which was attributed to more efficient desolvation of solvent related clusters over the extended ion accumulation periods. The TW SLIM FF IM module is anticipated to be especially effective as a front end for long path SLIM IM separation modules.« less

Computer modeling and simulation in inertial confinement fusion

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

McCrory, R.L.; Verdon, C.P.

1989-03-01

The complex hydrodynamic and transport processes associated with the implosion of an inertial confinement fusion (ICF) pellet place considerable demands on numerical simulation programs. Processes associated with implosion can usually be described using relatively simple models, but their complex interplay requires that programs model most of the relevant physical phenomena accurately. Most hydrodynamic codes used in ICF incorporate a one-fluid, two-temperature model. Electrons and ions are assumed to flow as one fluid (no charge separation). Due to the relatively weak coupling between the ions and electrons, each species is treated separately in terms of its temperature. In this paper wemore » describe some of the major components associated with an ICF hydrodynamics simulation code. To serve as an example we draw heavily on a two-dimensional Lagrangian hydrodynamic code (ORCHID) written at the University of Rochester's Laboratory for Laser Energetics. 46 refs., 19 figs., 1 tab.« less

48 CFR 871.201-2 - Requirements when contracts are not required.

Code of Federal Regulations, 2010 CFR

2010-10-01

..., fees, and charges for books, supplies, or services necessary to train or educate an eligible veteran..., including the rate of tuition, fees, and separate charges, if any, for books, supplies, and equipment... accordance with catalog or other published document (identify publication). The statement of charges may not...

Stacked white OLED having separate red, green and blue sub-elements

DOEpatents

Forrest, Stephen; Qi, Xiangfei; Slootsky, Michael

2014-07-01

The present invention relates to efficient organic light emitting devices (OLEDs). The devices employ three emissive sub-elements, typically emitting red, green and blue, to sufficiently cover the visible spectrum. Thus, the devices may be white-emitting OLEDs, or WOLEDs. Each sub-element comprises at least one organic layer which is an emissive layer--i.e., the layer is capable of emitting light when a voltage is applied across the stacked device. The sub-elements are vertically stacked and are separated by charge generating layers. The charge-generating layers are layers that inject charge carriers into the adjacent layer(s) but do not have a direct external connection.

Electrostatic Explorations.

ERIC Educational Resources Information Center

Gallai, Ditta; Stewart, Gay

1998-01-01

Presents a set of hands-on electrostatics experiments in the form of an activity guide and worksheet through which students discover the different types of electric charge, Coulomb's Law, induced charge separation, and grounding. (DDR)

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.

Cocatalysts in Semiconductor-based Photocatalytic CO2 Reduction: Achievements, Challenges, and Opportunities.

PubMed

Ran, Jingrun; Jaroniec, Mietek; Qiao, Shi-Zhang

2018-02-01

Ever-increasing fossil-fuel combustion along with massive CO 2 emissions has aroused a global energy crisis and climate change. Photocatalytic CO 2 reduction represents a promising strategy for clean, cost-effective, and environmentally friendly conversion of CO 2 into hydrocarbon fuels by utilizing solar energy. This strategy combines the reductive half-reaction of CO 2 conversion with an oxidative half reaction, e.g., H 2 O oxidation, to create a carbon-neutral cycle, presenting a viable solution to global energy and environmental problems. There are three pivotal processes in photocatalytic CO 2 conversion: (i) solar-light absorption, (ii) charge separation/migration, and (iii) catalytic CO 2 reduction and H 2 O oxidation. While significant progress is made in optimizing the first two processes, much less research is conducted toward enhancing the efficiency of the third step, which requires the presence of cocatalysts. In general, cocatalysts play four important roles: (i) boosting charge separation/transfer, (ii) improving the activity and selectivity of CO 2 reduction, (iii) enhancing the stability of photocatalysts, and (iv) suppressing side or back reactions. Herein, for the first time, all the developed CO 2 -reduction cocatalysts for semiconductor-based photocatalytic CO 2 conversion are summarized, and their functions and mechanisms are discussed. Finally, perspectives in this emerging area are provided. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Controlled Synthesis of CuS/TiO2 Heterostructured Nanocomposites for Enhanced Photocatalytic Hydrogen Generation through Water Splitting.

PubMed

Chandra, Moumita; Bhunia, Kousik; Pradhan, Debabrata

2018-04-16

Photocatalytic hydrogen (H 2 ) generation through water splitting has attracted substantial attention as a clean and renewable energy generation process that has enormous potential in converting solar-to-chemical energy using suitable photocatalysts. The major bottleneck in the development of semiconductor-based photocatalysts lies in poor light absorption and fast recombination of photogenerated electron-hole pairs. Herein we report the synthesis of CuS/TiO 2 heterostructured nanocomposites with varied TiO 2 contents via simple hydrothermal and solution-based process. The morphology, crystal structure, composition, and optical properties of the as-synthesized CuS/TiO 2 hybrids are evaluated in detail. Controlling the CuS/TiO 2 ratio to an optimum value leads to the highest photocatalytic H 2 production rate of 1262 μmol h -1 g -1 , which is 9.7 and 9.3 times higher than that of pristine TiO 2 nanospindles and CuS nanoflakes under irradiation, respectively. The enhancement in the H 2 evolution rate is attributed to increased light absorption and efficient charge separation with an optimum CuS coverage on TiO 2 . The photoluminescence and photoelectrochemical measurements further confirm the efficient separation of charge carriers in the CuS/TiO 2 hybrid. The mechanism and synergistic role of CuS and TiO 2 semiconductors for enhanced photoactivity is further delineated.

Magnetic-Nanoflocculant-Assisted Water-Nonpolar Solvent Interface Sieve for Microalgae Harvesting.

PubMed

Lee, Kyubock; Na, Jeong-Geol; Seo, Jung Yoon; Shim, Tae Soup; Kim, Bohwa; Praveenkumar, Ramasamy; Park, Ji-Yeon; Oh, You-Kwan; Jeon, Sang Goo

2015-08-26

Exploitation of magnetic flocculants is regarded as a very promising energy-saving approach to microalgae harvesting. However, its practical applicability remains limited, mainly because of the problem of the postharvest separation of magnetic flocculants from microalgal flocs, which is crucial both for magnetic-flocculant recycling and high-purity microalgal biomasses, but which is also a very challenging and energy-consuming step. In the present study, we designed magnetic nanoflocculants dually functionalizable by two different organosilane compounds, (3-aminopropyl)triethoxysilane (APTES) and octyltriethoxysilane (OTES), which flocculate negatively charged microalgae and are readily detachable at the water-nonpolar organic solvent (NOS) interface only by application of an external magnetic field. APTES functionalization imparts a positive zeta potential charge (29.6 mV) to magnetic nanoflocculants, thereby enabling microalgae flocculation with 98.5% harvesting efficiency (with a dosage of 1.6 g of dMNF/g of cells). OTES functionalization imparts lipophilicity to magnetic nanoflocculants to make them compatible with NOS, thus effecting efficient separation of magnetic flocculants passing through the water-NOS interface sieve from hydrophilic microalgae. Our new energy-saving approach to microalgae harvesting concentrates microalgal cultures (∼1.5 g/L) up to 60 g/L, which can be directly connected to the following process of NOS-assisted wet lipid extraction or biodiesel production, and therefore provides, by simplifying multiple downstream processes, a great potential cost reduction in microalgae-based biorefinement.

Enhanced charge separation of rutile TiO2 nanorods by trapping holes and transferring electrons for efficient cocatalyst-free photocatalytic conversion of CO2 to fuels.

PubMed

Wu, Jing; Lu, Hongwei; Zhang, Xuliang; Raziq, Fazal; Qu, Yang; Jing, Liqiang

2016-04-11

Modification with chloride and phosphate anions, and coupling with carbon nanotubes could effectively trap holes and transfer the electrons of rutile nanorods, respectively, so as to greatly promote photogenerated charge separation, leading to an obviously-improved cocatalyst-free photocatalytic conversion of CO2 to CH4 and CO, along with the positive effects of constructed phosphate bridges.

Report of investigations into charge cadmium reactivity: Nickel-cadmium cell ESD 91-86

NASA Technical Reports Server (NTRS)

Lewis, Harlan L.

1992-01-01

In Aug. 1990, a presentation was given at the 25th Ann. IECEC meeting on the results of Destructive Physical Analysis (DPA) on two successive sets of Ni-Cd cells. The cells were of two different separator types, Pellon 2505 and 2536. One cell of each separator type was analyzed on two occasions; the first pair were analyzed to establish baseline data on essentially new cells; the second pair were analyzed after the cells had been on charge-discharge cycling for a year in connection with a satellite simulation study. The gas composition found in the cells, the absence of charged cadmium in the analytical data, and the appearance of dried out portions on the Cd plates in the one year cell S/N 7 which used Pellon 2505 as its separator material, were questions which arose. These concerns are answered and the observational results are clarified.

Worm Algorithm simulations of the hole dynamics in the t-J model

NASA Astrophysics Data System (ADS)

Prokof'ev, Nikolai; Ruebenacker, Oliver

2001-03-01

In the limit of small J << t, relevant for HTSC materials and Mott-Hubbard systems, computer simulations have to be performed for large systems and at low temperatures. Despite convincing evidence against spin-charge separation obtained by various methods for J > 0.4t there is an ongoing argument that at smaller J spin-charge separation is still possible. Worm algorithm Monte Carlo simulations of the hole Green function for 0.1 < J/t < 0.4 were performed on lattices with up to 32x32 sites, and at temperature J/T = 40 (for the largest size). Spectral analysis reveals a single, delta-function sharp quasiparticle peak at the lowest edge of the spectrum and two distinct peaks above it at all studied J. We rule out the possibility of spin-charge separation in this parameter range, and present, apparently, the hole spectral function in the thermodynamic limit.

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.

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

PubMed

Lerch, Sarah; Reinhard, Björn M

2018-04-23

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

An improved model for computing the trajectories of conductive particles in roll-type electrostatic separator for recycling metals from WEEE.

PubMed

Wu, Jiang; Li, Jia; Xu, Zhenming

2009-08-15

Electrostatic separation presents an effective and environmentally friendly way for recycling metals and nonmetals from ground waste electrical and electronic equipment (WEEE). For this process, the trajectory of conductive particle is significant and some models have been established. However, the results of previous researches are limited by some simplifying assumptions and lead to a notable discrepancy between the model prediction and the experimental results. In the present research, a roll-type corona-electrostatic separator and ground printed circuit board (PCB) wastes were used to investigate the trajectory of the conductive particle. Two factors, the air drag force and the different charging situation, were introduced into the improved model. Their effects were analyzed and an improved model for the theoretical trajectory of conductive particle was established. Compared with the previous one, the improved model shows a good agreement with the experimental results. It provides a positive guidance for designing of separator and makes a progress for recycling the metals and nonmetals from WEEE.

Separators used in microbial electrochemical technologies: Current status and future prospects.

PubMed

Daud, Siti Mariam; Kim, Byung Hong; Ghasemi, Mostafa; Daud, Wan Ramli Wan

2015-11-01

Microbial electrochemical technologies (METs) are emerging green processes producing useful products from renewable sources without causing environmental pollution and treating wastes. The separator, an important part of METs that greatly affects the latter's performance, is commonly made of Nafion proton exchange membrane (PEM). However, many problems have been identified associated with the Nafion PEM such as high cost of membrane, significant oxygen and substrate crossovers, and transport of cations other than protons protons and biofouling. A variety of materials have been offered as alternative separators such as ion-exchange membranes, salt bridges, glass fibers, composite membranes and porous materials. It has been claimed that low cost porous materials perform better than PEM. These include J-cloth, nylon filter, glass fiber mat, non-woven cloth, earthen pot and ceramics that enable non-ion selective charge transfer. This paper provides an up-to-date review on porous separators and plots directions for future studies. Copyright © 2015 Elsevier Ltd. All rights reserved.

47 CFR 69.121 - Connection charges for expanded interconnection.

Code of Federal Regulations, 2010 CFR

2010-10-01

... separations. (2) Charges for subelements associated with physical collocation or virtual collocation, other... of the virtual collocation equipment described in § 64.1401(e)(1) of this chapter, may reasonably...

77 FR 19425 - Prescription Drugs Not Administered During Treatment; Update to Administrative Cost for Calendar...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-03-30

... that requires automobile accident reparations insurance. This updated administrative cost charge was... automobile accident reparations insurance, ``charges billed separately for such prescription drugs will...

Redox chemistry at liquid/liquid interfaces

NASA Technical Reports Server (NTRS)

Volkov, A. G.; Deamer, D. W.

1997-01-01

The interface between two immiscible liquids with immobilized photosynthetic pigments can serve as the simplest model of a biological membrane convenient for the investigation of photoprocesses accompanied by spatial separation of charges. As it follows from thermodynamics, if the resolvation energies of substrates and products are very different, the interface between two immiscible liquids may act as a catalyst. Theoretical aspects of charge transfer reactions at oil/water interfaces are discussed. Conditions under which the free energy of activation of the interfacial reaction of electron transfer decreases are established. The activation energy of electron transfer depends on the charges of the reactants and dielectric permittivity of the non-aqueous phase. This can be useful when choosing a pair of immiscible solvents to decrease the activation energy of the reaction in question or to inhibit an undesired process. Experimental interfacial catalytic systems are discussed. Amphiphilic molecules such as chlorophyll or porphyrins were studied as catalysts of electron transfer reactions at the oil/water interface.

Charge Transport in Trehalose-Derived Sugar Glasses

NASA Astrophysics Data System (ADS)

Nemzer, Louis; Navati, Mahantesh; Friedman, Joel; Epstein, Arthur

2013-03-01

Trehalose is a naturally occurring disaccharide with a well-known ability to preserve the biological function of proteins and cell membranes during periods of stress, including dehydration, by stabilizing the conformations of the macromolecules within a glassy matrix. This phenomenon makes use of the propensity of trehalose to interact strongly with protein functional groups and solvating water molecules via hydrogen bonding. Recently, it has been shown that trehalose sugar glasses also support long range charge transport in the form of oxidation-reduction reactions occurring between spatially separated donors and acceptors. Based on an Arrhenius conductivity analysis, along with IR-absorption and dielectric spectroscopy data, we propose that a Grotthuss-like proton hopping mechanism is responsible for the high charge carrier mobility and observed bias-dependent apparent activation energy. The possibility is raised for novel redox reactions to be performed on proteins constrained to specific 3D conformations. This could lead to a deeper understanding of biological processes, such as anhydrobiosis, as well as the development of new biomimetic photovoltaic devices.

Tribocharging Lunar Soil for Electrostatic Beneficiation

NASA Technical Reports Server (NTRS)

2008-01-01

Future human lunar habitation requires using in situ materials for both structural components and oxygen production. Lunar bases must be constructed from thermal-and radiation-shielding materials that will provide significant protection from the harmful cosmic energy which normally bombards the lunar surface. In addition, shipping oxygen from Earth is weight-prohibitive, and therefore investigating the production of breathable oxygen from oxidized mineral components is a major ongoing NASA research initiative. Lunar regolith may meet the needs for both structural protection and oxygen production. Already a number of oxygen production technologies are being tested, and full-scale bricks made of lunar simulant have been sintered. The beneficiation, or separation, of lunar minerals into a refined industrial feedstock could make production processes more efficient, requiring less energy to operate and maintain and producing higher-performance end products. The method of electrostatic beneficiation used in this research charges mineral powders (lunar simulant) by contact with materials of a different composition. The simulant acquires either a positive or negative charge depending upon its composition relative to the charging material.

A two-dimensional particle-in-cell model of a dusty plasma

NASA Technical Reports Server (NTRS)

Young, B.; Cravens, T. E.; Armstrong, T. P.; Friauf, R. J.

1994-01-01

Dusty plasmas are present in comets, in the ring systems of the outer planets, and in the interstellar medium. A two-dimensional particle-in-cell (PIC) model of a dusty plasma is presented in this paper. The PIC code is best suited for modeling the plasma-dust interaction for large grains, with diameters of the order of a centimeter. We have modeled the charging process for an individual dust grain and the associated potential pattern in the surrounding plasma. We have also considered the case of a large number of grains in a plasma, with intergrain separations of the order of the Debye length, and have shown that the plasma becomes depleted and the charge on a dust grain is reduced, as other workers in this field have predicted (cf. C. K. Goertz, 1989). We examine the electron and ion distribution functions in the vicinity of a charged grain and demonstrate that the ions near a grain have clearly been accelerated by the electrostatic potential.

Charging YOYO-1 on Capillary Wall for Online DNA Intercalation and Integrating This Approach with Multiplex PCR and Bare Narrow Capillary–Hydrodynamic Chromatography for Online DNA Analysis

PubMed Central

2016-01-01

Multiplex polymerase chain reaction (PCR) has been widely utilized for high-throughput pathogen identification. Often, a dye is used to intercalate the amplified DNA fragments, and identifications of the pathogens are carried out by DNA melting curve analysis or gel electrophoresis. Integrating DNA amplification and identification is a logic path toward maximizing the benefit of multiplex PCR. Although PCR and gel electrophoresis have been integrated, replenishing the gels after each run is tedious and time-consuming. In this technical note, we develop an approach to address this issue. We perform multiplex PCR inside a capillary, transfer the amplified fragments to a bare narrow capillary, and measure their lengths online using bare narrow capillary–hydrodynamic chromatography (BaNC-HDC), a new technique recently developed in our laboratory for free-solution DNA separation. To intercalate the DNA with YOYO-1 (a fluorescent dye) for BaNC-HDC, we flush the capillary column with a YOYO-1 solution; positively charged YOYO-1 is adsorbed (or charged) onto the negatively charged capillary wall. As DNA molecules are driven down the column for separation, they react with the YOYO-1 stored on the capillary wall and are online-intercalated with the dye. With a single YOYO-1 charging, the column can be used for more than 40 runs, although the fluorescence signal intensities of the DNA peaks decrease gradually. Although the dye-DNA intercalation occurs during the separation, it does not affect the retention times, separation efficiencies, or resolutions. PMID:25555111

Signals of strong electronic correlation in ion scattering processes

NASA Astrophysics Data System (ADS)

Bonetto, F.; Gonzalez, C.; Goldberg, E. C.

2016-05-01

Previous measurements of neutral atom fractions for S r+ scattered by gold polycrystalline surfaces show a singular dependence with the target temperature. There is still not a theoretical model that can properly describe the magnitude and the temperature dependence of the neutralization probabilities found. Here, we applied a first-principles quantum-mechanical theoretical formalism to describe the time-dependent scattering process. Three different electronic correlation approaches consistent with the system analyzed are used: (i) the spinless approach, where two charge channels are considered (S r0 and S r+ ) and the spin degeneration is neglected; (ii) the infinite-U approach, with the same charge channels (S r0 and S r+ ) but considering the spin degeneration; and (iii) the finite-U approach, where the first ionization and second ionization energy levels are considered very, but finitely, separated. Neutral fraction magnitudes and temperature dependence are better described by the finite-U approach, indicating that e -correlation plays a significant role in charge-transfer processes. However, none of them is able to explain the nonmonotonous temperature dependence experimentally obtained. Here, we suggest that small changes in the surface work function introduced by the target heating, and possibly not detected by experimental standard methods, could be responsible for that singular behavior. Additionally, we apply the same theoretical model using the infinite-U approximation for the Mg-Au system, obtaining an excellent description of the experimental neutral fractions measured.

Multiplicity evolution of identified particle charge-dependent correlations in Pb-Pb, p-Pb and pp collisions at the LHC with ALICE

NASA Astrophysics Data System (ADS)

Pan, Jinjin; Alice Collaboration

2017-09-01

The charge pair creation and transport processes in heavy-ion collisions are investigated experimentally by measurements of charge-dependent correlations of identified particle pairs, related to the Balance Function. The produced pair separation in rapidity is expected to be larger for hadrons arising from quark-antiquark pair creation in the early stages of the collision than for hadrons emerging from the later hadronization stage. Correlations are reported for charged-pion pairs in Pb-Pb, p-Pb and pp collisions at √{sNN } = 2.76, 5.02 and 7 TeV, respectively; and for charged-kaon pairs in Pb-Pb collisions at √{sNN } = 2.76 TeV. The correlations are measured as a function of relative rapidity Δy and azimuthal angle Δϕ , and are dominated by a peak centered at Δy = Δϕ = 0. We observe that the peak widths in Δy and Δϕ are narrower in higher multiplicity events in Pb-Pb, p-Pb, and pp collisions, which is consistent with the effects of radial flow, as well as the two-wave quark production mechanism. We investigate the charge transport and system evolution further by studying the Δϕ width of the peak as a function of Δy. Funded by the US Department of Energy.

Li-Ion Battery and Supercapacitor Hybrid Design for Long Extravehicular Activities

NASA Technical Reports Server (NTRS)

Jeevarajan, Judith

2013-01-01

With the need for long periods of extravehicular activities (EVAs) on the Moon or Mars or a near-asteroid, the need for long-performance batteries has increased significantly. The energy requirements for the EVA suit, as well as surface systems such as rovers, have increased significantly due to the number of applications they need to power at the same time. However, even with the best state-of-the-art Li-ion batteries, it is not possible to power the suit or the rovers for the extended period of performance. Carrying a charging system along with the batteries makes it cumbersome and requires a self-contained power source for the charging system that is usually not possible. An innovative method to charge and use the Li-ion batteries for long periods seems to be necessary and hence, with the advent of the Li-ion supercapacitors, a method has been developed to extend the performance period of the Li-ion power system for future exploration applications. The Li-ion supercapacitors have a working voltage range of 3.8 to 2.5 V, and are different from a traditional supercapacitor that typically has a working voltage of 1 V. The innovation is to use this Li-ion supercapacitor to charge Liion battery systems on an as-needed basis. The supercapacitors are charged using solar arrays and have battery systems of low capacity in parallel to be able to charge any one battery system while they provide power to the application. Supercapacitors can safely take up fast charge since the electrochemical process involved is still based on charge separation rather than the intercalation process seen in Li-ion batteries, thus preventing lithium metal deposition on the anodes. The lack of intercalation and eliminating wear of the supercapacitors allows for them to be charged and discharged safely for a few tens of thousands of cycles. The Li-ion supercapacitors can be charged from the solar cells during the day during an extended EVA. The Liion battery used can be half the capacity required for a nominal EVA. The small Li-ion battery can be divided into two parallel modules with independent charging ports that would allow the supercapacitors to charge one battery while the other is providing power to the rover or suit.

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.)

Photo-electrochemical properties of graphene wrapped hierarchically branched nanostructures obtained through hydrothermally transformed TiO2 nanotubes

NASA Astrophysics Data System (ADS)

Rambabu, Y.; Jaiswal, Manu; Roy, Somnath C.

2017-10-01

Hierarchically structured nanomaterials play an important role in both light absorption and separation of photo-generated charges. In the present study, hierarchically branched TiO2 nanostructures (HB-MLNTs) are obtained through hydrothermal transformation of electrochemically anodized TiO2 multi-leg nanotubes (MLNT) arrays. Photo-anodes based on HB-MLNTs demonstrated 5 fold increase in applied bias to photo-conversion efficiency (%ABPE) over that of TiO2 MLNTs without branches. Further, such nanostructures are wrapped with reduced graphene oxide (rGO) films to enhance the charge separation, which resulted in ∼6.5 times enhancement in %ABPE over that of bare MLNTs. We estimated charge transport (η tr) and charge transfer (η ct) efficiencies by analyzing the photo-current data. The ultra-fine nano branches grown on the MLNTs are effective in increasing light absorption through multiple scattering and improving charge transport/transfer efficiencies by enlarging semiconductor/electrolyte interface area. The charge transfer resistance, interfacial capacitance and electron decay time have been estimated through electrochemical impedance measurements which correlate with the results obtained from photocurrent measurements.

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

5 CFR 842.404 - Reductions in basic annuity.

Code of Federal Regulations, 2010 CFR

2010-01-01

... by removal for cause on charges of misconduct or delinquency; (2) A firefighter and/or law enforcement officer, except one separated by removal for cause on charges of misconduct of delinquency; or (3...

Electrophoresis demonstration on Apollo 16

NASA Technical Reports Server (NTRS)

Snyder, R. S.

1972-01-01

Free fluid electrophoresis, a process used to separate particulate species according to surface charge, size, or shape was suggested as a promising technique to utilize the near zero gravity condition of space. Fluid electrophoresis on earth is disturbed by gravity-induced thermal convection and sedimentation. An apparatus was developed to demonstrate the principle and possible problems of electrophoresis on Apollo 14 and the separation boundary between red and blue dye was photographed in space. The basic operating elements of the Apollo 14 unit were used for a second flight demonstration on Apollo 16. Polystyrene latex particles of two different sizes were used to simulate the electrophoresis of large biological particles. The particle bands in space were extremely stable compared to ground operation because convection in the fluid was negligible. Electrophoresis of the polystyrene latex particle groups according to size was accomplished although electro-osmosis in the flight apparatus prevented the clear separation of two particle bands.

Efficient charge-carrier extraction from Ag₂S quantum dots prepared by the SILAR method for utilization of multiple exciton generation.

PubMed

Zhang, Xiaoliang; Liu, Jianhua; Johansson, Erik M J

2015-01-28

The utilization of electron-hole pairs (EHPs) generated from multiple excitons in quantum dots (QDs) is of great interest toward efficient photovoltaic devices and other optoelectronic devices; however, extraction of charge carriers remains difficult. Herein, we extract photocharges from Ag2S QDs and investigate the dependence of the electric field on the extraction of charges from multiple exciton generation (MEG). Low toxic Ag2S QDs are directly grown on TiO2 mesoporous substrates by employing the successive ionic layer adsorption and reaction (SILAR) method. The contact between QDs is important for the initial charge separation after MEG and for the carrier transport, and the space between neighbor QDs decreases with more SILAR cycles, resulting in better charge extraction. At the optimal electric field for extraction of photocharges, the results suggest that the threshold energy (hνth) for MEG is 2.41Eg. The results reveal that Ag2S QD is a promising material for efficient extraction of charges from MEG and that QDs prepared by SILAR have an advantageous electrical contact facilitating charge separation and extraction.

An exploration into municipal waste charges for environmental management at local level: The case of Spain.

PubMed

Puig-Ventosa, Ignasi; Sastre Sanz, Sergio

2017-11-01

Municipal waste charges have been widely acknowledged as a crucial tool for waste management at the local level. This is because they contribute to financing the costly provision of waste collection and treatment services and they can be designed to provide an economic stimulus to encourage citizens and local businesses to improve separate collection and recycling. This work presents a methodology to evaluate a sample of 125 municipal waste charges in Spain for the year 2015, covering 33.91% of the Spanish population. The qualitative benchmarking of municipal waste charges shows that flat fees are frequent, whereas variable fees are set according to criteria that are weakly related to waste generation. The average fee per household is €82.2 per year, which does not provide full cost recovery. The current configuration of municipal waste charges penalises taxpayers contributing to source separation of waste, while subsidising less environmentally friendly behaviours. In this sense, municipal waste charges in Spain are far from applying the polluter pays principle. Furthermore, it is argued that municipal waste charges are ineffective for promoting the proper application of the so-called 'waste hierarchy'.

Observation of the retarded transportation of a photogenerated hole on epitaxial graphene.

PubMed

Wang, Shujie; Yuan, Xizhi; Bi, Xiaofeng; Wang, Xiaomei; Huang, Qingsong

2015-10-07

Graphene is usually adopted as an assistant additive for catalysts in photocatalytic processes, because of its ability to accelerate the separation of photogenerated charge carriers. To elucidate the mechanism, hydrogen peroxide is adopted to convert the O2(-)˙ active species into OH˙ for degradation of an organic dye. If the pH value is less than 7, the concentration of the OH˙ species can be reduced more quickly with the addition of graphene than without, because negatively charged electrons can be transported quickly on graphene. If the pH value is larger than 7, the concentration of OH˙ can be promoted by the catalyst SiC with photogenerated h(+) release and reaction with OH(-), however the concentration is reduced if the SiC catalyst is covered by a graphene sheet, as it retards h(+) release from the SiC substrate. Our findings have provided a certification for the role of graphene in photo-catalytic processes.

Contact electrification of insulating materials

NASA Astrophysics Data System (ADS)

Lacks, Daniel J.; Mohan Sankaran, R.

2011-11-01

The electrostatic charge that is generated when two materials are contacted or rubbed and then separated is a well-known physical process that has been studied for more than 2500 years. Contact electrification occurs in many contexts, both natural and technological. For example, in dust storms the collisions between particles lead to electrostatic charging and in extreme cases, extraordinary lightning displays. In electrophotography, toner particles are intentionally charged to guide their deposition in well-defined patterns. Despite such a long history and so many important consequences, a fundamental understanding of the mechanism behind contact electrification remains elusive. An open question is what type of species are transferred between the surfaces to generate charge—experiments suggest various species ranging from electrons to ions to nanoscopic bits of material, and theoretical work suggests that non-equilibrium states may play an important role. Another open question is the contact electrification that occurs when two insulating materials with identical physical properties touch—since there is no apparent driving force, it is not clear why charge transfer occurs. A third open question involves granular systems—models and experiments have shown that a particle-size dependence for the charging often exists. In this review, we discuss the fundamental aspects of contact electrification and highlight recent research efforts aimed at understanding these open questions.

Excellent photocatalytic hydrogen production over CdS nanorods via using noble metal-free copper molybdenum sulfide (Cu2MoS4) nanosheets as co-catalysts

NASA Astrophysics Data System (ADS)

Hong, Sangyeob; Kumar, D. Praveen; Reddy, D. Amaranatha; Choi, Jiha; Kim, Tae Kyu

2017-02-01

Charge carrier recombination and durability issues are major problems in photocatalytic hydrogen (H2) evolution processes. Thus, there is a very important necessitate to extend an efficient photocatalyst to control charge-carrier dynamics in the photocatalytic system. We have developed copper molybdenum sulfide (Cu2MoS4) nanosheets as co-catalysts with CdS nanorods for controlling charge carriers without recombination for use in photocatalytic H2 evolution under simulated solar light irradiation. Effective control and utilization of charge carriers are possible by loading Cu2MoS4 nanosheets onto the CdS nanorods. The loading compensates for the restrictions of CdS, and stimulated synergistic effects, such as efficient photoexcited charge separation, lead to an improvement in photostability because of the layered structure of the Cu2MoS4nanosheets. These layered Cu2MoS4 nanosheets have emerged as novel and active replacements for precious noble metal co-catalysts in photocatalytic H2 production by water splitting. We have obtained superior H2 production rates by using Cu2MoS4 loaded CdS nanorods. The physicochemical properties of the composites are analyzed by diverse characterization techniques.

Single-hole spectral function and spin-charge separation in the t-J model

NASA Astrophysics Data System (ADS)

Mishchenko, A. S.; Prokof'ev, N. V.; Svistunov, B. V.

2001-07-01

Worm algorithm Monte Carlo simulations of the hole Green function with subsequent spectral analysis were performed for 0.1<=J/t<=0.4 on lattices with up to L×L=32×32 sites at a temperature as low as T=J/40, and present, apparently, the hole spectral function in the thermodynamic limit. Spectral analysis reveals a δ-function-sharp quasiparticle peak at the lower edge of the spectrum that is incompatible with the power-law singularity and thus rules out the possibility of spin-charge separation in this parameter range. Spectral continuum features two peaks separated by a gap ~4÷5 t.

How to harvest solar energy with the photosynthetic reaction center

NASA Astrophysics Data System (ADS)

Balaeff, Alexander; Reyes, Justin

Photosynthetic reaction center (PRC) is a protein complex that performs a key step in photosynthesis: the electron-hole separation driven by photon absorbtion. The PRC has a great promise for applications in solar energy harvesting and photosensing. Such applications, however, are hampered by the difficulty in extracting the photogenerated electric charge from the PRC. To that end, it was proposed to attach the PRC to a molecular wire through which the charge could be collected. In order to find the attachment point for the wire that would maximize the rate of charge outflow from the PRC, we performed a computational study of the PRC from the R. virdis bacterium. An ensemble of PRC structures generated by a molecular dynamics simulation was used to calculate the rate of charge transport from the site of initial charge separation to several trial sites on the protein surface. The Pathways model was used to calculate the charge transfer rate in each step of the network of heme co-factors through which the charge transport was presumed to proceed. A simple kinetic model was then used to determine the overall rate of the multistep charge transport. The calculations revealed several candidate sites for the molecular wire attachment, recommended for experimental verification.

Nano-TiO2 decorated carbon coating on the separator to physically and chemically suppress the shuttle effect for lithium-sulfur battery

NASA Astrophysics Data System (ADS)

Shao, Hongyuan; Wang, Weikun; Zhang, Hao; Wang, Anbang; Chen, Xiaonong; Huang, Yaqin

2018-02-01

Despite recent progress in designing modified separators for lithium-sulfur (Li-S) batteries, detail in optimizing the synergistic effect between chemical and physical immobilization for lithium polysulfides (LiPS) in modified separator hasn't been investigated totally. Here, a nano-TiO2 decorated carbon layer (T-DCL) has been successfully applied to modify separator for the Li-S battery. The results indicate that appropriate weight percentage of nano-TiO2 uniformly distributed in conductive carbon layer is effective to chemically and physically immobilize for LiPS, and promote the electron transfer during discharge/charge process. The performance of the modified Li-S battery with T-DCL separator are significantly enhanced, with a specific capacity of 883 mAh g-1 retained after 180 cycles at 0.1 C and 762 mAh g-1 retained after 200 cycles at 0.5C, which are much higher than that of separators only coated with TiO2 layer or conductive carbon layer. Besides, the separator coated with T-DCL also shows low electrochemical impedance and good lithium anode protection. These results indicate that separator with T-DCL is promising to balance the physical and chemical LiPS trapping effect, and optimize the electrochemical performance for Li-S battery.

Light harvesting and charge management by Ni4S3 modified metal-organic frameworks and rGO in the process of photocatalysis.

PubMed

Liu, Duanduan; Jin, Zhiliang; Zhang, Yongke; Wang, Guorong; Ma, Bingzhen

2018-06-01

Harvesting and charge management is obtained by means of Ni 4 S 3 modified Metal-organic Frameworks (MOF) and rGO, namely, the Uio-66 (Zr)/rGO combined with Ni 4 S 3 photocatalyst was successfully prepared with the solvothermal method. The Ni 4 S 3 acted as the electron transfer agent greatly improve the electrons transmission from the excited state dye to the rGO/MOF surface for proton reduction reaction. The hydrogen production amount over EY-sensitized rGO/MOF/Ni 4 S 3 photocatalyst has reached 280 μmol for 5 h, which is about 14 times than that of the pure Ni 4 S 3 photocatalyst and 185 times than that of the pure rGO/MOF photocatalyst under visible light irradiation (λ ≥ 420 nm). In the composite, the rGO acts as electron-transfer mediator and Ni 4 S 3 serves as H 2 -evolution active site. A series of studies shown that the Ni 4 S 3 modified MOF and rGO provided more active sites and improved the efficiency of photo-generated charge separation by means of several characterizations such as SEM, XRD, XPS, Element Mapping, UV-vis DRS, BET, Photocurrent, Voltammetric Scanning, Fluorescence Spectra and FTIR. and the results of which were in good agreement with each other. The photoelectron migration rate and photogenerated charge separation efficiency of the composite can be obviously increased with graphene as a good electron acceptor and transfer medium and Ni 4 S 3 as hydrogen producing active site. Copyright © 2018 Elsevier Inc. All rights reserved.

Explicit symplectic algorithms based on generating functions for charged particle dynamics.

PubMed

Zhang, Ruili; Qin, Hong; Tang, Yifa; Liu, Jian; He, Yang; Xiao, Jianyuan

2016-07-01

Dynamics of a charged particle in the canonical coordinates is a Hamiltonian system, and the well-known symplectic algorithm has been regarded as the de facto method for numerical integration of Hamiltonian systems due to its long-term accuracy and fidelity. For long-term simulations with high efficiency, explicit symplectic algorithms are desirable. However, it is generally believed that explicit symplectic algorithms are only available for sum-separable Hamiltonians, and this restriction limits the application of explicit symplectic algorithms to charged particle dynamics. To overcome this difficulty, we combine the familiar sum-split method and a generating function method to construct second- and third-order explicit symplectic algorithms for dynamics of charged particle. The generating function method is designed to generate explicit symplectic algorithms for product-separable Hamiltonian with form of H(x,p)=p_{i}f(x) or H(x,p)=x_{i}g(p). Applied to the simulations of charged particle dynamics, the explicit symplectic algorithms based on generating functions demonstrate superiorities in conservation and efficiency.

Explicit symplectic algorithms based on generating functions for charged particle dynamics

NASA Astrophysics Data System (ADS)

Zhang, Ruili; Qin, Hong; Tang, Yifa; Liu, Jian; He, Yang; Xiao, Jianyuan

2016-07-01

Dynamics of a charged particle in the canonical coordinates is a Hamiltonian system, and the well-known symplectic algorithm has been regarded as the de facto method for numerical integration of Hamiltonian systems due to its long-term accuracy and fidelity. For long-term simulations with high efficiency, explicit symplectic algorithms are desirable. However, it is generally believed that explicit symplectic algorithms are only available for sum-separable Hamiltonians, and this restriction limits the application of explicit symplectic algorithms to charged particle dynamics. To overcome this difficulty, we combine the familiar sum-split method and a generating function method to construct second- and third-order explicit symplectic algorithms for dynamics of charged particle. The generating function method is designed to generate explicit symplectic algorithms for product-separable Hamiltonian with form of H (x ,p ) =pif (x ) or H (x ,p ) =xig (p ) . Applied to the simulations of charged particle dynamics, the explicit symplectic algorithms based on generating functions demonstrate superiorities in conservation and efficiency.

Impact of organic polyelectrolytes on coagulation of source-separated black water.

PubMed

Kozminykh, Pavlo; Heistad, Arve; Ratnaweera, Harsha C; Todt, Daniel

2016-01-01

Household wastewater is originated from common people's activities and has a potential harmful impact on the environment if discharged directly without proper treatment. Toilet wastewater or black water (BW) contains urine, faeces, toilet paper and flushing water and it contains the majority of pollutants obtained from a single household. In this study, the focus was on BW treatment using chemical methods. The main goal of current research was to define the possibility and applicability of conventional coagulants and flocculants in direct chemical treatment of vacuum-collected BW to remove particles, organic matter and phosphorous. After the definition of dosing ranges, based on the equivalent doses in conventional municipal and industrial wastewater treatment data, aluminium and iron coagulants, organic polyelectrolytes (polymers with anionic, neutral and cationic charge with different molecular weights) and their various combinations were tested using the well-known jar-test laboratory method to study aggregation and solid-liquid separation processes in raw BW. The most important process parameter during the coagulation was pH level, dependent on the type and doses of metal salts. Some side processes were found to occur while using iron-based coagulants. Dosing of either single coagulants or single polymers did not give satisfactory results, while a combination of aluminium salts and cationic polymers showed high removal rates in total suspended solids, total chemical oxygen demand and ortho-phosphates, reaching 97.8%, 92% and 98.6%, respectively, with the optimal doses of chemicals. Cationic polymers with the lowest molecular weight and highest charge density were the most efficient in combination with aluminium coagulants.

Thermodynamics Calculation and Experimental Study on Separation of Bismuth from a Bismuth Glance Concentrate Through a Low-Temperature Molten Salt Smelting Process

NASA Astrophysics Data System (ADS)

Yang, Jian-Guang; He, De-Wen; Tang, Chao-Bo; Chen, Yong-Ming; Sun, Ya-Hui; Tang, Mo-Tang

2011-08-01

The main purpose of this study is to characterize and separate bismuth from a bismuth glance concentrate through a low-temperature, sulfur-fixing smelting process. This article reports on a study conducted on the optimization of process parameters, such as Na2CO3 and zinc oxide wt pct in charging, smelting temperature, smelting duration on the bismuth yield, resultant crude bismuth grade, and sulfur-fixing rate. A maximum bismuth recovery of 97.31 pct, crude bismuth grade of 96.93 pct, and 98.23 pct sulfur-fixing rate are obtained when a charge (containing 63.50 wt pct of Na2CO3 and 22.50 wt pct of bismuth glance, as well as 5 pct in excess of the stoichiometric requirement of zinc oxide dosage) is smelted at 1000 K (727 °C) for 150 minutes. This smelting operation is free from atmospheric pollution because zinc oxide is used as the sulfur-fixing agent, which can capture sulfur from bismuth sulfide and form the more thermodynamic-stable compound, zinc sulfide. The solid residue is subjected to a mineral dressing operation to obtain suspension, which is filtered to produce a cake, representing the solid particles of zinc sulfide. Based on the results of the chemical content analysis of the as-resultant zinc sulfide, more than 93 pct zinc sulfide can be recovered, and the recovered zinc sulfide grade can reach 60.20 pct. This material can be sold as zinc sulfide concentrate or roasted to be regenerated as zinc oxide.

The impact of chemical structure and molecular packing on the electronic polarisation of fullerene arrays.

PubMed

Few, Sheridan; Chia, Cleaven; Teo, Daniel; Kirkpatrick, James; Nelson, Jenny

2017-07-19

Electronic polarisation contributes to the electronic landscape as seen by separating charges in organic materials. The nature of electronic polarisation depends on the polarisability, density, and arrangement of polarisable molecules. In this paper, we introduce a microscopic, coarse-grained model in which we treat each molecule as a polarisable site, and use an array of such polarisable dipoles to calculate the electric field and associated energy of any arrangement of charges in the medium. The model incorporates chemical structure via the molecular polarisability and molecular packing patterns via the structure of the array. We use this model to calculate energies of charge pairs undergoing separation in finite fullerene lattices of different chemical and crystal structures. The effective dielectric constants that we estimate from this approach are in good quantitative agreement with those measured experimentally in C 60 and phenyl-C 61 -butyric acid methyl ester (PCBM) films, but we find significant differences in dielectric constant depending on packing and on direction of separation, which we rationalise in terms of density of polarisable fullerene cages in regions of high field. In general, we find lattices containing molecules of more isotropic polarisability tensors exhibit higher dielectric constants. By exploring several model systems we conclude that differences in molecular polarisability (and therefore, chemical structure) appear to be less important than differences in molecular packing and separation direction in determining the energetic landscape for charge separation. We note that the results are relevant for finite lattices, but not necessarily for infinite systems. We propose that the model could be used to design molecular systems for effective electronic screening.

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.

The propagation of GPS signals through electrically charged plumes

NASA Astrophysics Data System (ADS)

Méndez Harper, J.; Steffes, P. G.; Dufek, J.

2017-12-01

Probing the interior dynamics of eruptive columns using electrostatic processes generated within the flows themselves has garnered much interest in the recent years. Indeed, large eruptions are often accompanied by brilliant displays of lightning, testifying to the high potentials that can be accumulated by a diverse set of electrification mechanisms. Unfortunately, lightning on its own cannot be used as a general remote sensing tool because not all volcanic eruptions produce spark discharges. As pointed out by McNutt and Williams, 2010, only 30-35% of volcanoes maintain lightning storms. The absence of lightning in two thirds of all eruptions indicates that most volcanoes produce flows with 1) inefficient or limited granular charging processes or 2) dynamics that do not promote the charge separation that sets up coherent electric fields needed for lightning. Yet, even if the prerequisites for spark discharges are not met, it is difficult to argue for plumes which are completely electrostatically neutral. The problems permeating passive electromagnetic sensing may be overcome through the use of active methods which involve interrogating charged volcanic plumes with electromagnetic radiation. The scattering of electromagnetic waves has been a common method to retrieve the physical properties of collections of particles, specifically those which cannot be accessed directly. By modifying the standard Mie formulation, Klavcka et al., 2007 showed that surface charge may influence the extinction properties of grains if such particles are much smaller than the wavelength of the incident radiation. Based on this model, we posit that the properties of charged clouds of particles can be readily assessed using robust, existing infrastructure-the Global Positioning System. In the present work, we numerically explore the manner in which electrostatic charge on particles affect the propagation of electromagnetic waves through volcanic plumes. We show that, for the range of complex dielectric constants measured in volcanic ash, the extinction efficiency of a charged particle is significantly larger than that associated with an equivalent neutral particle. Thus, this work represents the theoretical framework for a new method to explore charging in volcanic plumes.

Understanding performance limitation and suppression of leakage current or self-discharge in electrochemical capacitors: a review.

PubMed

Ike, Innocent S; Sigalas, Iakovos; Iyuke, Sunny

2016-01-14

Self-discharge is known to have considerable adverse effects on the performance and application of electrochemical capacitors (ECs). Thus, obtaining an understanding of EC self-discharge mechanism(s) and subsequent derivation and solution of EC models, subject to a particular mechanism or combination of mechanisms during charging, discharging and storage of the device, is the only way to solve problems associated with EC self-discharge. In this review, we summarize recent progress with respect to EC self-discharge by considering the two basic types, electric double-layer capacitors (EDLC) and pseudocapacitors, and their hybrids with their respective charge storage mechanisms, distinguishable self-discharge mechanisms, charge redistribution and charge/energy loss during self-discharge. It was clearly observed that most of the voltage reduction is not purely due to the self-discharge effect but is basically due to redistribution of charge carriers deep inside pores and can therefore be retrieved from a capacitor during long-time discharging. Tuning the self-discharge rate is therefore feasible for single-walled carbon nanotube (SWNT) ECs and can be achieved by simply adjusting the surface chemistry of the nanotubes. The effects of surface chemistry modification on EC self-discharge are very important in studying and suppressing the self-discharge process and will benefit potential applications of ECs with respect to energy retention. Self-discharge can be averted by the use of redox couples that are transformed to insoluble species via electrolysis and adsorbed onto the activated carbon electrode in redox-couple EDLCs, thus transforming the EDLC electrolyte into a material that can store charge. Self-discharge in ECs can also be successfully suppressed by utilizing an ion-interchange layer (ion-exchange membrane), separator or CuSO4 mobile electrolyte that can be converted into an insoluble species by electrolysis during the charge/discharge process. This will help in producing a modern-day blueprint for ECs with high capacitance and improved energy sustainability.

Specific ion effects on membrane potential and the permselectivity of ion exchange membranes.

PubMed

Geise, Geoffrey M; Cassady, Harrison J; Paul, Donald R; Logan, Bruce E; Hickner, Michael A

2014-10-21

Membrane potential and permselectivity are critical parameters for a variety of electrochemically-driven separation and energy technologies. An electric potential is developed when a membrane separates electrolyte solutions of different concentrations, and a permselective membrane allows specific species to be transported while restricting the passage of other species. Ion exchange membranes are commonly used in applications that require advanced ionic electrolytes and span technologies such as alkaline batteries to ammonium bicarbonate reverse electrodialysis, but membranes are often only characterized in sodium chloride solutions. Our goal in this work was to better understand membrane behaviour in aqueous ammonium bicarbonate, which is of interest for closed-loop energy generation processes. Here we characterized the permselectivity of four commercial ion exchange membranes in aqueous solutions of sodium chloride, ammonium chloride, sodium bicarbonate, and ammonium bicarbonate. This stepwise approach, using four different ions in aqueous solution, was used to better understand how these specific ions affect ion transport in ion exchange membranes. Characterization of cation and anion exchange membrane permselectivity, using these ions, is discussed from the perspective of the difference in the physical chemistry of the hydrated ions, along with an accompanying re-derivation and examination of the basic equations that describe membrane potential. In general, permselectivity was highest in sodium chloride and lowest in ammonium bicarbonate solutions, and the nature of both the counter- and co-ions appeared to influence measured permselectivity. The counter-ion type influences the binding affinity between counter-ions and polymer fixed charge groups, and higher binding affinity between fixed charge sites and counter-ions within the membrane decreases the effective membrane charge density. As a result permselectivity decreases. The charge density and polarizability of the co-ions also appeared to influence permselectivity leading to ion-specific effects; co-ions that are charge dense and have low polarizability tended to result in high membrane permselectivity.

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

A Nonfullerene Small Molecule Acceptor with 3D Interlocking Geometry Enabling Efficient Organic Solar Cells.

PubMed

Lee, Jaewon; Singh, Ranbir; Sin, Dong Hun; Kim, Heung Gyu; Song, Kyu Chan; Cho, Kilwon

2016-01-06

A new 3D nonfullerene small-molecule acceptor is reported. The 3D interlocking geometry of the small-molecule acceptor enables uniform molecular conformation and strong intermolecular connectivity, facilitating favorable nanoscale phase separation and electron charge transfer. By employing both a novel polymer donor and a nonfullerene small-molecule acceptor in the solution-processed organic solar cells, a high-power conversion efficiency of close to 6% is demonstrated. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Combined electrophoretic-separation and electrospray method and system

DOEpatents

Smith, Richard D.; Olivares, Jose A.

1989-01-01

A system and method for analyzing molecular constituents of a composition sample includes: forming a solution of the sample, separating the solution by capillary zone electrophoresis into an eluent of constituents longitudinally separated according to their relative electrophoretic mobilities, electrospraying the eluent to form a charged spray in which the molecular constituents have a temporal distribution; and detecting or collecting the separated constituents in accordance with the temporal distribution in the spray. A first high-voltage (e.g., 5-100 KVDC) is applied to the solution. The spray is charged by applying a second high voltage (e.g., .+-.2-8 KVDC) between the eluent at the capillary exit and a cathode spaced in front of the exit. A complete electrical circuit is formed by a conductor which directly contacts the eluent at the capillary exit.

A silica monolithic column prepared by the sol-gel process for enantiomeric separation by capillary electrochromatography.

PubMed

Kang, Jingwu; Wistuba, Dorothee; Schurig, Volker

2002-04-01

A method for the preparation of a silica monolithic capillary electrochromatography (CEC) column for the separation of enantiomers has been developed. The porous silica monolith was fabricated inside a fused-silica capillary column by using the sol-gel process. After gelation for 24 h, hydrothermal treatment at 100 degrees C for 24 h was performed to prevent the sol-gel matrix from cracking. The prepared monolith was then coated with Chirasil-beta-Dex which represents a chiral polymer prepared by grafting permethyl-beta-cyclodextrin to polymethylsiloxane with an octamethylene spacer. Immobilization of Chirasil-beta-Dex was performed by heat treatment at 120 degrees C for 48 h to give a nonextractable coating. The column performance was evaluated by using racemic hexobarbital as a model compound. The efficiency of 9.2 x 10(4) theoretical plates/m for the first eluted enantiomer of hexobarbital was obtained at an optimal flow rate of the mobile phase. The effect of mobile phase composition on enantiomeric separation of hexobarbital was also investigated. The column proved to be stable for more than one hundreds of runs during a two-months period. The enantiomers of several neutral and negatively charged chiral compounds were baseline separated on this column.

A semiempirical study for the ground and excited states of free-base and zinc porphyrin-fullerene dyads

NASA Technical Reports Server (NTRS)

Parusel, A. B.

2000-01-01

The ground and excited states of a covalently linked porphyrin-fullerene dyad in both its free-base and zinc forms (D. Kuciauskas et al., J. Phys. Chem. 100 (1996) 15926) have been investigated by semiempirical methods. The excited-state properties are discussed by investigation of the character of the molecular orbitals. All frontier MOs are mainly localized on either the donor or the acceptor subunit. Thus, the absorption spectra of both systems are best described as the sum of the spectra of the single components. The experimentally observed spectra are well reproduced by the theoretical computations. Both molecules undergo efficient electron transfer in polar but not in apolar solvents. This experimental finding is explained theoretically by explicitly considering solvent effects. The tenth excited state in the gas phase is of charge-separated character where an electron is transferred from the porphyrin donor to the fullerene acceptor subunit. This state is stabilized in energy in polar solvents due to its large formal dipole moment. The stabilization energy for an apolar environment such as benzene is not sufficient to lower this state to become the first excited singlet state. Thus, no electron transfer is observed, in agreement with experiment. In a polar environment such as acetonitrile, the charge-separated state becomes the S, state and electron transfer takes place, as observed experimentally. The flexible single bond connecting both the donor and acceptor subunits allows free rotation by ca. +/- 30 degrees about the optimized ground-state conformation. For the charge-separated state this optimized geometry has a maximum dipole moment. The geometry of the charge-separated state thus does not change relatively to the ground-state conformation. The electron-donating properties of porphyrin are enhanced in the zinc derivative due to a reduced porphyrin HOMO-LUMO energy gap. This yields a lower energy for the charge-separated state compared to the free-base dyad.

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.

System and method for charging a plug-in electric vehicle

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

Bassham, Marjorie A.; Spigno, Jr., Ciro A.; Muller, Brett T.

2017-05-02

A charging system and method that may be used to automatically apply customized charging settings to a plug-in electric vehicle, where application of the settings is based on the vehicle's location. According to an exemplary embodiment, a user may establish and save a separate charging profile with certain customized charging settings for each geographic location where they plan to charge their plug-in electric vehicle. Whenever the plug-in electric vehicle enters a new geographic area, the charging method may automatically apply the charging profile that corresponds to that area. Thus, the user does not have to manually change or manipulate themore » charging settings every time they charge the plug-in electric vehicle in a new location.« less

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.

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.

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

Development of Omniphobic Desalination Membranes Using a Charged Electrospun Nanofiber Scaffold.

PubMed

Lee, Jongho; Boo, Chanhee; Ryu, Won-Hee; Taylor, André D; Elimelech, Menachem

2016-05-04

In this study, we present a facile and scalable approach to fabricate omniphobic nanofiber membranes by constructing multilevel re-entrant structures with low surface energy. We first prepared positively charged nanofiber mats by electrospinning a blend polymer-surfactant solution of poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) and cationic surfactant (benzyltriethylammonium). Negatively charged silica nanoparticles (SiNPs) were grafted on the positively charged electrospun nanofibers via dip-coating to achieve multilevel re-entrant structures. Grafted SiNPs were then coated with fluoroalkylsilane to lower the surface energy of the membrane. The fabricated membrane showed excellent omniphobicity, as demonstrated by its wetting resistance to various low surface tension liquids, including ethanol with a surface tension of 22.1 mN/m. As a promising application, the prepared omniphobic membrane was tested in direct contact membrane distillation to extract water from highly saline feed solutions containing low surface tension substances, mimicking emerging industrial wastewaters (e.g., from shale gas production). While a control hydrophobic PVDF-HFP nanofiber membrane failed in the desalination/separation process due to low wetting resistance, our fabricated omniphobic membrane exhibited a stable desalination performance for 8 h of operation, successfully demonstrating clean water production from the low surface tension feedwater.

27 CFR 53.91 - Charges to be included in sale price.

Code of Federal Regulations, 2010 CFR

2010-04-01

... the Code and § 53.100. In the case of sales on credit, a carrying, finance, or service charge is... connection with collection). (b) Tools and dies. Separate charges for tools and dies used in the manufacture... manufacture taxable articles, the tools and dies used in production pass to the purchaser, only the amount of...

Energy level engineering in ternary organic solar cells: Evaluating exciton dissociation at organic semiconductor interfaces

NASA Astrophysics Data System (ADS)

Feron, Krishna; Thameel, Mahir N.; Al-Mudhaffer, Mohammed F.; Zhou, Xiaojing; Belcher, Warwick J.; Fell, Christopher J.; Dastoor, Paul C.

2017-03-01

Electronic energy level engineering, with the aim to improve the power conversion efficiency in ternary organic solar cells, is a complex problem since multiple charge transfer steps and exciton dissociation driving forces must be considered. Here, we examine exciton dissociation in the ternary system poly(3-hexylthiophene): [6,6]-phenyl-C61-butyric acid methyl ester:2,4-bis[4-(N,N-diisobutylamino)-2,6-dihydroxyphenyl] squaraine (P3HT:PCBM:DIBSq). Even though the energy level diagram suggests that exciton dissociation at the P3HT:DIBSq interface should be efficient, electron paramagnetic resonance and external quantum efficiency measurements of planar devices show that this interface is not capable of generating separated charge carriers. Efficient exciton dissociation is still realised via energy transfer, which transports excitons from the P3HT:DIBSq interface to the DIBSq:PCBM interface, where separated charge carriers can be generated efficiently. This work demonstrates that energy level diagrams alone cannot be relied upon to predict the exciton dissociation and charge separation capability of an organic semiconductor interface and that energy transfer relaxes the energy level constraints for optimised multi-component organic solar cells.

Analysis of pharmaceutical impurities using multi-heartcutting 2D LC coupled with UV-charged aerosol MS detection.

PubMed

Zhang, Kelly; Li, Yi; Tsang, Midco; Chetwyn, Nik P

2013-09-01

To overcome challenges in HPLC impurity analysis of pharmaceuticals, we developed an automated online multi-heartcutting 2D HPLC system with hyphenated UV-charged aerosol MS detection. The first dimension has a primary column and the second dimension has six orthogonal columns to enhance flexibility and selectivity. The two dimensions were interfaced by a pair of switching valves equipped with six trapping loops that allow multi-heartcutting of peaks of interest in the first dimension and also allow "peak parking." The hyphenated UV-charged aerosol MS detection provides comprehensive detection for compounds with and without UV chromophores, organics, and inorganics. It also provides structural information for impurity identification. A hidden degradation product that co-eluted with the drug main peak was revealed by RP × RP separation and thus enabled the stability-indicating method development. A poorly retained polar component with no UV chromophores was analyzed by RP × hydrophilic interaction liquid chromatography separation with charged aerosol detection. Furthermore, using this system, the structures of low-level impurities separated by a method using nonvolatile phosphate buffer were identified and tracked by MS in the second dimension. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ultrafast Electron Transfer across a Nanocapsular Wall: Coumarins as Donors, Viologen as Acceptor, and Octa Acid Capsule as the Mediator.

PubMed

Chuang, Chi-Hung; Porel, Mintu; Choudhury, Rajib; Burda, Clemens; Ramamurthy, V

2018-01-11

Results of our study on ultrafast electron transfer (eT) dynamics from coumarins (coumarin-1, coumarin-480, and coumarin-153) incarcerated within octa acid (OA) capsules as electron donors to methyl viologen dissolved in water as acceptor are presented. Upon photoexcitation, coumarin inside the OA capsule transfers an electron to the acceptor electrostatically attached to the capsule leading to a long-lived radical-ion pair separated by the OA capsular wall. This charge-separated state returns to the neutral ground state via back electron transfer on the nanosecond time scale. This system allows for ultrafast electron transfer processes through a molecular wall from the apolar capsular interior to the highly polar (aqueous) environment on the femtosecond time scale. Employing femtosecond transient absorption spectroscopy, distinct rates of both forward (1-25 ps) and backward eT (700-1200 ps) processes were measured. Further understanding of the energetics is provided using Rehm-Weller analysis for the investigated photoinduced eT reactions. The results provide the rates of the eT across a molecular wall, akin to an isotropic solution, depending on the standard free energy of the reaction. The insights from this work could be utilized in the future design of efficient electron transfer processes across interfaces separating apolar and polar environments.

Complex coacervation of supercharged proteins with polyelectrolytes.

PubMed

Obermeyer, Allie C; Mills, Carolyn E; Dong, Xue-Hui; Flores, Romeo J; Olsen, Bradley D

2016-04-21

Complexation of proteins with polyelectrolytes or block copolymers can lead to phase separation to generate a coacervate phase or self-assembly of coacervate core micelles. However, many proteins do not coacervate at conditions near neutral pH and physiological ionic strength. Here, protein supercharging is used to systematically explore the effect of protein charge on the complex coacervation with polycations. Four model proteins were anionically supercharged to varying degrees as quantified by mass spectrometry. Proteins phase separated with strong polycations when the ratio of negatively charged residues to positively charged residues on the protein (α) was greater than 1.1-1.2. Efficient partitioning of the protein into the coacervate phase required larger α (1.5-2.0). The preferred charge ratio for coacervation was shifted away from charge symmetry for three of the four model proteins and indicated an excess of positive charge in the coacervate phase. The composition of protein and polymer in the coacervate phase was determined using fluorescently labeled components, revealing that several of the coacervates likely have both induced charging and a macromolecular charge imbalance. The model proteins were also encapsulated in complex coacervate core micelles and micelles formed when the protein charge ratio α was greater than 1.3-1.4. Small angle neutron scattering and transmission electron microscopy showed that the micelles were spherical. The stability of the coacervate phase in both the bulk and micelles improved to increased ionic strength as the net charge on the protein increased. The micelles were also stable to dehydration and elevated temperatures.

Applications of Electrified Dust and Dust Devil Electrodynamics to Martian Atmospheric Electricity

NASA Astrophysics Data System (ADS)

Harrison, R. G.; Barth, E.; Esposito, F.; Merrison, J.; Montmessin, F.; Aplin, K. L.; Borlina, C.; Berthelier, J. J.; Déprez, G.; Farrell, W. M.; Houghton, I. M. P.; Renno, N. O.; Nicoll, K. A.; Tripathi, S. N.; Zimmerman, M.

2016-11-01

Atmospheric transport and suspension of dust frequently brings electrification, which may be substantial. Electric fields of 10 kV m-1 to 100 kV m-1 have been observed at the surface beneath suspended dust in the terrestrial atmosphere, and some electrification has been observed to persist in dust at levels to 5 km, as well as in volcanic plumes. The interaction between individual particles which causes the electrification is incompletely understood, and multiple processes are thought to be acting. A variation in particle charge with particle size, and the effect of gravitational separation explains to, some extent, the charge structures observed in terrestrial dust storms. More extensive flow-based modelling demonstrates that bulk electric fields in excess of 10 kV m-1 can be obtained rapidly (in less than 10 s) from rotating dust systems (dust devils) and that terrestrial breakdown fields can be obtained. Modelled profiles of electrical conductivity in the Martian atmosphere suggest the possibility of dust electrification, and dust devils have been suggested as a mechanism of charge separation able to maintain current flow between one region of the atmosphere and another, through a global circuit. Fundamental new understanding of Martian atmospheric electricity will result from the ExoMars mission, which carries the DREAMS (Dust characterization, Risk Assessment, and Environment Analyser on the Martian Surface)—MicroARES ( Atmospheric Radiation and Electricity Sensor) instrumentation to Mars in 2016 for the first in situ electrical measurements.

Applications of Electrified Dust and Dust Devil Electrodynamics to Martian Atmospheric Electricity

NASA Technical Reports Server (NTRS)

Harrison, R. G.; Barth, E.; Esposito, F.; Merrison, J.; Montmessin, F.; Aplin, K. L.; Borlina, C.; Berthelier, J J.; Deprez, G.; Farrell, William M.;

Particle astronomy with a superconducting magnet.

NASA Technical Reports Server (NTRS)

Buffington, A.

1972-01-01

The magnetic spectrometer measures deflections of charged particles moving in a magnetic field and provides a direct means of determining the rigidity of charged primary cosmic rays up to about 100 GV/c rigidity. The underlying concepts of the method are reviewed, and factors delineating the applicable momentum range and accuracy are described along with calibration techniques. Previous experiments employing this technique are summarized, and prospects for future applications are evaluated with emphasis on separate measurement of electron and positron spectra and on isotopic separation.

Surface and material analytics based on Dresden-EBIS platform technology

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

Schmidt, M., E-mail: mike.schmidt@dreebit.com; König, J., E-mail: mike.schmidt@dreebit.com; Bischoff, L.

2015-01-09

Nowadays widely used mass spectrometry systems utilize energetic ions hitting a sample and sputter material from the surface of a specimen. The generated secondary ions are separated and detected with high mass resolution to determine the target materials constitution. Based on this principle, we present an alternative approach implementing a compact Electron Beam Ion Source (EBIS) in combination with a Liquid Metal Ion Source (LMIS). An LMIS can deliver heavy elements which generate high sputter yields on a target surface. More than 90% of this sputtered material consists of mono- and polyatomic neutrals. These particles are able to penetrate themore » magnetic field of an EBIS and they will be ionized within the electron beam. A broad spectrum of singly up to highly charged ions can be extracted depending on the operation conditions. Polyatomic ions will decay during the charge-up process. A standard bending magnet or a Wien filter is used to separate the different ion species due to their mass-to-charge ratio. Using different charge states of ions as it is common with EBIS it is also possible to resolve interfering charge-to-mass ratios of only singly charged ions. Different setups for the realization of feeding the electron beam with sputtered atoms of solids will be presented and discussed. As an example the analysis of a copper surface is used to show high-resolution spectra with low background noise. Individual copper isotopes and clusters with different isotope compositions can be resolved at equal atomic numbers. These results are a first step for the development of a new compact low-cost and high-resolution mass spectrometry system. In a more general context, the described technique demonstrates an efficient method for feeding an EBIS with atoms of nearly all solid elements from various solid target materials. The new straightforward design of the presented setup should be of high interest for a broad range of applications in materials research as well as for applications connected to analyzing the biosphere, hydrosphere, lithosphere, cosmosphere and technosphere.« less

Fabrication of nano copper oxide evenly patched on cubic sodium tantalate for oriented photocatalytic reduction of carbon dioxide.

PubMed

Xiang, Tianyu; Xin, Feng; Zhao, Can; Lou, Shuo; Qu, Wenxiu; Wang, Yong; Song, Yuexiao; Zhang, Shuangfang; Yin, Xiaohong

2018-05-15

A synthetic process was exploited to fabricate patchy CuO evenly planted on cubic NaTaO 3 for photocatalytically reducing CO 2 in isopropanol. The nano patches of CuO with about 15 nm in size were uniformly distributed on the surface of NaTaO 3 via a phase-transfer protocol and solvothermal synthesis. The crystal phase, morphology, composition, optical absorption and charge separation of as-prepared CuO-NaTaO 3 were characterized by XRD, SEM, TEM, EDX, XPS, UV-Vis and PL. The results of photocatalytic reduction of CO 2 confirmed that the CuO patched NaTaO 3 possessed better ability to separate charge carriers and selectively reduce CO 2 to methanol than CuO directly loaded NaTaO 3 using the traditional liquid phase reduction procedure after comparing the methanol yields. Furthermore, 5 wt% CuO patched NaTaO 3 led to the highest methanol yield of 1302.22 μmol g -1 h -1 . A redox mechanism was proposed and illustrated in a schematic diagram. Copyright © 2018 Elsevier Inc. All rights reserved.

Investigation of electrodialysis anti-fouling configuration for desalting and treating tannery unhairing wastewater: Feasibility of by-products recovery and water recycling.

PubMed

Tamersit, Sabrina; Bouhidel, Kamel-Eddine; Zidani, Zakaria

2018-02-01

The desalination and treatment of tannery unhairing wastewater by electrodialysis (ED) is investigated in this research in order to separate, concentrate, recover and reuse low molecular weight charged species (S 2- , HS - , OH - , Cl - , Ca 2+ , Na + and amino acids), and to separate proteins and recycle treated water. Therefore, a novel electrodialysis membrane configuration was proposed. This was based on a double anti-fouling membrane. The ED anion exchange membrane (AEM), which is very sensitive to organic fouling, was protected by an ultra filtration membrane impermeable to the negatively charged proteins that could not reach the AEM surface. The experimental results were quite promising, and in spite of only one desalination compartment ED cell; the demineralization efficiency was 56 ± 1.25% (5.5-2.4 mS/cm), with a sensitive removal of sulphide, calcium and chloride. The organic matter (protein, peptides…) was isolated in the dilute compartment. The most important result was the total absence of membrane fouling. The experimental results remarkably proved the initial hypothesis, and suggested promising solutions for industrial pollution, where the membrane processes have never been successful. Copyright © 2017 Elsevier Ltd. All rights reserved.

Origin of the F685 and F695 fluorescence in photosystem II.

PubMed

Andrizhiyevskaya, Elena G; Chojnicka, Agnieszka; Bautista, James A; Diner, Bruce A; van Grondelle, Rienk; Dekker, Jan P

2005-06-01

The emission spectra of CP47-RC and core complexes of Photosystem II (PS II) were measured at different temperatures and excitation wavelengths in order to establish the origin of the emission and the role of the core antenna in the energy transfer and charge separation processes in PS II. Both types of particles reveal strong dependences of spectral shape and yield on temperature. The results indicate that the well-known F-695 emission at 77 K arises from excitations that are trapped on a red-absorbing CP47 chlorophyll, whereas the F-685 nm emission at 77 K arises from excitations that are transferred slowly from 683 nm states in CP47 and CP43 to the RC, where they are trapped by charge separation. We conclude that F-695 at 77 K originates from the low-energy part of the inhomogeneous distribution of the 690 nm absorbing chlorophyll of CP47, while at 4 K the fluorescence originates from the complete distribution of the 690 nm chlorophyll of CP47 and from the low-energy part of the inhomogeneous distribution of one or more CP43 chlorophylls.

Digital pulse shape discrimination methods for n-γ separation in an EJ-301 liquid scintillation detector

NASA Astrophysics Data System (ADS)

Wan, Bo; Zhang, Xue-Ying; Chen, Liang; Ge, Hong-Lin; Ma, Fei; Zhang, Hong-Bin; Ju, Yong-Qin; Zhang, Yan-Bin; Li, Yan-Yan; Xu, Xiao-Wei

2015-11-01

A digital pulse shape discrimination system based on a programmable module NI-5772 has been established and tested with an EJ-301 liquid scintillation detector. The module was operated by running programs developed in LabVIEW, with a sampling frequency up to 1.6 GS/s. Standard gamma sources 22Na, 137Cs and 60Co were used to calibrate the EJ-301 liquid scintillation detector, and the gamma response function was obtained. Digital algorithms for the charge comparison method and zero-crossing method have been developed. The experimental results show that both digital signal processing (DSP) algorithms can discriminate neutrons from γ-rays. Moreover, the zero-crossing method shows better n-γ discrimination at 80 keVee and lower, whereas the charge comparison method gives better results at higher thresholds. In addition, the figure-of-merit (FOM) for detectors of two different dimensions were extracted at 9 energy thresholds, and it was found that the smaller detector presented better n-γ separation for fission neutrons. Supported by National Natural Science Foundation of China (91226107, 11305229) and the Strategic Priority Research Program of the Chinese Academy of Sciences (XDA03030300)

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

PubMed

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

2018-03-28

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

A submicron device to rectify a square-wave angular velocity.

PubMed

Moradian, A; Miri, M F

2011-02-01

We study a system composed of two thick dielectric disks separated by a thin layer of an electrolyte solution. Initially both plates have the same surface charge distribution. The surface charge distribution has no rotational symmetry. We show that the top plate experiences a torque [Formula: see text]([Formula: see text]) if it rotates about its axis by an angle [Formula: see text] . The torque can be controlled by varying the electrolyte concentration, the separation and the surface charge density of the plates. For a specific example of charged rods attached to the plates, we find [Formula: see text]([Formula: see text]) [Formula: see text] sin(4[Formula: see text]) . We also study the dynamics of the system. We consider the case where the angular velocity of the bottom disk is a square-wave signal. We find that the average angular velocity of the top disk is not zero.

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.

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.

Separability of massive field equations for spin-0 and spin-1/2 charged particles in the general nonextremal rotating charged black hole spacetimes in minimal five-dimensional gauged supergravity

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

Wu Shuangqing

We continue to investigate the separability of massive field equations for spin-0 and spin-1/2 charged particles in the general, nonextremal, rotating, charged, Chong-Cvetic-Lue-Pope black holes with two independent angular momenta and a nonzero cosmological constant in minimal D=5 gauged supergravity theory. We show that the complex Klein-Gordon equation and the modified Dirac equation with the inclusion of an extra counterterm can be separated by variables into purely radial and purely angular parts in this general Einstein-Maxwell-Chern-Simons background spacetime. A second-order symmetry operator that commutes with the complex Laplacian operator is constructed from the separated solutions and expressed compactly in termsmore » of a rank-2 Staeckel-Killing tensor which admits a simple diagonal form in the chosen pentad one-forms so that it can be understood as the square of a rank-3 totally antisymmetric tensor. A first-order symmetry operator that commutes with the modified Dirac operator is expressed in terms of a rank-3 generalized Killing-Yano tensor and its covariant derivative. The Hodge dual of this generalized Killing-Yano tensor is a generalized principal conformal Killing-Yano tensor of rank-2, which can generate a 'tower' of generalized (conformal) Killing-Yano and Staeckel-Killing tensors that are responsible for the whole hidden symmetries of this general, rotating, charged, Kerr-anti-de Sitter black hole geometry. In addition, the first laws of black hole thermodynamics have been generalized to the case that the cosmological constant can be viewed as a thermodynamical variable.« less

Experimental studies of Debye-like process and structural relaxation in mixtures of 2-ethyl-1-hexanol and 2-ethyl-1-hexyl bromide

NASA Astrophysics Data System (ADS)

Preuß, M.; Gainaru, C.; Hecksher, T.; Bauer, S.; Dyre, J. C.; Richert, R.; Böhmer, R.

2012-10-01

Binary solutions of 2-ethyl-1-hexanol (2E1H) with 2-ethyl-1-hexyl bromide (2E1Br) are investigated by means of dielectric, shear mechanical, near-infrared, and solvation spectroscopy as well as dielectrically monitored physical aging. For moderately diluted 2E1H the slow Debye-like process, which dominates the dielectric spectra of the neat monohydroxy alcohol, separates significantly from the α-relaxation. For example, the separation in equimolar mixtures amounts to four decades in frequency. This situation of highly resolved processes allows one to demonstrate unambiguously that physical aging is governed by the α-process, but even under these ideal conditions the Debye process remains undetectable in shear mechanical experiments. Furthermore, the solvation experiments show that under constant charge conditions the microscopic polarization fluctuations take place on the time scale of the structural process. The hydrogen-bond populations monitored via near-infrared spectroscopy indicate the presence of a critical alcohol concentration, xc ≈ 0.5-0.6, thereby confirming the dielectric data. In the pure bromide a slow dielectric process of reduced intensity is present in addition to the main relaxation. This is taken as a sign of intermolecular cooperativity probably mediated via halogen bonds.

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.

Photoinitated charge separation in a hybrid titanium dioxide metalloporphyrin peptide material

NASA Astrophysics Data System (ADS)

Fry, H. Christopher; Liu, Yuzi; Dimitrijevic, Nada M.; Rajh, Tijana

2014-08-01

In natural systems, electron flow is mediated by proteins that spatially organize donor and acceptor molecules with great precision. Achieving this guided, directional flow of information is a desirable feature in photovoltaic media. Here, we design self-assembled peptide materials that organize multiple electronic components capable of performing photoinduced charge separation. Two peptides, c16-AHL3K3-CO2H and c16-AHL3K9-CO2H, self-assemble into fibres and provide a scaffold capable of binding a metalloporphyrin via histidine axial ligation and mineralize titanium dioxide (TiO2) on the lysine-rich surface of the resulting fibrous structures. Electron paramagnetic resonance studies of this self-assembled material under continuous light excitation demonstrate charge separation induced by excitation of the metalloporphyrin and mediated by the peptide assembly structure. This approach to dye-sensitized semiconducting materials offers a means to spatially control the dye molecule with respect to the semiconducting material through careful, strategic peptide design.

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

Lightning generation in Titan due to the electrical self-polarization properties of Methane

NASA Astrophysics Data System (ADS)

Quintero, A.; Falcón, N.

2009-05-01

We describe an electrical charge process in Titan's thunderclouds, due to the self-polarization properties or pyroelectricity of methane, which increases the internal electric field in thunderclouds and facilitates the charge generation and separation processes. Microphysics that generates lightning flashes is associated with the physical and chemical properties of the local atmosphere, so methane could be the principal agent of the electrical activity because of its great concentration in Titan's atmosphere. Besides, Titan's electrical activity should not be very influenced by Saturn's magnetosphere because lightning occurs at very low altitude above Titan's surface, compared with the greater distance of Saturn's magnetosphere and Titan's troposphere. Using an electrostatic treatment, we calculate the internal electric field of Titan's thunderclouds due to methane's pyroelectrical properties, 7.05×10^11 Vm^-1; and using the telluric capacitor approximation for thunderclouds, we calculate the total charge obtained for a typical Titan thundercloud, 2.67×10^9 C. However, it is not right to use an electrostatic treatment because charge times are very fast due to the large methane concentration in Titan's clouds and the life time of thunderclouds is very low (around 2 hours). We consider a time dependent mechanism, employing common Earth atmospheric approaches, because of the similitude in chemical composition of both atmospheres (mainly nitrogen), so the typical charge of a thundercloud in Titan should reach between 20 C to 40 C, like on Earth. We obtain that lightning occurs with a frequency between 2 and 6 KHz. In Titan's atmosphere, methane concentration is higher than on Earth, and atmospheric electrical activity is stronger, so this model could be consistent with the observed phenomenology.

Design and Synthesis of Novel Block Copolymers for Efficient Opto-Electronic Applications

NASA Technical Reports Server (NTRS)

Sun, Sam-Shajing; Fan, Zhen; Wang, Yiqing; Taft, Charles; Haliburton, James; Maaref, Shahin

2002-01-01

It has been predicted that nano-phase separated block copolymer systems containing electron rich donor blocks and electron deficient acceptor blocks may facilitate the charge carrier separation and migration in organic photovoltaic devices due to improved morphology in comparison to polymer blend system. This paper presents preliminary data describing the design and synthesis of a novel Donor-Bridge-Acceptor (D-B-A) block copolymer system for potential high efficient organic optoelectronic applications. Specifically, the donor block contains an electron donating alkyloxy derivatized polyphenylenevinylene (PPV), the acceptor block contains an electron withdrawing alkyl-sulfone derivatized polyphenylenevinylene (PPV), and the bridge block contains an electronically neutral non-conjugated aliphatic hydrocarbon chain. The key synthetic strategy includes the synthesis of each individual block first, then couple the blocks together. While the donor block stabilizes and facilitates the transport of the holes, the acceptor block stabilizes and facilitates the transport of the electrons, the bridge block is designed to hinder the probability of electron-hole recombination. Thus, improved charge separation and stability are expected with this system. In addition, charge migration toward electrodes may also be facilitated due to the potential nano-phase separated and highly ordered block copolymer ultra-structure.

Disentangling flow and signals of Chiral Magnetic Effect in U+U, Au+Au and p+Au collisions

NASA Astrophysics Data System (ADS)

Tribedy, Prithwish; STAR Collaboration

2017-11-01

We present STAR measurements of the charge-dependent three-particle correlator γ a , b = 〈 cos ⁡ (ϕ1a + ϕ2b - 2ϕ3) 〉 /v2 { 2 } and elliptic flow v2 { 2 } in U+U, Au+Au and p+Au collisions at RHIC. The difference Δγ = γ (opposite-sign) - γ (same-sign) measures charge separation across the reaction plane, a predicted signal of the Chiral Magnetic Effect (CME). Although charge separation has been observed, it has been argued that the measured separation can also be explained by elliptic flow related backgrounds. In order to separate the two effects we perform measurements of the γ-correlator where background expectations differ from magnetic field driven effects. A differential measurement of γ with the relative pseudorapidity (Δη) between the first and second particles indicate that Δγ in peripheral A+A and p+A collisions are dominated by short-range correlations in Δη. However, a relatively wider component of the correlation in Δη tends to vanish the same way as projected magnetic field as predicted by MC-Glauber simulations.

Explicit Solvent Simulations of Friction between Brush Layers of Charged and Neutral Bottle-Brush Macromolecules

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

Carrillo, Jan-Michael; Brown, W Michael; Dobrynin, Andrey

2012-01-01

We study friction between charged and neutral brush layers of bottle-brush macromolecules using molecular dynamics simulations. In our simulations the solvent molecules were treated explicitly. The deformation of the bottle-brush macromolecules under the shear were studied as a function of the substrate separation and shear stress. For charged bottle-brush layers we study effect of the added salt on the brush lubricating properties to elucidate factors responsible for energy dissipation in charged and neutral brush systems. Our simulations have shown that for both charged and neutral brush systems the main deformation mode of the bottle-brush macromolecule is associated with the backbonemore » deformation. This deformation mode manifests itself in the backbone deformation ratio, , and shear viscosity, , to be universal functions of the Weissenberg number W. The value of the friction coefficient, , and viscosity, , are larger for the charged bottle-brush coatings in comparison with those for neutral brushes at the same separation distance, D, between substrates. The additional energy dissipation generated by brush sliding in charged bottle-brush systems is due to electrostatic coupling between bottle-brush and counterion motion. This coupling weakens as salt concentration, cs, increases resulting in values of the viscosity, , and friction coefficient, , approaching corresponding values obtained for neutral brush systems.« less