Optical spectra of La2-xSrxCuO4: Effect of carrier doping on the electronic structure of the CuO2 plane

NASA Astrophysics Data System (ADS)

Uchida, S.; Ido, T.; Takagi, H.; Arima, T.; Tokura, Y.; Tajima, S.

1991-04-01

Optical reflectivity spectra are studied for single crystals of the prototypical high-Tc system La2-xSrxCuO4 over a wide compositional range 0<=x<=0.34, which covers insulating, superconducting, and normal metallic phases. The measurements are made at room temperature over an energy range from 0.004 to 35 eV for the polarization parallel to the CuO2 planes. They are also extended to the perpendicular polarization to study anisotropy and to discriminate the contribution from the CuO2 plane. The present study focuses on the x dependence of the optical spectrum, which makes it possible to sort out the features of the excitations in the CuO2 plane and thus to characterize the electronic structure of the CuO2 plane in the respective phase. Upon doping into the parent insulator La2CuO4 with a charge-transfer energy gap of about 2 eV the spectral weight is rapidly transferred from the charge-transfer excitation to low-energy excitations below 1.5 eV. The low-energy spectrum is apparently composed of two contributions; a Drude-type one peaked at ω=0 and a broad continuum centered in the midinfrared range. The high-Tc superconductivity is realized as doping proceeds and when the transfer of the spectrum weight is saturated. The resulting spectrum in the high-Tc regime is suggestive of a strongly itinerant character of the state in the moderately doped CuO2 plane while appreciable weight remains in the charge-transfer energy region. The spectrum exhibits a second drastic change for heavy doping (x~0.25) corresponding to the superconductor-to-normal-metal transition and becomes close to that of a Fermi liquid. The results are universal for all the known cuprate superconductors including the electron-doped compounds, and they reconcile the dc transport properties with the high-energy spectroscopic results.

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

NASA Astrophysics Data System (ADS)

Nistor, Razvan A.

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

Charge transfer in TATB and HMX under extreme conditions.

PubMed

Zhang, Chaoyang; Ma, Yu; Jiang, Daojian

2012-11-01

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

Molecular control of pentacene/ZnO photoinduced charge transfer

NASA Astrophysics Data System (ADS)

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

2011-03-01

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

Specificity and kinetics of alpha-synuclein binding to model membranes determined with fluorescent excited state intramolecular proton transfer (ESIPT) probe.

PubMed

Shvadchak, Volodymyr V; Falomir-Lockhart, Lisandro J; Yushchenko, Dmytro A; Jovin, Thomas M

2011-04-15

Parkinson disease is characterized cytopathologically by the deposition in the midbrain of aggregates composed primarily of the presynaptic neuronal protein α-synuclein (AS). Neurotoxicity is currently attributed to oligomeric microaggregates subjected to oxidative modification and promoting mitochondrial and proteasomal dysfunction. Unphysiological binding to membranes of these and other organelles is presumably involved. In this study, we performed a systematic determination of the influence of charge, phase, curvature, defects, and lipid unsaturation on AS binding to model membranes using a new sensitive solvatochromic fluorescent probe. The interaction of AS with vesicular membranes is fast and reversible. The protein dissociates from neutral membranes upon thermal transition to the liquid disordered phase and transfers to vesicles with higher affinity. The binding of AS to neutral and negatively charged membranes occurs by apparently different mechanisms. Interaction with neutral bilayers requires the presence of membrane defects; binding increases with membrane curvature and rigidity and decreases in the presence of cholesterol. The association with negatively charged membranes is much stronger and much less sensitive to membrane curvature, phase, and cholesterol content. The presence of unsaturated lipids increases binding in all cases. These findings provide insight into the relation between membrane physical properties and AS binding affinity and dynamics that presumably define protein localization in vivo and, thereby, the role of AS in the physiopathology of Parkinson disease.

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

Role of the Charge-Transfer State in Reduced Langevin Recombination in Organic Solar Cells: A Theoretical Study

PubMed Central

2015-01-01

Reduced Langevin recombination has been observed in organic solar cells (OSCs) for many years, but its origin is still unclear. A recent work by Burke et al. (Adv. Energy Mater.2015, 5, 1500123-1) was inspired by this reduced Langevin recombination, and they proposed an equilibrium model of charge-transfer (CT) states that correlates the open-circuit voltage of OSCs with experimentally available device parameters. In this work, we extend Burke et al.’s CT model further and for the first time directly correlate the reduced Langevin recombination with the energetic and dynamic behavior of the CT state. Recombination through CT states leads in a straightforward manner to a decrease in the Langevin reduction factor with increasing temperature, without explicit consideration of the temperature dependence of the mobility. To verify the correlation between the CT states and reduced Langevin recombination, we incorporated this CT model and the reduced Langevin model into drift-diffusion simulations of a bilayer OSC. The simulations not only successfully reproduced realistic current–voltage (J–V) characteristics of the bilayer OSC, but also demonstrate that the two models consistently lead to same value of the apparent Langevin reduction factor. PMID:26640611

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

NASA Astrophysics Data System (ADS)

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

2006-03-01

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

Charge-exchange x-ray spectra: Evidence for significant contributions from radiative decays of doubly excited states

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

Ali, R.; Beiersdorfer, P.; Harris, C. L.

2016-01-21

Charge-exchange collisions of slow Ne 10+ ions with He, Ne, and Ar targets were studied with simultaneous x-ray and cold-target recoil-ion-momentum spectroscopy proving the contribution of several mechanisms to the radiative stabilization of apparent (4,4) doubly excited states for He and Ne targets and of (5,6) states for Ar. In particular, the stabilization efficiency of the mechanism of dynamic auto-transfer to Rydberg states is confirmed. Moreover, we present evidence for direct radiative decays of (4,4) states populated in collisions with He, which is an experimental indication of the population of so-called unnatural-parity states in such collisions. Lastly, these mechanisms leadmore » to the emission of x-rays that have considerably higher energies than those predicted by current spectral models and may explain recent observations of anomalously large x-ray emission from Rydberg levels.« less

Consideration of Cost of Care in Pediatric Emergency Transfer-An Opportunity for Improvement.

PubMed

Gattu, Rajender K; De Fee, Ann-Sophie; Lichenstein, Richard; Teshome, Getachew

2017-05-01

Pediatric interhospital transfers are an economic burden to the health care, especially when deemed unnecessary. Physicians may be unaware of the cost implications of pediatric emergency transfers. A cost analysis may be relevant to reduce cost. To characterize children transferred from outlying emergency departments (EDs) to pediatric ED (PED) with a specific focus on transfers who were discharged home in 12 hours or less after transfer without intervention in PED and analyze charges associated with them. Charts of 352 patients (age, 0-18 years) transferred from 31 outlying EDs to PED during July 2009 to June 2010 were reviewed. Data were collected on the range, unit charge and volume of services provided in PED, length of stay, and final disposition. The average charge per patient transfer is calculated based on unit charge times total service units per 1000 patients per year and divided by 1000. Hospital charges were divided into fixed and variable. Of 352 patients transferred, 108 (30.7%) were admitted to pediatric inpatient service, 42 (11.9%) to intensive care; 36 (10.2%) went to the operating room, and 166 (47.2%) were discharged home. The average hospital charge per transfer was US $4843. Most (89%) of the charges were fixed, and 11% were variable. One hundred one (28.7%) patients were discharged home from PED in 12 hours or less without intervention. The hospital charges for these transfers were US $489,143. Significant number of transfers was discharged 12 hours or less without any additional intervention in PED. Fixed charges contribute to majority of total charges. Cost saving can be achieved by preventing unnecessary transfer.

Retrieval of charge mobility from apparent charge packet movements in LDPE thin films

NASA Astrophysics Data System (ADS)

Meng, Jia; Zhang, Yewen; Holé, Stéphane; Zheng, Feihu; An, Zhenlian

2017-03-01

The charge packet phenomenon observed in polyethylene materials has been reported extensively during the last decades. To explain its movement, Negative Differential Mobility (NDM) theory is a competitive model among several proposed mechanisms. However, as a key concept of this theory, a sufficiently acute relationship between charge mobility and electric field has never been reported until now, which makes it hard to precisely describe the migration of charge packets with this theory. Based on the substantial negative-charge packet observations with a sufficiently by wide electric field range from 15 kV/mm to 50 kV/mm, the present contribution successfully retrieved the negative-charge mobility from the apparent charge packet movements, which reveals a much closer relationship between the NDM theory and charge packet migrations. Back simulations of charge packets with the retrieved charge mobility offer a good agreement with the experimental data.

Alternating electron and proton transfer steps in photosynthetic water oxidation

PubMed Central

Klauss, André; Haumann, Michael; Dau, Holger

2012-01-01

Water oxidation by cyanobacteria, algae, and plants is pivotal in oxygenic photosynthesis, the process that powers life on Earth, and is the paradigm for engineering solar fuel–production systems. Each complete reaction cycle of photosynthetic water oxidation requires the removal of four electrons and four protons from the catalytic site, a manganese–calcium complex and its protein environment in photosystem II. In time-resolved photothermal beam deflection experiments, we monitored apparent volume changes of the photosystem II protein associated with charge creation by light-induced electron transfer (contraction) and charge-compensating proton relocation (expansion). Two previously invisible proton removal steps were detected, thereby filling two gaps in the basic reaction-cycle model of photosynthetic water oxidation. In the S2 → S3 transition of the classical S-state cycle, an intermediate is formed by deprotonation clearly before electron transfer to the oxidant (). The rate-determining elementary step (τ, approximately 30 µs at 20 °C) in the long-distance proton relocation toward the protein–water interface is characterized by a high activation energy (Ea = 0.46 ± 0.05 eV) and strong H/D kinetic isotope effect (approximately 6). The characteristics of a proton transfer step during the S0 → S1 transition are similar (τ, approximately 100 µs; Ea = 0.34 ± 0.08 eV; kinetic isotope effect, approximately 3); however, the proton removal from the Mn complex proceeds after electron transfer to . By discovery of the transient formation of two further intermediate states in the reaction cycle of photosynthetic water oxidation, a temporal sequence of strictly alternating removal of electrons and protons from the catalytic site is established. PMID:22988080

Alternating electron and proton transfer steps in photosynthetic water oxidation.

PubMed

Klauss, André; Haumann, Michael; Dau, Holger

2012-10-02

Water oxidation by cyanobacteria, algae, and plants is pivotal in oxygenic photosynthesis, the process that powers life on Earth, and is the paradigm for engineering solar fuel-production systems. Each complete reaction cycle of photosynthetic water oxidation requires the removal of four electrons and four protons from the catalytic site, a manganese-calcium complex and its protein environment in photosystem II. In time-resolved photothermal beam deflection experiments, we monitored apparent volume changes of the photosystem II protein associated with charge creation by light-induced electron transfer (contraction) and charge-compensating proton relocation (expansion). Two previously invisible proton removal steps were detected, thereby filling two gaps in the basic reaction-cycle model of photosynthetic water oxidation. In the S(2) → S(3) transition of the classical S-state cycle, an intermediate is formed by deprotonation clearly before electron transfer to the oxidant (Y Z OX). The rate-determining elementary step (τ, approximately 30 µs at 20 °C) in the long-distance proton relocation toward the protein-water interface is characterized by a high activation energy (E(a) = 0.46 ± 0.05 eV) and strong H/D kinetic isotope effect (approximately 6). The characteristics of a proton transfer step during the S(0) → S(1) transition are similar (τ, approximately 100 µs; E(a) = 0.34 ± 0.08 eV; kinetic isotope effect, approximately 3); however, the proton removal from the Mn complex proceeds after electron transfer to . By discovery of the transient formation of two further intermediate states in the reaction cycle of photosynthetic water oxidation, a temporal sequence of strictly alternating removal of electrons and protons from the catalytic site is established.

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

PubMed

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

2017-10-26

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

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

NASA Astrophysics Data System (ADS)

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

2016-11-01

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

A benchmark study of electronic excitation energies, transition moments, and excited-state energy gradients on the nicotine molecule

NASA Astrophysics Data System (ADS)

Egidi, Franco; Segado, Mireia; Koch, Henrik; Cappelli, Chiara; Barone, Vincenzo

2014-12-01

In this work, we report a comparative study of computed excitation energies, oscillator strengths, and excited-state energy gradients of (S)-nicotine, chosen as a test case, using multireference methods, coupled cluster singles and doubles, and methods based on time-dependent density functional theory. This system was chosen because its apparent simplicity hides a complex electronic structure, as several different types of valence excitations are possible, including n-π*, π-π*, and charge-transfer states, and in order to simulate its spectrum it is necessary to describe all of them consistently well by the chosen method.

A benchmark study of electronic excitation energies, transition moments, and excited-state energy gradients on the nicotine molecule

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

Egidi, Franco, E-mail: franco.egidi@sns.it; Segado, Mireia; Barone, Vincenzo, E-mail: vincenzo.barone@sns.it

In this work, we report a comparative study of computed excitation energies, oscillator strengths, and excited-state energy gradients of (S)-nicotine, chosen as a test case, using multireference methods, coupled cluster singles and doubles, and methods based on time-dependent density functional theory. This system was chosen because its apparent simplicity hides a complex electronic structure, as several different types of valence excitations are possible, including n-π{sup *}, π-π{sup *}, and charge-transfer states, and in order to simulate its spectrum it is necessary to describe all of them consistently well by the chosen method.

Oxygen reactivity of the biferrous site in the de novo designed four helix bundle peptide DFsc: nature of the "intermediate" and reaction mechanism.

PubMed

Calhoun, Jennifer R; Bell, Caleb B; Smith, Thomas J; Thamann, Thomas J; DeGrado, William F; Solomon, Edward I

2008-07-23

The DFsc and DFscE11D de novo designed protein scaffolds support biomimetic diiron cofactor sites that react with dioxygen forming a 520 nm "intermediate" species with an apparent pseudo-first-order formation rate constant of 2.2 and 4.8 s-1, respectively. Resonance Raman spectroscopy shows that this absorption feature is due to a phenolate-to-ferric charge transfer transition arising from a single tyrosine residue coordinating terminally to one of the ferric ions in the site. Phenol coordination could provide a proton to promote rapid loss of a putative peroxo species.

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

NASA Astrophysics Data System (ADS)

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

2015-03-01

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

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

DOE PAGES

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

2016-05-10

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

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

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

Wang, Han; Bang, Junhyeok; Sun, Yiyang

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

Thermodynamic and kinetic studies of As2O3 toxicological effects on human insulin in generation diabetes mellitus

NASA Astrophysics Data System (ADS)

Mohsennia, Mohsen; Motaharinejad, Atieh; Rafiee-Pour, Hossain-Ali; Torabbeigi, Marzieh

2017-12-01

The interaction of arsenic trioxide with human insulin was investigated by circular dichroism (CD), cyclic voltammetry and electrophoresis techniques. The interfacial behavior of insulin in presence of As2O3 onto the Ag electrode surface was studied at 310 K in phosphate buffer solution (PBS). According to Far-UV CD spectroscopy results, As2O3 caused to decrease in structural compactness and variety of alpha helix into beta structures. Near-UV CD indicated that As2O3 dissociates disulfide linkage in insulin structure. The kinetic parameters, including charge-transfer coefficient and apparent heterogeneous electron transfer rate constant were also determined. The thermodynamic parameters of insulin denaturation in presence of arsenic trioxide were calculated and reported. The obtained results indicated strong adsorption of insulin in presence of arsenic trioxide onto the Ag surface via chemisorptions.

Pentachlorophenol radical cations generated on Fe(III)-montmorillonite initiate octachlorodibenzo-p-dioxin formation in clays: DFT and FTIR studies

PubMed Central

Gu, Cheng; Liu, Cun; Johnston, Cliff T.; Teppen, Brian J.; Li, Hui; Boyd, Stephen A.

2011-01-01

Octachlorodibenzodioxin (OCDD) forms spontaneously from pentachlorophenol (PCP) on the surfaces of Fe(III)-saturated smectite clay (1). Here, we used in situ FTIR methods and quantum mechanical calculations to determine the mechanism by which this reaction is initiated. As the clay was dehydrated, vibrational spectra showed new peaks that grew and then reversibly disappeared as the clay rehydrated. First principle DFT calculations of hydrated Fe-PCP clusters reproduced these transient FTIR peaks when inner-sphere complexation and concomitant electron transfer produced Fe(II) and PCP radical cations. Thus, our experimental (FTIR) and theoretical (quantum mechanical) results mutually support the hypothesis that OCDD formation on Fe-smectite surfaces is initiated by the reversible formation of metastable PCP radical cations via single electron transfer from PCP to Fe(III). The negatively charged clay surface apparently selects for this reaction mechanism by stabilizing PCP radical cations. PMID:21254769

Charge migration and charge transfer in molecular systems

PubMed Central

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

2017-01-01

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

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.

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

NASA Technical Reports Server (NTRS)

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

2001-01-01

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

Carbon fiber enhanced bioelectricity generation in soil microbial fuel cells.

PubMed

Li, Xiaojing; Wang, Xin; Zhao, Qian; Wan, Lili; Li, Yongtao; Zhou, Qixing

2016-11-15

The soil microbial fuel cell (MFC) is a promising biotechnology for the bioelectricity recovery as well as the remediation of organics contaminated soil. However, the electricity production and the remediation efficiency of soil MFC are seriously limited by the tremendous internal resistance of soil. Conductive carbon fiber was mixed with petroleum hydrocarbons contaminated soil and significantly enhanced the performance of soil MFC. The maximum current density, the maximum power density and the accumulated charge output of MFC mixed carbon fiber (MC) were 10, 22 and 16 times as high as those of closed circuit control due to the carbon fiber productively assisted the anode to collect the electron. The internal resistance of MC reduced by 58%, 83% of which owed to the charge transfer resistance, resulting in a high efficiency of electron transfer from soil to anode. The degradation rates of total petroleum hydrocarbons enhanced by 100% and 329% compared to closed and opened circuit controls without the carbon fiber respectively. The effective range of remediation and the bioelectricity recovery was extended from 6 to 20cm with the same area of air-cathode. The mixed carbon fiber apparently enhanced the bioelectricity generation and the remediation efficiency of soil MFC by means of promoting the electron transfer rate from soil to anode. The use of conductively functional materials (e.g. carbon fiber) is very meaningful for the remediation and bioelectricity recovery in the bioelectrochemical remediation. Copyright © 2016 Elsevier B.V. All rights reserved.

Spontaneous charged lipid transfer between lipid vesicles.

PubMed

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

2017-10-03

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

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

NASA Technical Reports Server (NTRS)

Kwong, Victor H. S.

1996-01-01

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

Enhancing light harvesting and charge transport in organic solar cells via integrating lanthanide-doped upconversation materials

NASA Astrophysics Data System (ADS)

Wang, Fei; Yang, Xiao-Yu; Niu, Meng-si; Feng, Lin; Lv, Cheng-kun; Zhang, Kang-ning; Bi, Peng-qing; Yang, Junliang; Hao, Xiao-Tao

2018-07-01

Irradiation of lanthanide-doped upconversion nanoparticles with infrared light can lead to the emission of visible light, which is subsequently absorbed by the organic photoactive layer resulting in the performance enhancement of organic solar cells (OSCs). In this work, OSCs based on poly (3-hexylthiophene) (P3HT) and Phenyl C61 butyric acid methyl ester (PC61BM) blending ytterbium(III), erbium(III) co-doped sodium yttrium fluoride (NaYF4: Yb3+, Er3+) nanoparticles were fabricated with inverted structures. The results indicated that the short current density (J sc) and fill factor were apparently enhanced from 8.60 mA cm‑2 to 9.31 mA cm‑2 and from 57.96% to 64.84%, respectively, leading to an increment of power conversion efficiency (PCE). The photocurrent improvement may have attributed to the additional absorption light generated from upconversion with 980 nm excitation. The active layers with upconversion nanoparticles were investigated to prove enhanced light harvesting, charge transport and energy transfer from upconversion nanoparticles to P3HT. A synergistic effect of broadening light harvesting, efficient energy transfer process, increased carrier mobility and enhanced exciton dissociation in the polymer bulk heterojunction may contribute to the performance enhancement.

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

USGS Publications Warehouse

Sherman, David M.

1987-01-01

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

Charge transfer transitions in optical spectra of NicMg1-cO oxides

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

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.

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.

Spontaneous electrorheological effect in nematic liquid crystals under Taylor-Couette flow configuration

NASA Astrophysics Data System (ADS)

Dhar, Jayabrata; Chakraborty, Suman

2017-09-01

Electrorheological (ER) characteristics of Nematic Liquid Crystals (NLCs) have been a topic of immense interest in the field of soft matter physics owing to its rheological modulation capabilities. Here we explore the augmentation in rheological characteristics of the nematic fluid confined within the annular region of the concentric cylindrical space with an Electrical Double Layer (EDL) induced at the fluid-substrate interface due to certain physico-chemical interactions. Using a Taylor-Couette flow configuration associated with an EDL induced at the inner cylinder wall, we show that a spontaneous electrorheological effect is generated owing to the intrinsic director anisotropy and structural order of complex nematic fluids. We seek to find the enhancement in torque transfer capability due to the inherent electrorheological nature of the nematic medium, apart from exploiting the innate nature of such homogeneous media to remain free of coagulation, a fact which makes it an excellent candidate for the applications in microfluidic environment. Our analysis reveals that with stronger induced charge density within the EDL, the apparent viscosity enhances, which, in turn, augments torque transfer across the concentric cylinder. The velocity profile tends to flatten in comparison to the classical circular Couette flow in annular geometry as one increases the surface charge density. We further observe a more pronounced ER effect for the nematic medium having larger electrical permittivity anisotropy. Besides the torque transfer qualifications, we also explore the distinct scenarios, wherein the same NLC medium exhibits shear thinning and shear thickening characteristics. The present configuration of the efficient torque transfer mechanism may be proficiently downscaled to micro-level and is relevant in the fabrication of micro-clutch and micro-dampers.

[Effect of Charge-Transfer Complex on Ultraviolet-Visible (UV-Vis) Absorption Property of Chromophoric Dissolved Organic Matter (CDOM) in Waters of Typical Water-Level Fluctuation Zones of the Three Gorges Reservoir Areas].

PubMed

Jiang, Tao; Liang, Jian; Zhang, Mu-xue; Wang, Ding-yong; Wei, Shi-qiang; Lu, Song

2016-02-15

As an important fraction of dissolved organic matter (DOM), chromophoric dissolved organic matter (CDOM) plays a key role in decision of the optical properties and photogeochemistry of DOM, and further affects pollutant fate and global carbon cycle. These optical properties are ascribed to two chromophoric systems including superposition of individual chromophores and charge-transfer (CT) complexation between electron donor (e.g., phenols and indoles) and acceptor (e.g., quinones and other oxidized aromatics) in DOM structures. Thus in this study, based on the "double-chromophoric system" model, DOM samples from four typical water-level fluctuation zones of Three Gorges Reservoir (TGR) areas were selected, to investigate the effect and contribution of charge-transfer complex to ultraviolet-visible (UV-Vis) absorption property of CDOM. Using NaBH, reduction method, original featureless absorption curve was classified into two independent curves caused by individual chromophoric group, which were derived from a simple superposition of independent chromophore and charge-transfer complex, respectively. Also, the changes in curve properties and specific parameters before and after NaBH4 reduction were compared. The results showed that in all DOM samples from the four sites of TGR, more than 35% of absorption was attributed from CT complex. Shibaozhai of Zhongxian and Zhenxi of Fuling showed the highest proportion ( > 50%). It suggested that the role of CT complex in CDOM property could not be neglected. After removal of CT complex, absorption curve showed blue-shift and CDOM concentration [a (355)] decreased significantly. Meanwhile, because of deforming of bonds by reduction, DOM structures became more dispersive and the molecular size was decreased, resulting in the lower spectral slope (S) observed, which evidentially supported that the supermolecular association structure of DOM was self-assembled through CT complex. Meanwhile, deceasing hydrophobic components led to decreased apparent aromaticity (lower SUVA values), whereas specific parameters including SUVA, CDOM and SR still were applicable for comparison among different DOM samples instead of the same sample without consideration of "double-cbromopboric system" model involving tbe role of CT complex. Comparatively, S(275-295) was dynamic due to tbe impact of CT effect. Furtbermore, establisbing DOC estimation model by short-wavelength range of CDOM was recommended because of its stability despite of CT complex.

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

NASA Astrophysics Data System (ADS)

Kobayashi, Hajime; Tokita, Yuichi

2015-03-01

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

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.

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

PubMed

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

2015-08-11

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

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.

Ionothermal Synthesis of Triazine-Heptazine Based Co-frameworks with Apparent Quantum Yields of 60 % at 420 nm for Solar Hydrogen Production from "Sea Water".

PubMed

Zhang, Guigang; Lin, Lihua; Li, Guosheng; Zhang, Yongfan; Savateev, Aleksandr; Wang, Xinchen; Antonietti, Markus

2018-05-31

Polymeric carbon nitride (PCN), either in triazine or heptazine forms, has been regarded as promising metal-free, environmental benign and sustainable photocatalysts for solar hydrogen production. However, PCN in most cases only exhibits moderate activities due to the inherent properties such as rapid charge carrier recombination. Here we present a triazine-heptazine copolymer synthesized from simple post-calcination of PCN in eutectic salts, i.e. NaCl/KCl, to modulate the polymerization process and optimize the structure. The construction of internal triazine-heptazine donor-acceptor (D-A) heterostructures is affirmed to significantly accelerate the charge transfer (CT) and thus corporately boost the photocatalytic activity (AQY= 60 % at 420 nm). This study highlights the construction of intermolecular D-A copolymers in NaCl/KCl molten salts with higher melting points but absence of lithium to modulate the polymerization process and chemical structure of PCN. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Properties of Structurally Excellent N-doped TiO2 Rutile

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

Chambers, Scott A.; Cheung, Sau H.; Shutthanandan, V.

2007-10-15

We have used plasma-assisted molecular beam epitaxy to synthesize structurally near-perfect crystalline films of TiO2-xNx rutile for the first time. These materials allow the properties of TiO2-xNx to be elucidated without the interfering effects of oxygen vacancy defects. In the absence of such defects, the extent of N incorporation in the lattice is limited to 2 ± 1 at. % of the anions. Substitutional N (NO) exhibits a -3 formal charge due to charge transfer from shallow-donor interstitial Ti(III), which forms during epitaxial growth. Hybridization between NO and adjacent lattice Ti ions occurs, resulting in new states off the topmore » of the rutile valence band and an apparent band gap reduction of ~ 0.5 eV. It is not yet known if these new states result in mobile electron-hole pair creation upon irradiation, but experiments are planned to answer this important question.« less

A pK change of acidic residues contributes to cation countertransport in the Ca-ATPase of sarcoplasmic reticulum. Role of H+ in Ca(2+)-ATPase countertransport.

PubMed

Yu, X; Hao, L; Inesi, G

1994-06-17

Proteoliposomal vesicles reconstituted with sarcoplasmic reticulum ATPase and exogenous lipids sustain ATP-dependent Ca2+ uptake and H+ ejection, as well as net charge displacement by Ca2+. We have studied the effect of lumenal (inner) and medium (extravesicular) pH variations on the countertransport ratios of H+ and Ca2+. We find that the Ca2+/H+ molar ratio is approximately 1 when the lumenal and medium pH is near neutrality, but changes with a specific pattern when the medium pH is varied in the presence of a constant lumenal pH and when the lumenal pH is varied in the presence of a constant medium pH. Empirical analysis of the experimental data shows that the apparent pK of the residue(s) releasing H+ into the medium is approximately 6.1, whereas the apparent pK of the residue(s) binding lumenal H+ is approximately 7.7. Assuming that the same acidic residues are involved in H+ and Ca2+ countertransport, our findings suggest a lower affinity for H+ in their outward orientation (prevalent in the ground state of the enzyme) and a higher affinity for H+ in lumenal orientation (prevalent in the phosphorylated state of the enzyme). Cyclic pK changes, coupled to ATP utilization, promote cation exchange, Ca2+ uptake, and H+ ejection by the vesicles. The stoichiometry of countertransport and net charge displacement is matched by a corresponding electrogenic behavior. A calculation of voltage development related to initial rates of charge transfer (dV/dt = (dQ/dt)/Cm) is given as a corrective replacement of a previous steady state calculation.

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

PubMed

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

2016-09-14

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

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

PubMed

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

2011-08-28

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

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

PubMed Central

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

2011-01-01

Molecular fragmentation algorithms provide a powerful approach to extending electronic structure methods to very large systems. Here we present a method for including charge transfer between molecular fragments in the explicit polarization (X-Pol) fragment method for calculating potential energy surfaces. In the conventional X-Pol method, the total charge of each fragment is preserved, and charge transfer between fragments is not allowed. The description of charge transfer is made possible by treating each fragment as an open system with respect to the number of electrons. To achieve this, we applied Mermin's finite temperature method to the X-Pol wave function. In the application of this method to X-Pol, the fragments are open systems that partially equilibrate their number of electrons through a quasithermodynamics electron reservoir. The number of electrons in a given fragment can take a fractional value, and the electrons of each fragment obey the Fermi–Dirac distribution. The equilibrium state for the electrons is determined by electronegativity equalization with conservation of the total number of electrons. The amount of charge transfer is controlled by re-interpreting the temperature parameter in the Fermi–Dirac distribution function as a coupling strength parameter. We determined this coupling parameter so as to reproduce the charge transfer energy obtained by block localized energy decomposition analysis. We apply the new method to ten systems, and we show that it can yield reasonable approximations to potential energy profiles, to charge transfer stabilization energies, and to the direction and amount of charge transferred. PMID:21895159

Performing the Millikan experiment at the molecular scale: Determination of atomic Millikan-Thomson charges by computationally measuring atomic forces.

PubMed

Rogers, T Ryan; Wang, Feng

2017-10-28

An atomic version of the Millikan oil drop experiment is performed computationally. It is shown that for planar molecules, the atomic version of the Millikan experiment can be used to define an atomic partial charge that is free from charge flow contributions. We refer to this charge as the Millikan-Thomson (MT) charge. Since the MT charge is directly proportional to the atomic forces under a uniform electric field, it is the most relevant charge for force field developments. The MT charge shows good stability with respect to different choices of the basis set. In addition, the MT charge can be easily calculated even at post-Hartree-Fock levels of theory. With the MT charge, it is shown that for a planar water dimer, the charge transfer from the proton acceptor to the proton donor is about -0.052 e. While both planar hydrated cations and anions show signs of charge transfer, anions show a much more significant charge transfer to the hydration water than the corresponding cations. It might be important to explicitly model the ion charge transfer to water in a force field at least for the anions.

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

NASA Astrophysics Data System (ADS)

Hestand, Nicholas J.

The field of organic electronics has received considerable attention over the past several years due to the promise of novel electronic materials that are cheap, flexible and light weight. While some devices based on organic materials have already emerged on the market (e.g. organic light emitting diodes), a deeper understanding of the excited states within the condensed phase is necessary both to improve current commercial products and to develop new materials for applications that are currently in the commercial pipeline (e.g. organic photovoltaics, wearable displays, and field effect transistors). To this end, a model for pi-conjugated molecular aggregates and crystals is developed and analyzed. The model considers two types of electronic excitations, namely Frenkel and charge-transfer excitons, both of which play a prominent role in determining the nature of the excited states within tightly-packed organic systems. The former consist of an electron-hole pair bound to the same molecule while in the later the electron and hole are located on different molecules. The model also considers the important nuclear reorganization that occurs when the system switches between electronic states. This is achieved using a Holstein-style Hamiltonian that includes linear vibronic coupling of the electronic states to the nuclear motion associated with the high frequency vinyl-stretching and ring-breathing modes. Analysis of the model reveals spectroscopic signatures of charge-transfer mediated J- and H-aggregation in systems where the photophysical properties are determined primarily by charge-transfer interactions. Importantly, such signatures are found to be sensitive to the relative phase of the intermolecular electron and hole transfer integrals, and the relative energy of the Frenkel and charge-transfer states. When the charge-transfer integrals are in phase and the energy of the charge-transfer state is higher than the Frenkel state, the system exhibits J-aggregate characteristics including a positive band curvature, a red shifted main absorption peak, and an increase in the ratio of the first two vibronic peaks relative to the monomer. On the other hand, when the charge-transfer integrals are out of phase and the energy of the charge-transfer state is higher than the Frenkel state, the system exhibits H-aggregate characteristics including a negative band curvature, a blue shifted main absorption peak, and a decrease in the ratio of the first two vibronic peaks relative to the monomer. Notably, these signatures are consistent with those exhibited by Coulombically coupled J- and H-aggregates. Additional signatures of charge-transfer J- and H-aggregation are also discovered, the most notable of which is the appearance of a second absorption band when the charge-transfer integrals are in phase and the charge-transfer and Frenkel excitons are near resonance. In such instances, the peak-to-peak spacing is found to be proportional to the sum of the electron and hole transfer integrals. Further analysis of the charge-transfer interactions within the context of an effective Frenkel exciton coupling reveals that the charge-transfer interactions interfere directly with the intermolecular Coulombic coupling. The interference can be either constructive or destructive resulting in either enhanced or suppressed J- or H- aggregate behavior relative to what is expected based on Coulombic coupling alone. Such interferences result in four new aggregate types, namely HH-, HJ-, JH-, and JJ-aggregates, where the first letter indicates the nature of the Coulombic coupling and the second indicates the nature of the charge-transfer coupling. Vibronic signatures of such aggregates are developed and provide a means by which to rapidly screen materials for certain electronic characteristics. Notably, a large total (Coulombic plus charge-transfer) exciton coupling is associated with an absorption spectrum in which the ratio of the first two vibronic peaks deviates significantly from that of the unaggregated monomer. Hence, strongly coupled, high exciton mobility aggregates can be readily distinguished from low mobility aggregates by the ratio of their first two vibronic peaks. (Abstract shortened by ProQuest.).

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

PubMed

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

2012-11-27

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

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

PubMed

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

2017-12-26

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

Energetic Residues and Crater Geometries from the Firing of 120-mm High-Explosive Mortar Projectiles into Eagle River Flats, June 2007

DTIC Science & Technology

2008-07-01

samples. ERDC/CRREL TR-08-10 15 c. US DH-48 isokinetic sampler. Figure 7 (cont’d). The second activity was the collection of soil at the...3 0.28 Mc1/3 0.3 Mc1/3 Ra Apparent radius of the crater in meters Mc Mass of the explosive charge in kilograms Da Apparent depth of the crater in... meters The apparent depth and radius of a crater will increase with the depth of explosive charge below the surface down to a maximum depth called

Supramolecular networks with electron transfer in two dimensions

DOEpatents

Stupp, Samuel I.; Stoddart, J. Fraser; Shveyd, Alexander K.; Tayi, Alok S.; Sue, Chi-Hau; Narayanan, Ashwin

2016-09-13

Organic charge-transfer (CT) co-crystals in a crossed stack system are disclosed. The co-crystals exhibit bidirectional charge transfer interactions where one donor molecule shares electrons with two different acceptors, one acceptor face-to-face and the other edge-to-face. The assembly and charge transfer interaction results in a pleochroic material whereby the optical absorption continuously changes depending on the polarization angle of incident light.

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

NASA Technical Reports Server (NTRS)

Chakraverty, B. K.

1990-01-01

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

Two-phase charge-coupled device

NASA Technical Reports Server (NTRS)

Kosonocky, W. F.; Carnes, J. E.

1973-01-01

A charge-transfer efficiency of 99.99% per stage was achieved in the fat-zero mode of operation of 64- and 128-stage two-phase charge-coupled shift registers at 1.0-MHz clock frequency. The experimental two-phase charge-coupled shift registers were constructed in the form of polysilicon gates overlapped by aluminum gates. The unidirectional signal flow was accomplished by using n-type substrates with 0.5 to 1.0 ohm-cm resistivity in conjunction with a channel oxide thickness of 1000 A for the polysilicon gates and 3000 A for the aluminum gates. The operation of the tested shift registers with fat zero is in good agreement with the free-charge transfer characteristics expected for the tested structures. The charge-transfer losses observed when operating the experimental shift registers without the fat zero are attributed to fast interface state trapping. The analytical part of the report contains a review backed up by an extensive appendix of the free-charge transfer characteristics of CCD's in terms of thermal diffusion, self-induced drift, and fringing field drift. Also, a model was developed for the charge-transfer losses resulting from charge trapping by fast interface states. The proposed model was verified by the operation of the experimental two-phase charge-coupled shift registers.

A quantum mechanical-Poisson-Boltzmann equation approach for studying charge flow between ions and a dielectric continuum

NASA Astrophysics Data System (ADS)

Gogonea, Valentin; Merz, Kenneth M.

2000-02-01

This paper presents a theoretical model for the investigation of charge transfer between ions and a solvent treated as a dielectric continuum media. The method is a combination of a semiempirical effective Hamiltonian with a modified Poisson-Boltzmann equation which includes charge transfer in the form of a surface charge density positioned at the dielectric interface. The new Poisson-Boltzmann equation together with new boundary conditions results in a new set of equations for the electrostatic potential (or polarization charge densities). Charge transfer adds a new free energy component to the solvation free energy term, which accounts for all interactions between the transferred charge at the dielectric interface, the solute wave function and the solvent polarization charges. Practical calculations on a set of 19 anions and 17 cations demonstrate that charge exchange with a dielectric is present and it is in the range of 0.06-0.4 eu. Furthermore, the pattern of the magnitudes of charge transfer can be related to the acid-base properties of the ions in many cases, but exceptions are also found. Finally, we show that the method leads to an energy decomposition scheme of the total electrostatic energy, which can be used in mechanistic studies on protein and DNA interaction with water.

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

PubMed

Sukhomlinov, Sergey V; Müser, Martin H

2015-12-14

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

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

NASA Astrophysics Data System (ADS)

Sukhomlinov, Sergey V.; Müser, Martin H.

2015-12-01

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

Charge mobility retrieval approach from apparent charge packet movements based on the negative differential resistance theory.

PubMed

Meng, Jia; Zhang, Yewen; Holé, Stéphane; Zheng, Feihu; An, Zhenlian

2018-04-12

Space charge migration characteristics play an important role in the evaluation of polymer insulation performance. However, an accurate description of charge carrier mobility in several typical insulating polymers such as polyethylene, polypropylene is currently not available. Recently, with the observation of a series of negative charge packet movements associated with the negative differential resistance characteristic of charge mobility in LDPE films, the extraction of charge mobility from the apparent charge packet movement has been attempted using appropriate methods. Based on the previous report of the successful derivation of charge mobility from experimental results using numerical methods, the present research improves the derivation accuracy and describes the details of the charge mobility derivation procedure. Back simulation results under several typical polarizing fields using the derived charge mobility are exhibited. The results indicate that both the NDR theory and the simulation models for the polyethylene materials are reasonable. A significant migration velocity difference between the charge carrier and the charge packet is observed. Back simulations of the charge packet under several typical polarizing fields using the obtained E-v curve show good agreement with the experimental results. The charge packet shapes during the migrations were also found to vary with the polarizing field.

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.

Artificial Neural Network with Hardware Training and Hardware Refresh

NASA Technical Reports Server (NTRS)

Duong, Tuan A. (Inventor)

2003-01-01

A neural network circuit is provided having a plurality of circuits capable of charge storage. Also provided is a plurality of circuits each coupled to at least one of the plurality of charge storage circuits and constructed to generate an output in accordance with a neuron transfer function. Each of a plurality of circuits is coupled to one of the plurality of neuron transfer function circuits and constructed to generate a derivative of the output. A weight update circuit updates the charge storage circuits based upon output from the plurality of transfer function circuits and output from the plurality of derivative circuits. In preferred embodiments, separate training and validation networks share the same set of charge storage circuits and may operate concurrently. The validation network has a separate transfer function circuits each being coupled to the charge storage circuits so as to replicate the training network s coupling of the plurality of charge storage to the plurality of transfer function circuits. The plurality of transfer function circuits may be constructed each having a transconductance amplifier providing differential currents combined to provide an output in accordance with a transfer function. The derivative circuits may have a circuit constructed to generate a biased differential currents combined so as to provide the derivative of the transfer function.

Redox shuttle mechanism enhances photocatalytic H2 generation on Ni-decorated CdS nanorods

NASA Astrophysics Data System (ADS)

Simon, Thomas; Bouchonville, Nicolas; Berr, Maximilian J.; Vaneski, Aleksandar; Adrović, Asmir; Volbers, David; Wyrwich, Regina; Döblinger, Markus; Susha, Andrei S.; Rogach, Andrey L.; Jäckel, Frank; Stolarczyk, Jacek K.; Feldmann, Jochen

2014-11-01

Photocatalytic conversion of solar energy to fuels, such as hydrogen, is attracting enormous interest, driven by the promise of addressing both energy supply and storage. Colloidal semiconductor nanocrystals have been at the forefront of these efforts owing to their favourable and tunable optical and electronic properties as well as advances in their synthesis. The efficiency of the photocatalysts is often limited by the slow transfer and subsequent reactions of the photoexcited holes and the ensuing high charge recombination rates. Here we propose that employing a hydroxyl anion/radical redox couple to efficiently relay the hole from the semiconductor to the scavenger leads to a marked increase in the H2 generation rate without using expensive noble metal co-catalysts. The apparent quantum yield and the formation rate under 447 nm laser illumination exceeded 53% and 63 mmol g-1 h-1, respectively. The fast hole transfer confers long-term photostability on the system and opens new pathways to improve the oxidation side of full water splitting.

Two-dimensional porous architecture of protonated GCN and reduced graphene oxide via electrostatic self-assembly strategy for high photocatalytic hydrogen evolution under visible light

NASA Astrophysics Data System (ADS)

Pu, Chenchen; Wan, Jun; Liu, Enzhou; Yin, Yunchao; Li, Juan; Ma, Yongning; Fan, Jun; Hu, Xiaoyun

2017-03-01

Herein, porous protonated graphitic carbon nitride (pGCN) is prepared from bulk g-C3N4 (GCN) directly by acidic cutting and hydrothermal process. The holey structure not only provides a lot of bounds on the accelerated and photo induced charge transfer and thus reduce the aggregation, but also endows the GCN with more exposure to the active site. The pGCN is obtained with an increased band gap of 2.91 eV together with a higher specific surface area of 82.76 m2g-1. Meanwhile, the positively charged GCN resulted from the protonation pretreatment is beneficial for improving the interaction with negatively charged GO sheets. Compared with GCN, pGCN-rGO displays a significant decrease of PL intensities and an apparently enhancement of visible-light absorption, resulting a lower charge recombination rate and a better light absorption. Besides, the enhanced charge separation is demonstrated by photoluminescence emission spectroscopy and the transient photocurrent measurement. The photocatalytic performance studies for the degradation of MB indicate that pGCN-rGO exhibits the highest adsorption ability towards dye molecules. In addition, the pGCN-5 wt% rGO composite shows the optimal photocatalytic activity, the photodegradation rate of MB is 99.4% after 80 min of irradiation and the H2 evolution performance up to 557 μmol g-1h-1 under visible light, which is much higher than the other control samples.

Tuning charge transfer in the LaTiO3/RO/LaNiO3 (R = rare-earth) superlattices by the rare-earth oxides interfaces from a first-principles calculation

NASA Astrophysics Data System (ADS)

Yao, Fen; Zhang, Lifang; Meng, Junling; Liu, Xiaojuan; Zhang, Xiong; Zhang, Wenwen; Meng, Jian; Zhang, Hongjie

2018-03-01

We investigate the internal charge transfer at the isopolar interfaces in LaTiO3/RO/LaNiO3 (R = La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, and Lu) superlattices by means of density functional theory calculations. The charge transfer from Ti sites to Ni sites in all superlattices is induced by the electronegativity difference between the elements Ti and Ni, and the lanthanide oxides interfaces can modulate the amount of charge transfer. Comparison of the perovskite heterostructures with the different rare-earth interfaces shows that increasing the deviations of bond angles from 180.0° and the oxygen motions near the interfaces enhance charge transfer. The 4f electrons themselves of rare-earth elements have faint influences on charge transfer. In addition, the reasons why our calculated 4f states of Sm and Tm elements disagree with the experimental systems have been provided. It is hoped that all the calculated results could be used to design new functional nanoelectronic devices in perovskite oxides.

An Ab Initio Exciton Model Including Charge-Transfer Excited States

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

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

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

An Ab Initio Exciton Model Including Charge-Transfer Excited States

DOE PAGES

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

2017-06-15

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

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

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

PubMed

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

2017-08-08

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

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

PubMed

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

2018-08-31

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

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

NASA Astrophysics Data System (ADS)

Kozankiewicz, B.; Prochorow, J.

1989-08-01

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

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

NASA Astrophysics Data System (ADS)

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

2016-11-01

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

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

NASA Technical Reports Server (NTRS)

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

1992-01-01

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

33 CFR 156.115 - Person in charge: Limitations.

Code of Federal Regulations, 2011 CFR

2011-07-01

... transfer operations on more than one vessel at a time during transfers between vessels or between two or... (CONTINUED) POLLUTION OIL AND HAZARDOUS MATERIAL TRANSFER OPERATIONS Oil and Hazardous Material Transfer... charge of both a vessel and a facility during transfer operations unless authorized by the COTP. [CGD 75...

33 CFR 156.115 - Person in charge: Limitations.

Code of Federal Regulations, 2012 CFR

2012-07-01

... transfer operations on more than one vessel at a time during transfers between vessels or between two or... (CONTINUED) POLLUTION OIL AND HAZARDOUS MATERIAL TRANSFER OPERATIONS Oil and Hazardous Material Transfer... charge of both a vessel and a facility during transfer operations unless authorized by the COTP. [CGD 75...

33 CFR 156.115 - Person in charge: Limitations.

Code of Federal Regulations, 2010 CFR

2010-07-01

... transfer operations on more than one vessel at a time during transfers between vessels or between two or... (CONTINUED) POLLUTION OIL AND HAZARDOUS MATERIAL TRANSFER OPERATIONS Oil and Hazardous Material Transfer... charge of both a vessel and a facility during transfer operations unless authorized by the COTP. [CGD 75...

33 CFR 156.115 - Person in charge: Limitations.

Code of Federal Regulations, 2013 CFR

2013-07-01

... transfer operations on more than one vessel at a time during transfers between vessels or between two or... (CONTINUED) POLLUTION OIL AND HAZARDOUS MATERIAL TRANSFER OPERATIONS Oil and Hazardous Material Transfer... charge of both a vessel and a facility during transfer operations unless authorized by the COTP. [CGD 75...

33 CFR 156.115 - Person in charge: Limitations.

Code of Federal Regulations, 2014 CFR

2014-07-01

... transfer operations on more than one vessel at a time during transfers between vessels or between two or... (CONTINUED) POLLUTION OIL AND HAZARDOUS MATERIAL TRANSFER OPERATIONS Oil and Hazardous Material Transfer... charge of both a vessel and a facility during transfer operations unless authorized by the COTP. [CGD 75...

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

NASA Astrophysics Data System (ADS)

Jurgensen, Charles Willard

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

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.

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

NASA Astrophysics Data System (ADS)

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

2011-09-01

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

Are Hyperion and Phoebe Linked to Iapetus?

NASA Technical Reports Server (NTRS)

Jarvis, Kandy S.; Vilas, Faith; Larson, Stephen M.; Gaffey, Michael J.

1999-01-01

Narrowband reflectance spectra of the Saturnian satellites S VII Hyperion and S IX Phoebe were obtained across the 0.4 - 0.8 micron spectral region. The spectrum of Phoebe is similar to the spectrum of a C-class asteroid, with an absorption feature centered near 0.43 micron superimposed on the UV/blue intervalence charge transfer transition present in the spectrum. The spectrum of Hyperion shows the strong spectral slope apparent in spectra of many outer Solar System materials and attributed to organics. We use a linear mixing model to separate the reflectance spectrum of the dark material on Hyperion from the icy material. A distinct absorption feature centered at 0.67 micron is present. A slight inflection near 0.4 - 0.6 micron and change in slope near 0.73 micron suggesting the lower wavelength edge of an absorption are also present. These absorptions are very similar to those identified in the spectrum of the dark material on the surface of Iapetus, suggesting that the dark material on these two satellites is compositionally similar and has a similar origin. These absorption features are attributed to the (6)A(sub 1) yields (4)T(sub 2)(G) and (6)A(sub 1) yields (4)T(sub 1)(G) ferric charge transfer transitions in iron alteration minerals such as goethite and hematite that are products of the aqueous alteration of anhydrous silicates.

Spectrophotometric Determination of Mycophenolate Mofetil as Its Charge-Transfer Complexes with Two π-Acceptors

PubMed Central

Vinay, K. B.; Revanasiddappa, H. D.; Raghu, M. S.; Abdulrahman, Sameer. A. M.; Rajendraprasad, N.

2012-01-01

Two simple, selective, and rapid spectrophotometric methods are described for the determination of mycophenolate mofetil (MPM) in pure form and in tablets. Both methods are based on charge-transfer complexation reaction of MPM with p-chloranilic acid (p-CA) or 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) in dioxane-acetonitrile medium resulting in coloured product measurable at 520 nm (p-CA) or 580 nm (DDQ). Beer's law is obeyed over the concentration ranges of 40–400 and 12–120 μg mL−1 MPM for p-CA and DDQ, respectively, with correlation coefficients (r) of 0.9995 and 0.9947. The apparent molar absorptivity values are calculated to be 1.06 × 103 and 3.87 × 103 L mol−1 cm−1, respectively, and the corresponding Sandell's sensitivities are 0.4106 and 0.1119 μg cm−1. The limits of detection (LOD) and quantification (LOQ) are also reported for both methods. The described methods were successfully applied to the determination of MPM in tablets. Statistical comparison of the results with those of the reference method showed excellent agreement. No interference was observed from the common excipients present in tablets. Both methods were validated statistically for accuracy and precision. The accuracy and reliability of the methods were further ascertained by recovery studies via standard addition procedure. PMID:22567572

Proton affinity determinations and proton-bound dimer structure indications in C2 to C15, (alpha),(omega)-alkyldiamines

NASA Technical Reports Server (NTRS)

Karpas, Z.; Harden, C. S.; Smith, P. B. W.

1995-01-01

The 'kinetic method' was used to determine the proton affinity (PA) of a,coalkyldiamines from collision induced dissociation (CID) studies of protonated heterodimers. These PA values were consistently lower than those reported in the proton affinity scale. The apparent discrepancy was rationalized in terms of differences in the conformation of the protonated diamine monomers. The minimum energy species, formed by equilibrium proton transfer processes, have a cyclic conformation and the ion charge is shared by both amino-groups which are bridged by the proton. On the other hand, the species formed through dissociation of protonated dimers have a linear structure and the charge is localized on one of the amino-groups. Thus, the difference in the PA values obtained by both methods is a measure of the additional stability acquired by the protonated diamines through cyclization and charge delocalization. The major collision dissociation pathway of the protonated diamine monomers involved elimination of an ammonia moiety. Other reactions observed included loss of the second amino-group and several other bond cleavages. CID of the protonated dimers involved primarily formation of a protonated monomer through cleavage of the weaker hydrogen bond and subsequently loss of ammonia at higher collision energies. As observed from the CID studies, doubly charged ions were also formed from the diamines under conditions of the electrospray ionization.

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

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

Cramer, Christopher J.

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

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

NASA Astrophysics Data System (ADS)

Wang, Xin; Liang, Shi-Dong

2013-02-01

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

78 FR 63268 - Self-Regulatory Organizations; Financial Industry Regulatory Authority, Inc.; Notice of Filing...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-10-23

... Transfer Transaction Fees Charged by One Member to Another Member October 17, 2013. Pursuant to Section 19... Facility (the ``FINRA/NYSE TRF'') to transfer transaction fees charged by one member to another member on... agree in advance to transfer a transaction fee charged by one member to another member on over-the...

33 CFR 155.710 - Qualifications of person in charge.

Code of Federal Regulations, 2010 CFR

2010-07-01

... available to the PIC on the tankship at all times during the transfer or cargo-tank cleaning; and (iii) Is... Transfer Personnel, Procedures, Equipment, and Records § 155.710 Qualifications of person in charge. (a) On... the vessel, or the person who arranges and hires a person to be in charge either of a transfer of...

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

PubMed

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

2012-02-23

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

Determination of the apparent transfer coefficient for CO oxidation on Pt(poly), Pt(111), Pt(665) and Pt(332) using a potential modulation technique.

PubMed

Wang, Han-Chun; Ernst, Siegfried; Baltruschat, Helmut

2010-03-07

The apparent transfer coefficient, which gives the magnitude of the potential dependence of the electrochemical reaction rates, is the key quantity for the elucidation of electrochemical reaction mechanisms. We introduce the application of an ac method to determine the apparent transfer coefficient alpha' for the oxidation of pre-adsorbed CO at polycrystalline and single-crystalline Pt electrodes in sulfuric acid. The method allows to record alpha' quasi continuously as a function of potential (and time) in cyclic voltammetry or at a fixed potential, with the reaction rate varying with time. At all surfaces (Pt(poly), Pt(111), Pt(665), and Pt(332)) we clearly observed a transition of the apparent transfer coefficient from values around 1.5 at low potentials to values around 0.5 at higher potentials. Changes of the apparent transfer coefficients for the CO oxidation with potential were observed previously, but only from around 0.7 to values as low as 0.2. In contrast, our experimental findings completely agree with the simulation by Koper et al., J. Chem. Phys., 1998, 109, 6051-6062. They can be understood in the framework of a Langmuir-Hinshelwood mechanism. The transition occurs when the sum of the rate constants for the forward reaction (first step: potential dependent OH adsorption, second step: potential dependent oxidation of CO(ad) with OH(ad)) exceeds the rate constant for the back-reaction of the first step. We expect that the ac method for the determination of the apparent transfer coefficient, which we used here, will be of great help also in many other cases, especially under steady conditions, where the major limitations of the method are avoided.

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

NASA Astrophysics Data System (ADS)

Foggiatto, Alexandre L.; Sakurai, Takeaki

2018-03-01

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

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

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

Park, Changwon; Atalla, Viktor; Smith, Sean

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

Interfacial charge transfer absorption: Application to metal molecule assemblies

NASA Astrophysics Data System (ADS)

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

2006-05-01

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

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

DOE PAGES

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

2017-06-16

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

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

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

PubMed Central

Liu, Jian; McLuckey, Scott A.

2012-01-01

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

DCE-MRI-Derived Volume Transfer Constant (Ktrans) and DWI Apparent Diffusion Coefficient as Predictive Markers of Short- and Long-Term Efficacy of Chemoradiotherapy in Patients With Esophageal Cancer.

PubMed

Ye, Zhi-Min; Dai, Shu-Jun; Yan, Feng-Qin; Wang, Lei; Fang, Jun; Fu, Zhen-Fu; Wang, Yue-Zhen

2018-01-01

This study aimed to evaluate both the short- and long-term efficacies of chemoradiotherapy in relation to the treatment of esophageal cancer . This was achieved through the use of dynamic contrast-enhanced magnetic resonance imaging-derived volume transfer constant and diffusion weighted imaging-derived apparent diffusion coefficient . Patients with esophageal cancer were assigned into the sensitive and resistant groups based on respective efficacies in chemoradiotherapy. Dynamic contrast-enhanced magnetic resonance imaging and diffusion weighted imaging were used to measure volume transfer constant and apparent diffusion coefficient, while computed tomography was used to calculate tumor size reduction rate. Pearson correlation analyses were conducted to analyze correlation between volume transfer constant, apparent diffusion coefficient, and the tumor size reduction rate. Receiver operating characteristic curve was constructed to analyze the short-term efficacy of volume transfer constant and apparent diffusion coefficient, while Kaplan-Meier curve was employed for survival rate analysis. Cox proportional hazard model was used for the risk factors for prognosis of patients with esophageal cancer. Our results indicated reduced levels of volume transfer constant, while increased levels were observed in ADC min , ADC mean , and ADC max following chemoradiotherapy. A negative correlation was determined between ADC min , ADC mean , and ADC max , as well as in the tumor size reduction rate prior to chemoradiotherapy, whereas a positive correlation was uncovered postchemoradiotherapy. Volume transfer constant was positively correlated with tumor size reduction rate both before and after chemoradiotherapy. The 5-year survival rate of patients with esophageal cancer having high ADC min , ADC mean , and ADC max and volume transfer constant before chemoradiotherapy was greater than those with respectively lower values. According to the Cox proportional hazard model, ADC mean , clinical stage, degree of differentiation, and tumor stage were all confirmed as being independent risk factors in regard to the prognosis of patients with EC. The findings of this study provide evidence suggesting that volume transfer constant and apparent diffusion coefficient as being tools allowing for the evaluation of both the short- and long-term efficacies of chemoradiotherapy esophageal cancer treatment.

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

PubMed

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

2018-05-04

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

Proton transfer complexes based on some π-acceptors having acidic protons with 3-amino-6-[2-(2-thienyl)vinyl]-1,2,4-triazin-5(4 H)-one donor: Synthesis and spectroscopic characterizations

NASA Astrophysics Data System (ADS)

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

2011-05-01

Charge transfer complexes based on 3-amino-6-[2-(2-thienyl)vinyl]-1,2,4-triazin-5(4 H)-one (ArNH 2) organic basic donor and pi-acceptors having acidic protons such as picric acid (PiA), hydroquinone (Q(OH) 2) and 3,5-dinitrobenzene (DNB) have been synthesized and spectroscopically studied. The sbnd NH3+ ammonium ion was formed under the acid-base theory through proton transfer from an acidic to basic centers in all charge transfer complexes resulted. The values of formation constant ( KCT) and molar extinction coefficient ( ɛCT) which were estimated from the spectrophotometric studies have a dramatic effect for the charge transfer complexes with differentiation of pi-acceptors. For further studies the vibrational spectroscopy of the [( ArNH3+)(PiA -)] (1), [( ArNH3+)(Q (OH)2-)] (2) and [( ArNH3+)(DNB -)] (3) of (1:1) charge transfer complexes of (donor: acceptor) were characterized by elemental analysis, infrared spectra, Raman spectra, 1H and 13CNMR spectra. The experimental data of elemental analyses of the charge transfer complexes (1), (2) and (3) were in agreement with calculated data. The IR and Raman spectra of (1), (2) and (3) are indicated to the presence of bands around 3100 and 1600 cm -1 distinguish to sbnd NH3+. The thermogravimetric analysis (TG) and differential scanning calorimetry (DSC) techniques were performed to give knowledge about thermal stability behavior of the synthesized charge transfer complexes. The morphological features of start materials and charge transfer complexes were investigated using scanning electron microscopy (SEM) and optical microscopy.

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

NASA Astrophysics Data System (ADS)

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

2014-11-01

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

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

PubMed

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

2018-06-01

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

Monte-Carlo modelling of nano-material photocatalysis: bridging photocatalytic activity and microscopic charge kinetics.

PubMed

Liu, Baoshun

2016-04-28

In photocatalysis, it is known that light intensity, organic concentration, and temperature affect the photocatalytic activity by changing the microscopic kinetics of holes and electrons. However, how the microscopic kinetics of holes and electrons relates to the photocatalytic activity was not well known. In the present research, we developed a Monte-Carlo random walking model that involved all of the charge kinetics, including the photo-generation, the recombination, the transport, and the interfacial transfer of holes and electrons, to simulate the overall photocatalytic reaction, which we called a "computer experiment" of photocatalysis. By using this model, we simulated the effect of light intensity, temperature, and organic surface coverage on the photocatalytic activity and the density of the free electrons that accumulate in the simulated system. It was seen that the increase of light intensity increases the electron density and its mobility, which increases the probability for a hole/electron to find an electron/hole for recombination, and consequently led to an apparent kinetics that the quantum yield (QY) decreases with the increase of light intensity. It was also seen that the increase of organic surface coverage could increase the rate of hole interfacial transfer and result in the decrease of the probability for an electron to recombine with a hole. Moreover, the increase of organic coverage on the nano-material surface can also increase the accumulation of electrons, which enhances the mobility for electrons to undergo interfacial transfer, and finally leads to the increase of photocatalytic activity. The simulation showed that the temperature had a more complicated effect, as it can simultaneously change the activation of electrons, the interfacial transfer of holes, and the interfacial transfer of electrons. It was shown that the interfacial transfer of holes might play a main role at low temperature, with the temperature-dependence of QY conforming to the Arrhenius model. The activation of electrons from the traps to the conduction band might become important at high temperature, which accelerates the electron movement for recombination and leads to a temperature dependence of QY that deviates from the Arrhenius model.

Detailed electrochemical studies of the tetraruthenium polyoxometalate water oxidation catalyst in acidic media: identification of an extended oxidation series using Fourier transformed alternating current voltammetry.

PubMed

Lee, Chong-Yong; Guo, Si-Xuan; Murphy, Aidan F; McCormac, Timothy; Zhang, Jie; Bond, Alan M; Zhu, Guibo; Hill, Craig L; Geletii, Yurii V

2012-11-05

The electrochemistry of the water oxidation catalyst, Rb(8)K(2)[{Ru(4)O(4)(OH)(2)(H(2)O)(4)}(γ-SiW(10)O(36))(2)] (Rb(8)K(2)-1(0)) has been studied in the presence and absence of potassium cations in both hydrochloric and sulfuric acid solutions by transient direct current (dc) cyclic voltammetry, a steady state dc method in the rotating disk configuration and the kinetically sensitive technique of Fourier transformed large-amplitude alternating current (ac) voltammetry. In acidic media, the presence of potassium ions affects the kinetics (apparent rate of electron transfer) and thermodynamics (reversible potentials) of the eight processes (A'/A to H/H') that are readily detected under dc voltammetric conditions. The six most positive processes (A'/A to F/F'), each involve a one electron ruthenium based charge transfer step (A'/A, B'/B are Ru(IV/V) oxidation and C/C' to F/F' are Ru(IV/III) reduction). The apparent rate of electron transfer of the ruthenium centers in sulfuric acid is higher than in hydrochloric acid. The addition of potassium cations increases the apparent rates and gives rise to a small shift of reversible potential. Simulations of the Fourier transformed ac voltammetry method show that the B'/B, E/E', and F/F' processes are quasi-reversible, while the others are close to reversible. A third Ru(IV/V) oxidation process is observed just prior to the positive potential limit via dc methods. Importantly, the ability of the higher harmonic components of the ac method to discriminate against the irreversible background solvent process allows this (process I) as well as an additional fourth reversible ruthenium based process (J) to be readily identified. The steady-state rotating disk electrode (RDE) method confirmed that all four Ru-centers in Rb(8)K(2)-1(0) are in oxidation state IV. The dc and ac data indicate that reversible potentials of the four ruthenium centers are evenly spaced, which may be relevant to understanding of the water oxidation electrocatalysis. A profound effect of the potassium cation is observed for the one-electron transfer process (G/G') assigned to Ru(III/II) reduction and the multiple electron transfer reduction process (H/H') that arise from the tungstate polyoxometalate framework. A significant shift of E°' to a more positive potential value for process H/H' was observed on removal of K(+) (~100 mV in H(2)SO(4) and ~50 mV in HCl).

Charge transport in electrically doped amorphous organic semiconductors.

PubMed

Yoo, Seung-Jun; Kim, Jang-Joo

2015-06-01

This article reviews recent progress on charge generation by doping and its influence on the carrier mobility in organic semiconductors (OSs). The doping induced charge generation efficiency is generally low in OSs which was explained by the integer charge transfer model and the hybrid charge transfer model. The ionized dopants formed by charge transfer between hosts and dopants can act as Coulomb traps for mobile charges, and the presence of Coulomb traps in OSs broadens the density of states (DOS) in doped organic films. The Coulomb traps strongly reduce the carrier hopping rate and thereby change the carrier mobility, which was confirmed by experiments in recent years. In order to fully understand the doping mechanism in OSs, further quantitative and systematic analyses of charge transport characteristics must be accomplished. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

NASA Astrophysics Data System (ADS)

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

2015-02-01

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

Voltage and frequency dependence of prestin-associated charge transfer

PubMed Central

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

2009-01-01

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

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

PubMed

Young, Meggie N; Bleiholder, Christian

2017-04-01

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

Experimental studies on the effect of moisture content and volume resistivity on electrostatic behaviour of pharmaceutical powders.

PubMed

Choi, Kwangseok; Taghavivand, Milad; Zhang, Lifeng

2017-03-15

Pharmaceutical powders are mainly organic materials and are likely to be charged due to repeated inter-particle and particle-wall contacts during industrial processes. This study experimentally investigated the effect of moisture content (ranging from approximately 1.8 to 30wt.%) on tribocharging behaviour of pharmaceutical granules, as well as their apparent volume resistivity. The tribocharging behaviour of pharmaceutical granules was investigated using a rotating device and apparent volume resistivity was measured in a conventional volume resistivity test cell. Additional measurements were performed on individual ingredients, each having the same moisture content as that of the granules, in order to investigate the effect of each single ingredient on the apparent volume resistivity of granules. In this work, the individual ingredients used for granules were: α-Lactose Monohydrate (α-LMH), Microcrystalline Cellulose (MCC), Hydroxypropyl Methylcellulose (HPMC), and Croscarmellose Sodium (CCS). The results showed that the specific charge of granules began to increase at the moisture contents below 5wt.%, which can be referred as critical moisture content of granules. The apparent volume resistivity showed the same behaviour, indicating that the specific charge could be due to an increase in apparent volume resistivity of granules at reduced moisture content. Finally, it was shown that the apparent volume resistivity measured for granules was mainly affected by that of the α-LMH, the major component of granules accounting for 40wt.%. Copyright © 2017 Elsevier B.V. All rights reserved.

Rollover of Apparent Wave Attenuation in Ice Covered Seas

NASA Astrophysics Data System (ADS)

Li, Jingkai; Kohout, Alison L.; Doble, Martin J.; Wadhams, Peter; Guan, Changlong; Shen, Hayley H.

2017-11-01

Wave attenuation from two field experiments in the ice-covered Southern Ocean is examined. Instead of monotonically increasing with shorter waves, the measured apparent attenuation rate peaks at an intermediate wave period. This "rollover" phenomenon has been postulated as the result of wind input and nonlinear energy transfer between wave frequencies. Using WAVEWATCH III®, we first validate the model results with available buoy data, then use the model data to analyze the apparent wave attenuation. With the choice of source parameterizations used in this study, it is shown that rollover of the apparent attenuation exists when wind input and nonlinear transfer are present, independent of the different wave attenuation models used. The period of rollover increases with increasing distance between buoys. Furthermore, the apparent attenuation for shorter waves drops with increasing separation between buoys or increasing wind input. These phenomena are direct consequences of the wind input and nonlinear energy transfer, which offset the damping caused by the intervening ice.

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.

Nano-Advantage in Enhanced Drug Delivery with Biodegradable Nanoparticles: Contribution of Reduced Clearance

PubMed Central

Kadam, Rajendra S.; Bourne, David W. A.

2012-01-01

The aim of this study was to investigate the contribution of reduced apparent clearance to the enhanced exposure reported for biodegradable nanoparticles after extravascular and intravascular routes of administration. Plasma concentration profiles for drug and nanoparticle formulations after administration by intravenous, intraduodenal, and oral routes were extracted from the literature. Data were fit to pharmacokinetic models using BOOMER. The compartmental pharmacokinetic analysis of literature data for six drugs (camptothecin, 9-nitrocamptothecin, epirubicin, vinpocetine, clozapine, and cyclosporine) showed that the encapsulation of drug molecules in nanoparticles significantly reduced the apparent clearance and prolonged the apparent circulation half-life compared with those for the plain drug. Positively charged nanoparticles assessed in this study had lower apparent clearance, lower elimination rate constant values, and longer apparent circulation half-life than neutral and negatively charged nanoparticles. After oral administration, a reduction in apparent clearance contributed substantially to elevations in plasma drug exposure with nanoparticles. For the drugs and delivery systems examined, the nano-advantage in drug delivery enhancement can be explained, in part, by reduced clearance. PMID:22498894

Synergistic Effect of a Molecular Cocatalyst and a Heterojunction in a 1 D Semiconductor Photocatalyst for Robust and Highly Efficient Solar Hydrogen Production.

PubMed

Jiang, Daochuan; Irfan, Rana Muhammad; Sun, Zijun; Lu, Dapeng; Du, Pingwu

2016-11-09

Photocatalytic production of hydrogen by water splitting is a promising pathway for the conversion of solar energy into chemical energy. However, the photocatalytic conversion efficiency is often limited by the sluggish transfer of the photogenerated charge carriers, charge recombination, and subsequent slow catalytic reactions. Herein, we report a highly active noble-metal-free photocatalytic system for hydrogen production in water. The system contains a water-soluble nickel complex as a molecular cocatalyst and zinc sulfide on 1D cadmium sulfide as the heterojunction photocatalyst. The complex can efficiently transport photogenerated electrons and holes over a heterojunction photocatalyst to hamper charge recombination, leading to highly improved catalytic efficiency and durability of a heterojunction photocatalyst- molecular cocatalyst system. The results show that under optimal conditions, the average apparent quantum yield was approximately 58.3 % after 7 h of irradiation with monochromatic 420 nm light. In contrast, the value is only 16.8 % if the molecular cocatalyst is absent. Such a remarkable performance in a molecular cocatalyst-based photocatalytic system without any noble metal loading has, to the best of our knowledge, not been reported to date. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

NASA Astrophysics Data System (ADS)

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

2017-07-01

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

Charge Transfer and Catalysis at the Metal Support Interface

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

Baker, Lawrence Robert

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

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

NASA Astrophysics Data System (ADS)

Mandal, Krishnagopal; Demas, J. N.

1981-12-01

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

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

NASA Technical Reports Server (NTRS)

Kwong, Victor H. S.

1997-01-01

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

Molecular orbital (SCF-X-α-SW) theory of Fe2+-Mn3+, Fe3+-Mn2+, and Fe3+-Mn3+ charge transfer and magnetic exchange in oxides and silicates

USGS Publications Warehouse

Sherman, David M.

1990-01-01

Metal-metal charge-transfer and magnetic exchange interactions have important effects on the optical spectra, crystal chemistry, and physics of minerals. Previous molecular orbital calculations have provided insight on the nature of Fe2+-Fe3+ and Fe2+-Ti4+ charge-transfer transitions in oxides and silicates. In this work, spin-unrestricted molecular orbital calculations on (FeMnO10) clusters are used to study the nature of magnetic exchange and electron delocalization (charge transfer) associated with Fe3+-Mn2+, Fe3+-Mn3+, and Fe2+-Mn3+ interactions in oxides and silicates. 

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

PubMed

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

2011-04-01

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

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

NASA Astrophysics Data System (ADS)

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

2011-11-01

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

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

NASA Astrophysics Data System (ADS)

Shukla, Madhulata; Srivastava, Nitin; Saha, Satyen

2012-08-01

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

Charge transfer in iridate-manganite superlattices

DOE PAGES

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

2017-03-03

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

How can we make stable linear monoatomic chains? Gold-cesium binary subnanowires as an example of a charge-transfer-driven approach to alloying.

PubMed

Choi, Young Cheol; Lee, Han Myoung; Kim, Woo Youn; Kwon, S K; Nautiyal, Tashi; Cheng, Da-Yong; Vishwanathan, K; Kim, Kwang S

2007-02-16

On the basis of first-principles calculations of clusters and one dimensional infinitely long subnanowires of the binary systems, we find that alkali-noble metal alloy wires show better linearity and stability than either pure alkali metal or noble metal wires. The enhanced alternating charge buildup on atoms by charge transfer helps the atoms line up straight. The cesium doped gold wires showing significant charge transfer from cesium to gold can be stabilized as linear or circular monoatomic chains.

Inductive High Power Transfer Technologies for Electric Vehicles

NASA Astrophysics Data System (ADS)

Madzharov, Nikolay D.; Tonchev, Anton T.

2014-03-01

Problems associated with "how to charge the battery pack of the electric vehicle" become more important every passing day. Most logical solution currently is the non-contact method of charge, possessing a number of advantages over standard contact methods for charging. This article focuses on methods for Inductive high power contact-less transfer of energy at relatively small distances, their advantages and disadvantages. Described is a developed Inductive Power Transfer (IPT) system for fast charging of electric vehicles with nominal power of 30 kW over 7 to 9 cm air gap.

Charge-pump voltage converter

DOEpatents

Brainard, John P [Albuquerque, NM; Christenson, Todd R [Albuquerque, NM

2009-11-03

A charge-pump voltage converter for converting a low voltage provided by a low-voltage source to a higher voltage. Charge is inductively generated on a transfer rotor electrode during its transit past an inductor stator electrode and subsequently transferred by the rotating rotor to a collector stator electrode for storage or use. Repetition of the charge transfer process leads to a build-up of voltage on a charge-receiving device. Connection of multiple charge-pump voltage converters in series can generate higher voltages, and connection of multiple charge-pump voltage converters in parallel can generate higher currents. Microelectromechanical (MEMS) embodiments of this invention provide a small and compact high-voltage (several hundred V) voltage source starting with a few-V initial voltage source. The microscale size of many embodiments of this invention make it ideally suited for MEMS- and other micro-applications where integration of the voltage or charge source in a small package is highly desirable.

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

PubMed

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

2016-12-07

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

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

PubMed Central

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

2016-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2014-09-01

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

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

PubMed

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

2017-02-08

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

Opposites Attract: Organic Charge Transfer Salts

ERIC Educational Resources Information Center

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

2015-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

Charge-transfer channel in quantum dot-graphene hybrid materials

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

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

PubMed

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

2018-04-06

The energy band theory of a classical semiconductor can qualitatively explain the charge-transfer process in low-dimensional hybrid colloidal quantum dot (QD)-graphene (GR) materials; however, the definite charge-transfer channels are not clear. Using density functional theory (DFT) and time-dependent DFT, we simulate the hybrid QD-GR nanostructure, and by constructing its orbital interaction diagram, we show the quantitative coupling characteristics of the molecular orbitals (MOs) of the hybrid structure. The main MOs are derived from the fragment MOs (FOs) of GR, and the Cd 13 Se 13 QD FOs merge with the GR FOs in a certain proportion to afford the hybrid system. Upon photoexcitation, electrons in the GR FOs jump to the QD FOs, leaving holes in the GR FOs, and the definite charge-transfer channels can be found by analyzing the complex MOs coupling. The excited electrons and remaining holes can also be localized in the GR or the QD or transfer between the QD and GR with different absorption energies. The charge-transfer process for the selected excited states of the hybrid QD-GR structure are testified by the charge difference density isosurface. The natural transition orbitals, charge-transfer length analysis and 2D site representation of the transition density matrix also verify the electron-hole delocalization, localization, or coherence chacracteristics of the selected excited states. Therefore, our research enhances understanding of the coupling mechanism of low-dimensional hybrid materials and will aid in the design and manipulation of hybrid photoelectric devices for practical application in many fields.

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

DOE PAGES

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

2015-09-12

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

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

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

Frenkel versus charge-transfer exciton dispersion in molecular crystals

NASA Astrophysics Data System (ADS)

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

2013-11-01

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

Cross-linking of the electron-transfer flavoprotein to electron-transfer flavoprotein-ubiquinone oxidoreductase with heterobifunctional reagents.

PubMed Central

Steenkamp, D J

1988-01-01

The mitochondrial electron-transfer flavoprotein (ETF) is a heterodimer containing only one FAD. In previous work on the structure-function relationships of ETF, its interaction with the general acyl-CoA dehydrogenase (GAD) was studied by chemical cross-linking with heterobifunctional reagents [D. J. Steenkamp (1987) Biochem. J. 243, 519-524]. GAD whose lysine residues were substituted with 3-(2-pyridyldithio)propionyl groups was preferentially cross-linked to the small subunit of ETF, the lysine residues of which had been substituted with 4-mercaptobutyramidine (MBA) groups. This work was extended to the interaction of ETF with ETF-ubiquinone oxidoreductase (ETF-Q ox). ETF-Q ox was partially inactivated by modification with N-succinimidyl 3-(2-pyridyldithio)propionate to introduce pyridyl disulphide structures. A similar modification of ETF caused a large increase in the apparent Michaelis constant of ETF-Q ox for modified ETF owing to the loss of positive charge on some critical lysines of ETF. When ETF-Q ox was modified with 2-iminothiolane to introduce 4-mercaptobutyramidine groups, only a minor effect on the activity of the enzyme was observed. To retain the positive charges on the lysine residues of ETF, pyridyl disulphide structures were introduced by treating ETF with 2-iminothiolane in the presence of 2,2'-dithiodipyridyl. The electron-transfer activity of the resultant ETF preparation containing 4-(2-pyridyldithio)butyramidine (PDBA) groups was only slightly affected. When ETF-Q ox substituted with MBA groups was mixed with ETF bearing PDBA groups, at least 70% of the cross-links formed between the two proteins were between the small subunit of ETF and ETF-Q ox. ETF-Q ox, therefore, interacts predominantly with the same subunit of ETF as GAD. Variables which affect the selectivity of ETF-Q ox cross-linking to the subunits of ETF are considered. Images Fig. 4. Fig. 5. Fig. 6. PMID:3145738

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

NASA Astrophysics Data System (ADS)

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

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

New instrument for tribocharge measurement due to single particle impacts.

PubMed

Watanabe, Hideo; Ghadiri, Mojtaba; Matsuyama, Tatsushi; Ding, Yu Long; Pitt, Kendal G

2007-02-01

During particulate solid processing, particle-particle and particle-wall collisions can generate electrostatic charges. This may lead to a variety of problems ranging from fire and explosion hazards to segregation, caking, and blocking. A fundamental understanding of the particle charging in such situations is therefore essential. For this purpose we have developed a new device that can measure charge transfer due to impact between a single particle and a metal plate. The device consists of an impact test system and two sets of Faraday cage and preamplifier for charge measurement. With current amplifiers, high-resolution measurements of particle charges of approximately 1 and 10 fC have been achieved before and after the impact, respectively. The device allows charge measurements of single particles with a size as small as approximately 100 microm impacting on the target at different incident angles with a velocity up to about 80 m/s. Further analyses of the charge transfer as a function of particle initial charge define an equilibrium charge, i.e., an initial charge level prior to impact for which no net charge transfer would occur as a result of impact.

New instrument for tribocharge measurement due to single particle impacts

NASA Astrophysics Data System (ADS)

Watanabe, Hideo; Ghadiri, Mojtaba; Matsuyama, Tatsushi; Long Ding, Yu; Pitt, Kendal G.

2007-02-01

During particulate solid processing, particle-particle and particle-wall collisions can generate electrostatic charges. This may lead to a variety of problems ranging from fire and explosion hazards to segregation, caking, and blocking. A fundamental understanding of the particle charging in such situations is therefore essential. For this purpose we have developed a new device that can measure charge transfer due to impact between a single particle and a metal plate. The device consists of an impact test system and two sets of Faraday cage and preamplifier for charge measurement. With current amplifiers, high-resolution measurements of particle charges of approximately 1 and 10fC have been achieved before and after the impact, respectively. The device allows charge measurements of single particles with a size as small as ˜100μm impacting on the target at different incident angles with a velocity up to about 80m/s. Further analyses of the charge transfer as a function of particle initial charge define an equilibrium charge, i.e., an initial charge level prior to impact for which no net charge transfer would occur as a result of impact.

Magnetic field enhancement of organic photovoltaic cells performance.

PubMed

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

2017-06-27

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

Investigation of the electrocatalytic oxygen reduction and evolution reactions in lithium–oxygen batteries

DOE PAGES

Zheng, Dong; Zhang, Xuran; Qu, Deyu; ...

2015-04-21

Oxygen reduction and oxygen evolution reactions were examined on graphite electrodes with different crystal orientations. The kinetics for the redox couple O 2/O 2 •- are very fast, therefore no catalyst seems necessary to assist the charge transfer process. Apparently, the main source of the overpotential for the O 2 reduction reaction is from mass diffusion. Li 2O 2 becomes soluble in non-aqueous electrolytes in the presence of the tetraethylammonium tetrafluoroborate additive. The soluble B-O 2 2- ions can be oxidized electro-catalytically. The edge orientation of graphite demonstrates superior catalytic activity for the oxidation over basal orientation. The findings revealmore » an opportunity for recharging Li-air batteries efficiently and a new strategy of developing the catalyst for oxygen evolution reaction.« less

Enhanced photocatalytic hydrogen evolution from in situ formation of few-layered MoS2/CdS nanosheet-based van der Waals heterostructures.

PubMed

Iqbal, Shahid; Pan, Ziwei; Zhou, Kebin

2017-05-25

Here we report for the first time that the H 2 bubbles generated by photocatalytic water splitting are effective in the layer-by-layer exfoliation of MoS 2 nanocrystals (NCs) into few layers. The as-obtained few layers can be in situ assembled with CdS nanosheets (NSs) into van der Waals heterostructures (vdWHs) of few-layered MoS 2 /CdS NSs which, in turn, are effective in charge separation and transfer, leading to enhanced photocatalytic H 2 production activity. The few-layered MoS 2 /CdS vdWHs exhibited a H 2 evolution rate of 140 mmol g (CdS) -1 h -1 and achieved an apparent quantum yield of 66% at 420 nm.

33 CFR 127.1317 - Declaration of Inspection.

Code of Federal Regulations, 2010 CFR

2010-07-01

...— (1) The name of the vessel and that of the facility; (2) The date and time that the transfer begins... to begin transfer; and (5) The signature of each relief person in charge and the date and time of... Inspection. (a) Each person in charge of transfer for the facility shall ensure that no person transfers LHG...

33 CFR 127.1317 - Declaration of Inspection.

Code of Federal Regulations, 2013 CFR

2013-07-01

...— (1) The name of the vessel and that of the facility; (2) The date and time that the transfer begins... to begin transfer; and (5) The signature of each relief person in charge and the date and time of... Inspection. (a) Each person in charge of transfer for the facility shall ensure that no person transfers LHG...

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.

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

DTIC Science & Technology

2016-04-12

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

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

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

NASA Technical Reports Server (NTRS)

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

1992-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2015-09-01

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

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.

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

PubMed

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

2017-12-13

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

Charge-transfer crystallites as molecular electrical dopants

PubMed Central

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

2015-01-01

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

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.

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

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

Patwardhan, Sameer; Schatz, George C.

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

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

NASA Astrophysics Data System (ADS)

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

2012-02-01

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

Ultrafast investigation of photoinduced charge transfer in aminoanthraquinone pharmaceutical product

NASA Astrophysics Data System (ADS)

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

2017-02-01

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

Interfacial characteristics and leakage current transfer mechanisms in organometal trihalide perovskite gate-controlled devices via doping of PCBM

NASA Astrophysics Data System (ADS)

Wang, Yucheng; Zhang, Yuming; Liu, Yintao; Pang, Tiqiang; Hu, Ziyang; Zhu, Yuejin; Luan, Suzhen; Jia, Renxu

2017-11-01

Two types of perovskite (with and without doping of PCBM) based metal-oxide-semiconductor (MOS) gate-controlled devices were fabricated and characterized. The study of the interfacial characteristics and charge transfer mechanisms by doping of PCBM were analyzed by material and electrical measurements. Doping of PCBM does not affect the size and crystallinity of perovskite films, but has an impact on carrier extraction in perovskite MOS devices. The electrical hysteresis observed in capacitance-voltage and current-voltage measurements can be alleviated by doping of PCBM. Experimental results demonstrate that extremely low trap densities are found for the perovskite device without doping, while the doped sample leads to higher density of interface state. Three mechanisms including Ohm’s law, trap-filled-limit (TFL) emission, and child’s law were used to analyze possible charge transfer mechanisms. Ohm’s law mechanism is well suitable for charge transfer of both the perovskite MOS devices under light condition at large voltage, while TFL emission well addresses the behavior of charge transfer under dark at small voltage. This change of charge transfer mechanism is attributed to the impact of the ion drift within perovskites.

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

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

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

2016-03-14

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

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

NASA Astrophysics Data System (ADS)

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

2016-01-01

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

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

PubMed

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

2014-06-28

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

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

PubMed

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

2016-11-15

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

Variationally consistent approximation scheme for charge transfer

NASA Technical Reports Server (NTRS)

Halpern, A. M.

1978-01-01

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

Excited State Charge Transfer reaction with dual emission from 5-(4-dimethylamino-phenyl)-penta-2,4-dienenitrile: Spectral measurement and theoretical density functional theory calculation

NASA Astrophysics Data System (ADS)

Jana, Sankar; Dalapati, Sasanka; Ghosh, Shalini; Kar, Samiran; Guchhait, Nikhil

2011-07-01

The excited state intramolecular charge transfer process in donor-chromophore-acceptor system 5-(4-dimethylamino-phenyl)-penta-2,4-dienenitrile (DMAPPDN) has been investigated by steady state absorption and emission spectroscopy in combination with Density Functional Theory (DFT) calculations. This flexible donor acceptor molecule DMAPPDN shows dual fluorescence corresponding to emission from locally excited and charge transfer state in polar solvent. Large solvatochromic emission shift, effect of variation of pH and HOMO-LUMO molecular orbital pictures support excited state intramolecular charge transfer process. The experimental findings have been correlated with the calculated structure and potential energy surfaces based on the Twisted Intramolecular Charge Transfer (TICT) model obtained at DFT level using B3LYP functional and 6-31+G( d, p) basis set. The theoretical potential energy surfaces for the excited states have been generated in vacuo and acetonitrile solvent using Time Dependent Density Functional Theory (TDDFT) and Time Dependent Density Functional Theory Polarized Continuum Model (TDDFT-PCM) method, respectively. All the theoretical results show well agreement with the experimental observations.

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

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

PubMed Central

2017-01-01

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

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.

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

PubMed

Zhou, Changjie; Yang, Weihuang; Zhu, Huili

2015-06-07

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

Charge transfer properties of pentacene adsorbed on silver: DFT study

NASA Astrophysics Data System (ADS)

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

2015-06-01

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

Femtochemistry of Intramolecular Charge and Proton Transfer Reactions in Solution

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

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

2005-03-17

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

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

PubMed

Ahmadivand, Arash; Gerislioglu, Burak; Pala, Nezih

2017-11-01

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

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

PubMed

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

1971-01-15

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

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

NASA Astrophysics Data System (ADS)

Bohr, Henrik G.; Malik, F. Bary

2013-11-01

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

Synthesis and electrochemical studies of charge-transfer complexes of thiazolidine-2,4-dione with σ and π acceptors

NASA Astrophysics Data System (ADS)

Singh, Prashant; Kumar, Pradeep; Katyal, Anju; Kalra, Rashmi; Dass, Sujata K.; Prakash, Satya; Chandra, Ramesh

2010-03-01

In the present work, we report the synthesis and characterization of novel charge-transfer complexes of thiazolidine-2,4-dione (TZD) with sigma acceptor (iodine) and pi acceptors (chloranil, dichlorodicyanoquinone, picric acid and duraquinone). We also evaluated their thermal and electrochemical properties and we conclude that these complexes are frequency dependent. Charge-transfer complex between thiazolidine-2,4-dione and iodine give best conductivity. In conclusion, complex with sigma acceptors are more conducting than with pi acceptors.

Measurement techniques and applications of charge transfer to aerospace research

NASA Technical Reports Server (NTRS)

Smith, A.

1978-01-01

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

CCD charge collection efficiency and the photon transfer technique

NASA Technical Reports Server (NTRS)

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

1985-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2017-11-01

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

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

PubMed

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

2017-11-29

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

Electron storage in single wall carbon nanotubes. Fermi level equilibration in semiconductor-SWCNT suspensions.

PubMed

Kongkanand, Anusorn; Kamat, Prashant V

2007-08-01

The use of single wall carbon nanotubes (SWCNTs) as conduits for transporting electrons in a photoelectrochemical solar cell and electronic devices requires better understanding of their electron-accepting properties. When in contact with photoirradiated TiO(2) nanoparticles, SWCNTs accept and store electrons. The Fermi level equilibration with photoirradiated TiO(2) particles indicates storage of up to 1 electron per 32 carbon atoms in the SWCNT. The stored electrons are readily discharged on demand upon addition of electron acceptors such as thiazine and oxazine dyes (reduction potential less negative than that of the SWCNT conduction band) to the TiO(2)-SWCNT suspension. The stepwise electron transfer from photoirradiated TiO(2) nanoparticles --> SWCNT --> redox couple has enabled us to probe the electron equilibration process and determine the apparent Fermi level of the TiO(2)-SWCNT system. A positive shift in apparent Fermi level (20-30 mV) indicates the ability of SWCNTs to undergo charge equilibration with photoirradiated TiO(2) particles. The dependence of discharge capacity on the reduction potential of the dye redox couple is compared for TiO(2) and TiO(2)-SWCNT systems under equilibration conditions.

Long-lived, charge-shift states in heterometallic, porphyrin-based dendrimers formed via click chemistry.

PubMed

Le Pleux, Loïc; Pellegrin, Yann; Blart, Errol; Odobel, Fabrice; Harriman, Anthony

2011-05-26

A series of multiporphyrin clusters has been synthesized and characterized in which there exists a logical gradient for either energy or electron transfer between the porphyrins. A central free-base porphyrin (FbP), for example, is equipped with peripheral zinc(II) porphyrins (ZnP) which act as ancillary light harvesters and transfer excitation energy to the FbP under visible light illumination. Additional energy-transfer steps occur at the triplet level, and the series is expanded by including magnesium(II) porphyrins and/or tin(IV) porphyrins as chromophores. Light-induced electron transfer is made possible by incorporating a gold(III) porphyrin (AuP(+)) into the array. Although interesting by themselves, these clusters serve as control compounds by which to understand the photophysical processes occurring within a three-stage dendrimer comprising an AuP(+) core, a second layer formed from four FbP units, and an outer layer containing 12 ZnP residues. Here, illumination into a peripheral ZnP leads to highly efficient electronic energy transfer to FbP, followed by charge transfer to the central AuP(+). Charge recombination within the resultant charge-shift state is intercepted by secondary hole transfer to the ZnP, which occurs with a quantum yield of around 20%. The final charge-shift state survives for some microseconds in fluid solution at room temperature.

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.

Theoretical study on naphthobischalcogenadiazole conjugated polymer systems and C61 derivative as organic photovoltaic semiconductors

NASA Astrophysics Data System (ADS)

Fujita, Takehiro; Matsui, Toru; Sumita, Masato; Imamura, Yutaka; Morihashi, Kenji

2018-02-01

We investigated the charge-transfer reactions of solar cells including a quaterthiophene copolymer with naphtho-bis-thiadiazole (PNTz4T) and naphtho-bis-oxadiazole (PNOz4T) using constrained density functional theory (CDFT). According to our calculations, the high electron-transfer rate results in a highly efficient solar cell, and the stable charge-transfer state results in low energy loss. Our computations imply that the following three factors are crucial to improve the performance of semiconducting polymers: (i) large structural changes following charge-transfer, (ii) narrow band gap, and (iii) spatially delocalized lowest unoccupied molecular orbital (LUMO) of the ground state.

Three-dimensional nonsteady heat-transfer analysis of an indirect heating furnace

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

Ito, H.; Umeda, Y.; Nakamura, Y.

1991-01-01

This paper reports on an accurate design method for industrial furnaces from the viewpoint of heat transfer. The authors carried out a three-dimensional nonsteady heat-transfer analysis for a practical-size heat- treatment furnace equipped with radiant heaters. The authors applied three software package programs, STREAM, MORSE, and TRUMP, for the analysis of the combined heat-transfer problems of radiation, conduction, and convection. The authors also carried out experiments of the heating of a charge consisting of packed bolts. The authors found that the air swirled inside the furnace. As for the temperature in each part in the furnace, analytical results were generallymore » in close agreement with the experimental ones. This suggests that our analytical method is useful for a fundamental heat- transfer-based design of a practical-size industrial furnace with an actual charge such as packed bolts. As for the temperature distribution inside the bolt charge (work), the analytical results were also in close agreement with the experimental ones. Consequently, it was found that the heat transfer in the bolt charge could be described with an effective thermal conductivity.« less

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

NASA Astrophysics Data System (ADS)

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

2017-09-01

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

Thermal energy and charge currents in multi-terminal nanorings

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

Kramer, Tobias; Konrad-Zuse-Zentrum für Informationstechnik Berlin, 14195 Berlin; Kreisbeck, Christoph

2016-06-15

We study in experiment and theory thermal energy and charge transfer close to the quantum limit in a ballistic nanodevice, consisting of multiply connected one-dimensional electron waveguides. The fabricated device is based on an AlGaAs/GaAs heterostructure and is covered by a global top-gate to steer the thermal energy and charge transfer in the presence of a temperature gradient, which is established by a heating current. The estimate of the heat transfer by means of thermal noise measurements shows the device acting as a switch for charge and thermal energy transfer. The wave-packet simulations are based on the multi-terminal Landauer-Büttiker approachmore » and confirm the experimental finding of a mode-dependent redistribution of the thermal energy current, if a scatterer breaks the device symmetry.« less

Absorption spectrometric study of charge transfer complex formation between 4-acetamidophenol (paracetamol) and a series of quinones including Vitamin K 3

NASA Astrophysics Data System (ADS)

Saha, Avijit; Mukherjee, Asok K.

2004-07-01

The formation of charge transfer (CT) complexes of 4-acetamidophenol (commonly called 'paracetamol') and a series of quinones (including Vitamin K 3) has been studied spectrophotometrically in ethanol medium. The vertical ionisation potential of paracetamol and the degrees of charge transfer of the complexes in their ground state has been estimated from the trends in the charge transfer bands. The oscillator and transition dipole strengths of the complexes have been determined from the CT absorption spectra at 298 K. The complexes have been found by Job's method of continuous variation to have the uncommon 2:1 (paracetamol:quinone) stoichiometry in each case. The enthalpies and entropies of formation of the complexes have been obtained by determining their formation constants at five different temperatures.

Probe-based measurement of lateral single-electron transfer between individual molecules

PubMed Central

Steurer, Wolfram; Fatayer, Shadi; Gross, Leo; Meyer, Gerhard

2015-01-01

The field of molecular electronics aims at using single molecules as functional building blocks for electronics components, such as switches, rectifiers or transistors. A key challenge is to perform measurements with atomistic control over the alignment of the molecule and its contacting electrodes. Here we use atomic force microscopy to examine charge transfer between weakly coupled pentacene molecules on insulating films with single-electron sensitivity and control over the atomistic details. We show that, in addition to the imaging capability, the probe tip can be used to control the charge state of individual molecules and to detect charge transfers to/from the tip, as well as between individual molecules. Our approach represents a novel route for molecular charge transfer studies with a host of opportunities, especially in combination with single atom/molecule manipulation and nanopatterning techniques. PMID:26387533

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

NASA Astrophysics Data System (ADS)

Teleb, Said M.; Gaballa, Akmal S.

2005-11-01

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

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

PubMed

Teleb, Said M; Gaballa, Akmal S

2005-11-01

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

Energy gap law of electron transfer in nonpolar solvents.

PubMed

Tachiya, M; Seki, Kazuhiko

2007-09-27

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

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.

Modeling the Partial Atomic Charges in Inorganometallic Molecules and Solids and Charge Redistribution in Lithium-Ion Cathodes

DOE PAGES

Wang, Bo; Li, Shaohong L.; Truhlar, Donald G.

2014-10-30

Partial atomic charges are widely used for the description of charge distributions of molecules and solids. These charges are useful to indicate the extent of charge transfer and charge flow during chemical reactions in batteries, fuel cells, and catalysts and to characterize charge distributions in capacitors, liquid-phase electrolytes, and solids and at electrochemical interfaces. However, partial atomic charges given by various charge models differ significantly, especially for systems containing metal atoms. In the present study, we have compared various charge models on both molecular systems and extended systems, including Hirshfeld, CM5, MK, ChElPG, Mulliken, MBS, NPA, DDEC, LoProp, and Badermore » charges. Their merits and drawbacks are compared. The CM5 charge model is found to perform well on the molecular systems, with a mean unsigned percentage deviation of only 9% for the dipole moments. We therefore formulated it for extended systems and applied it to study charge flow during the delithiation process in lithium-containing oxides used as cathodes. Our calculations show that the charges given by the CM5 charge model are reasonable and that during the delithiation process, the charge flow can occur not only on the transition metal but also on the anions. The oxygen atoms can lose a significant density of electrons, especially for deeply delithiated materials. We also discuss other methods in current use to analyze the charge transfer and charge flow in batteries, in particular the use of formal charge, spin density, and orbital occupancy. Here, we conclude that CM5 charges provide useful information in describing charge distributions in various materials and are very promising for the study of charge transfer and charge flows in both molecules and solids.« less

Modeling the Partial Atomic Charges in Inorganometallic Molecules and Solids and Charge Redistribution in Lithium-Ion Cathodes.

PubMed

Wang, Bo; Li, Shaohong L; Truhlar, Donald G

2014-12-09

Partial atomic charges are widely used for the description of charge distributions of molecules and solids. These charges are useful to indicate the extent of charge transfer and charge flow during chemical reactions in batteries, fuel cells, and catalysts and to characterize charge distributions in capacitors, liquid-phase electrolytes, and solids and at electrochemical interfaces. However, partial atomic charges given by various charge models differ significantly, especially for systems containing metal atoms. In the present study, we have compared various charge models on both molecular systems and extended systems, including Hirshfeld, CM5, MK, ChElPG, Mulliken, MBS, NPA, DDEC, LoProp, and Bader charges. Their merits and drawbacks are compared. The CM5 charge model is found to perform well on the molecular systems, with a mean unsigned percentage deviation of only 9% for the dipole moments. We therefore formulated it for extended systems and applied it to study charge flow during the delithiation process in lithium-containing oxides used as cathodes. Our calculations show that the charges given by the CM5 charge model are reasonable and that during the delithiation process, the charge flow can occur not only on the transition metal but also on the anions. The oxygen atoms can lose a significant density of electrons, especially for deeply delithiated materials. We also discuss other methods in current use to analyze the charge transfer and charge flow in batteries, in particular the use of formal charge, spin density, and orbital occupancy. We conclude that CM5 charges provide useful information in describing charge distributions in various materials and are very promising for the study of charge transfer and charge flows in both molecules and solids.

Analysis of pure and malachite green doped polysulfone sample using FT-IR technique

NASA Astrophysics Data System (ADS)

Nayak, Rashmi J.; Khare, P. K.; Nayak, J. G.

2018-05-01

The sample of pure and malachite green doped Polysulfone in the form of foil was prepared by isothermal immersion technique. For the preparation of pure sample 4 gm of Polysulfone was dissolved in 50 ml of Dimethyl farmamide (DMF) solvent, while for the preparation of doped sample 10 mg, 50 mg and 100 mg Malachite Green was mixed with 4 gm of Polysulfone respectively. For the study of structural characterization of these pure and doped sample, Fourier Transform Infra-Red Spectroscopy (FT-IR) technique was used. This study shows that the intensity of transmittance decreases as the ratio of doping increases in pure polysulfone. The reduction in intensity of transmittance is clearly apparent in the present case more over the bands were broader which indicates towards charge transfer interaction between the donar and acceptor molecule.

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.

Boundary layer charge dynamics in ionic liquid-ionic polymer transducers

NASA Astrophysics Data System (ADS)

Davidson, Jacob D.; Goulbourne, N. C.

2011-01-01

Ionic polymer transducers (IPTs), also known as ionic polymer-metal composites, are soft sensors and actuators which operate through a coupling of microscale chemical, electrical, and mechanical interactions. The use of an ionic liquid as solvent for an IPT has been shown to dramatically increase transducer lifetime in free-air use, while also allowing for higher applied voltages without electrolysis. In this work, we apply Nernst-Planck/Poisson theory to model charge transport in an ionic liquid IPT by considering a certain fraction of the ionic liquid ions as mobile charge carriers, a phenomenon which is unique to ionic liquid IPTs compared to their water-based counterparts. Numerical simulations are performed using the finite element method to examine how the introduction of another pair of mobile ions affects boundary layer charge dynamics, concentration, and charge density distributions in the electric double layer, and the overall charge transferred and current response of the IPT. Due to interactions with the Nafion ionomer, not all of the ionic liquid ions will function as mobile charge carriers; only a certain fraction will exist as "free" ions. The presence of mobile ionic liquid ions in the transducer will increase the overall charge transferred when a voltage is applied, and cause the current in the transducer to decay more slowly. The additional mobile ions also cause the ionic concentration profiles to exhibit a nonlinear dynamic response, characterized by nonmonotonic ionic concentration profiles in space and time. Although the presence of mobile ionic liquid ions increases the overall amount of charge transferred, this additional charge transfer occurs in a somewhat symmetric manner. Therefore, the additional charge transferred due to the ionic liquid ions does not greatly increase the net bending moment of the transducer; in fact, it is possible that ionic liquid ion movement actually decreases the observed bending response. This suggests that an optimal electromechanical conversion efficiency for bending actuation is achieved by using an ionic liquid where only a relatively small fraction of the ionic liquid ions exist as free ions. Conversely, if it is desired to increase the overall amount of charge transferred, an ionic liquid with a large fraction of free ions should be used. These theoretical considerations are found to be in good qualitative agreement with recent experimental results.

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

PubMed

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

2016-09-15

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

Electroluminescence Properties of IrQ(ppy)2 Dual-Emitter Organometallic Compound in Organic Light-Emitting Devices

NASA Astrophysics Data System (ADS)

Ciobotaru, Constantin Claudiu; Polosan, Silviu; Ciobotaru, Iulia Corina

2018-02-01

This paper reports the influence of the charge carrier mobility on the electroluminescent properties of a dual-emitter organometallic compound dispersed in two conjugated organic small-molecule host materials and embedded in organic light-emitting devices (OLEDs). The electroluminescent processes in OLEDs are strongly influenced by the host-guest interaction. The charge carrier mobility in the host material plays an important role in the electroluminescent processes but also depends on the triplet-triplet interaction with the organometallic compound. The low charge carrier mobility in 4,4'-bis( N-carbazolyl)-1,1'-biphenyl (CBP) host material reduces the electroluminescent processes, but they are slightly enhanced by the triplet-triplet exothermic charge transfer. The higher charge carrier mobility in the case of N, N'-bis(3-methylphenyl)- N, N'-diphenylbenzidine (TPD) host material influences the electroluminescent processes by the endothermic energy transfer at room temperature, which facilitates the triplet-triplet harvesting in the host-guest system. The excitation is transferred to the guest molecules by triplet-triplet interaction as a Dexter transfer, which occurs by endothermic transfer from the triplet exciton in the host to the triplet exciton in the guest.

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

NASA Astrophysics Data System (ADS)

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

2011-08-01

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

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

PubMed

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

2011-08-01

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

Protein-membrane interaction and fatty acid transfer from intestinal fatty acid-binding protein to membranes. Support for a multistep process.

PubMed

Falomir-Lockhart, Lisandro J; Laborde, Lisandro; Kahn, Peter C; Storch, Judith; Córsico, Betina

2006-05-19

Fatty acid transfer from intestinal fatty acid-binding protein (IFABP) to phospholipid membranes occurs during protein-membrane collisions. Electrostatic interactions involving the alpha-helical "portal" region of the protein have been shown to be of great importance. In the present study, the role of specific lysine residues in the alpha-helical region of IFABP was directly examined. A series of point mutants in rat IFABP was engineered in which the lysine positive charges in this domain were eliminated or reversed. Using a fluorescence resonance energy transfer assay, we analyzed the rates and mechanism of fatty acid transfer from wild type and mutant proteins to acceptor membranes. Most of the alpha-helical domain mutants showed slower absolute fatty acid transfer rates to zwitterionic membranes, with substitution of one of the lysines of the alpha2 helix, Lys27, resulting in a particularly dramatic decrease in the fatty acid transfer rate. Sensitivity to negatively charged phospholipid membranes was also reduced, with charge reversal mutants in the alpha2 helix the most affected. The results support the hypothesis that the portal region undergoes a conformational change during protein-membrane interaction, which leads to release of the bound fatty acid to the membrane and that the alpha2 segment is of particular importance in the establishment of charge-charge interactions between IFABP and membranes. Cross-linking experiments with a phospholipid-photoactivable reagent underscored the importance of charge-charge interactions, showing that the physical interaction between wild-type intestinal fatty acid-binding protein and phospholipid membranes is enhanced by electrostatic interactions. Protein-membrane interactions were also found to be enhanced by the presence of ligand, suggesting different collisional complex structures for holo- and apo-IFABP.

Associative charge transfer reactions. Temperature effects and mechanism of the gas-phase polymerization of propene initiated by a benzene radical cation.

PubMed

Ibrahim, Yehia; Meot-Ner Mautner, Michael; El-Shall, M Samy

2006-07-13

In associative charge transfer (ACT) reactions, a core ion activates ligand molecules by partial charge transfer. The activated ligand polymerizes, and the product oligomer takes up the full charge from the core ion. In the present system, benzene(+*) (Bz(+*)) reacts with two propene (Pr) molecules to form a covalently bonded ion, C(6)H(6)(+*) + 2 C(3)H(6) --> C(6)H(12)(+*) + C(6)H(6). The ACT reaction is activated by a partial charge transfer from Bz(+*) to Pr in the complex, and driven to completion by the formation of a covalent bond in the polymerized product. An alternative channel forms a stable association product (Bz.Pr)(+*), with an ACT/association product ratio of 60:40% that is independent of pressure and temperature. In contrast to the Bz(+*)/propene system, ACT polymerization is not observed in the Bz(+*)/ethylene (Et) system since charge transfer in the Bz(+*)(Et) complex is inefficient to activate the reaction. The roles of charge transfer in these complexes are verified by ab initio calculations. The overall reaction of Bz(+*) with Pr follows second-order kinetics with a rate constant of k (304 K) = 2.1 x 10(-12) cm(3) s(-1) and a negative temperature coefficient of k = aT(-5.9) (or an activation energy of -3 kcal/mol). The kinetic behavior is similar to sterically hindered reactions and suggests a [Bz(+*) (Pr)]* activated complex that proceeds to products through a low-entropy transition state. The temperature dependence shows that ACT reactions can reach a unit collision efficiency below 100 K, suggesting that ACT can initiate polymerization in cold astrochemical environments.

Advanced investigation of two-phase charge-coupled devices

NASA Technical Reports Server (NTRS)

Kosonocky, W. F.; Carnes, J. E.

1973-01-01

The performance of experimental two phase, charge-coupled shift registers constructed using polysilicon gates overlapped by aluminum gates was studied. Shift registers with 64, 128, and 500 stages were built and operated. Devices were operated at the maximum clock frequency of 20 MHz. Loss per transfer of less than .0001 was demonstrated for fat zero operation. The effect upon transfer efficiency of various structural and materials parameters was investigated including substrate orientation, resistivity, and conductivity type; channel width and channel length; and method of channel confinement. Operation of the devices with and without fat zero was studied as well as operation in the complete charge transfer mode and the bias charge, or bucket brigade mode.

Influence of Processing Additives on Charge-Transfer Time Scales and Sound Velocity in Organic Bulk Heterojunction Films.

PubMed

Kaake, Loren G; Welch, Gregory C; Moses, Daniel; Bazan, Guillermo C; Heeger, Alan J

2012-05-17

The role of processing additives in organic bulk heterojunction thin films was investigated by means of transient absorption spectroscopy. The rate of ultrafast charge transfer was found to increase when a small amount of diiodooctane was used during film formation. In addition, coherent acoustic phonons were observed, and their velocity was determined. A strong correlation between the sound velocity and the charge-transfer time scale was observed, both of which could be explained by a subtle increase in thin film density.

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

NASA Technical Reports Server (NTRS)

Steigman, G.

1975-01-01

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

Electric field changes on Au nanoparticles on semiconductor supports--the molecular voltmeter and other methods to observe adsorbate-induced charge-transfer effects in Au/TiO2 nanocatalysts.

PubMed

McEntee, Monica; Stevanovic, Ana; Tang, Wenjie; Neurock, Matthew; Yates, John T

2015-02-11

Infrared (IR) studies of Au/TiO2 catalyst particles indicate that charge transfer from van der Waals-bound donor or acceptor molecules on TiO2 to or from Au occurs via transport of charge carriers in the semiconductor TiO2 support. The ΔνCO on Au is shown to be proportional to the polarizability of the TiO2 support fully covered with donor or acceptor molecules, producing a proportional frequency shift in νCO. Charge transfer through TiO2 is associated with the population of electron trap sites in the bandgap of TiO2 and can be independently followed by changes in photoluminescence intensity and by shifts in the broad IR absorbance region for electron trap sites, which is also proportional to the polarizability of donors by IR excitation. Density functional theory calculations show that electron transfer from the donor molecules to TiO2 and to supported Au particles produces a negative charge on the Au, whereas the transfer from the Au particles to the TiO2 support into acceptor molecules results in a positive charge on the Au. These changes along with the magnitudes of the shifts are consistent with the Stark effect. A number of experiments show that the ∼3 nm Au particles act as "molecular voltmeters" in influencing ΔνCO. Insulator particles, such as SiO2, do not display electron-transfer effects to Au particles on their surface. These studies are preliminary to doping studies of semiconductor-oxide particles by metal ions which modify Lewis acid/base oxide properties and possibly strongly modify the electron-transfer and catalytic activity of supported metal catalyst particles.

Role of Au(NPs) in the enhanced response of Au(NPs)-decorated MWCNT electrochemical biosensor

PubMed Central

Mehmood, Shahid; Ciancio, Regina; Carlino, Elvio; Bhatti, Arshad S

2018-01-01

Background The combination of Au-metallic-NPs and CNTs are a new class of hybrid nanomaterials for the development of electrochemical biosensor. Concentration of Au(nanoparticles [NPs]) in the electrochemical biosensor is crucial for the efficient charge transfer between the Au-NPs-MWCNTs modified electrode and electrolytic solution. Methods In this work, the charge transfer kinetics in the glassy carbon electrode (GCE) modified with Au(NPs)–multiwalled carbon nanotube (MWCNT) nanohybrid with varied concentrations of Au(NPs) in the range 40–100 nM was studied using electrochemical impedance spectroscopy (EIS). Field emission scanning electron microscopy and transmission electron microscopy confirmed the attachment of Au(NPs) on the surface of MWCNTs. Results The cyclic voltammetry and EIS results showed that the charge transfer mechanism was diffusion controlled and the rate of charge transfer was dependent on the concentration of Au(NPs) in the nanohybrid. The formation of spherical diffusion zone, which was dependent on the concentration of Au(NPs) in nanohybrids, was attributed to result in 3 times the increase in the charge transfer rate ks, 5 times increase in mass transfer, and 5% (9%) increase in Ipa (Ipc) observed in cyclic voltammetry in 80 nM Au(NP) nanohybrid-modified GCE from MWCNT-modified GCE. The work was extended to probe the effect of charge transfer rates at various concentrations of Au(NPs) in the nanohybrid-modified electrodes in the presence of Escherichia coli. The cyclic voltammetry results clearly showed the best results for 80 nM Au(NPs) in nanohybrid electrode. Conclusion The present study suggested that the formation of spherical diffusion zone in nanohybrid-modified electrodes is critical for the enhanced electrochemical biosensing applications. PMID:29713161

An improved limit on the charge of antihydrogen from stochastic acceleration.

PubMed

Ahmadi, M; Baquero-Ruiz, M; Bertsche, W; Butler, E; Capra, A; Carruth, C; Cesar, C L; Charlton, M; Charman, A E; Eriksson, S; Evans, L T; Evetts, N; Fajans, J; Friesen, T; Fujiwara, M C; Gill, D R; Gutierrez, A; Hangst, J S; Hardy, W N; Hayden, M E; Isaac, C A; Ishida, A; Jones, S A; Jonsell, S; Kurchaninov, L; Madsen, N; Maxwell, D; McKenna, J T K; Menary, S; Michan, J M; Momose, T; Munich, J J; Nolan, P; Olchanski, K; Olin, A; Povilus, A; Pusa, P; Rasmussen, C Ø; Robicheaux, F; Sacramento, R L; Sameed, M; Sarid, E; Silveira, D M; So, C; Tharp, T D; Thompson, R I; van der Werf, D P; Wurtele, J S; Zhmoginov, A I

2016-01-21

Antimatter continues to intrigue physicists because of its apparent absence in the observable Universe. Current theory requires that matter and antimatter appeared in equal quantities after the Big Bang, but the Standard Model of particle physics offers no quantitative explanation for the apparent disappearance of half the Universe. It has recently become possible to study trapped atoms of antihydrogen to search for possible, as yet unobserved, differences in the physical behaviour of matter and antimatter. Here we consider the charge neutrality of the antihydrogen atom. By applying stochastic acceleration to trapped antihydrogen atoms, we determine an experimental bound on the antihydrogen charge, Qe, of |Q| < 0.71 parts per billion (one standard deviation), in which e is the elementary charge. This bound is a factor of 20 less than that determined from the best previous measurement of the antihydrogen charge. The electrical charge of atoms and molecules of normal matter is known to be no greater than about 10(-21)e for a diverse range of species including H2, He and SF6. Charge-parity-time symmetry and quantum anomaly cancellation demand that the charge of antihydrogen be similarly small. Thus, our measurement constitutes an improved limit and a test of fundamental aspects of the Standard Model. If we assume charge superposition and use the best measured value of the antiproton charge, then we can place a new limit on the positron charge anomaly (the relative difference between the positron and elementary charge) of about one part per billion (one standard deviation), a 25-fold reduction compared to the current best measurement.

Poly(methylene blue) functionalized graphene modified carbon ionic liquid electrode for the electrochemical detection of dopamine.

PubMed

Sun, Wei; Wang, Yuhua; Zhang, Yuanyuan; Ju, Xiaomei; Li, Guangjiu; Sun, Zhenfan

2012-11-02

An ionic liquid 1-butylpyridinium hexafluorophosphate based carbon ionic liquid electrode (CILE) was used as the substrate electrode and a poly(methylene blue) (PMB) functionalized graphene (GR) composite film was co-electrodeposited on CILE surface by cyclic voltammetry. The PMB-GR/CILE exhibited better electrochemical performances with higher conductivity and lower electron transfer resistance. Electrochemical behavior of dopamine (DA) was further investigated by cyclic voltammetry and a pair of well-defined redox peaks appeared with the peak-to-peak separation (ΔE(p)) as 0.058V in 0.1 mol L(-1) pH 6.0 phosphate buffer solution, which proved a fast quasi-reversible electron transfer process on the modified electrode. Electrochemical parameters of DA on PMB-GR/CILE were calculated with the electron transfer number as 1.83, the charge transfer coefficients as 0.70, the apparent heterogeneous electron transfer rate constant as 1.72 s(-1) and the diffusional coefficient (D) as 3.45×10(-4) cm(2) s(-1), respectively. Under the optimal conditions with differential pulse voltammetric measurement, the linear relationship between the oxidation peak current of DA and its concentration was obtained in the range from 0.02 to 800.0 μmol L(-1) with the detection limit as 5.6 nmol L(-1) (3σ). The coexisting substances exhibited no interference and PMB-GR/CILE was applied to the detection of DA injection samples and human urine samples with satisfactory results. Copyright © 2012 Elsevier B.V. All rights reserved.

Possible Dynamically Gated Conductance along Heme Wires in Bacterial Multiheme Cytochromes

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

Smith, Dayle MA; Rosso, Kevin M.

2014-07-24

The staggered cross decaheme configuration of electron transfer co-factors in the outer-membrane cytochrome MtrF may serve as a prototype for conformationally-gated multi-heme electron transport. Derived from the bacterium Shewanella oneidensis, the staggered cross configuration reveals intersecting c-type octaheme and tetraheme “wires” containing thermodynamic “hills” and “valleys”, suggesting that the protein structure may include a dynamical mechanism for conductance and pathway switching depending on enzymatic functional need. Recent molecular simulations have established the pair-wise electronic couplings, redox potentials, and reorganization energies to predict the maximum conductance along the various heme wire pathways by sequential hopping of a single electron (PNAS (2014)more » 11,611-616). Here, we expand this information with classical molecular and statistical mechanics calculations of large-amplitude protein dynamics in MtrF, to address its potential to modulate pathway conductance, including assessment of the effect of the total charge state. Explicit solvent molecular dynamics simulations of fully oxidized and fully reduced MtrF employing ten independent 50-ns simulations at 300 K and 1 atm showed that reduced MtrF is more expanded and explores more conformational space than oxidized MtrF, and that heme reduction leads to increased heme solvent exposure. The slowest mode of collective decaheme motion is 90% similar between the oxidized and reduced states, and consists primarily of inter-heme separation with minor rotational contributions. The frequency of this motion is 1.7×107 s 1 for fully-oxidized and fully-reduced MtrF, respectively, slower than the downhill electron transfer rates between stacked heme pairs at the octaheme termini and faster than the electron transfer rates between parallel hemes in the tetraheme chain. This implies that MtrF uses slow conformational fluctuations to modulate electron flow along the octaheme pathway, apparently for the purpose of increasing the residence time of electrons on lowest potential hemes 4 and 9. This apparent gating mechanism should increase the success rate of electron transfer from MtrF to low potential environmental acceptors via these two solvent-exposed hemes.« less

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

PubMed Central

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

2016-01-01

Ultrafast electron transfer in dissociating iodomethane and fluoromethane molecules was studied at the Linac Coherent Light Source free-electron laser using an ultraviolet-pump, X-ray-probe scheme. The results for both molecules are discussed with respect to the nature of their UV excitation and different chemical properties. Signatures of long-distance intramolecular charge transfer are observed for both species, and a quantitative analysis of its distance dependence in iodomethane is carried out for charge states up to I21+. The reconstructed critical distances for electron transfer are in good agreement with a classical over-the-barrier model and with an earlier experiment employing a near-infrared pump pulse. PMID:27051675

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

NASA Technical Reports Server (NTRS)

Kwong, Victor H. S.

2003-01-01

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

Charge Transfer Reactions

NASA Astrophysics Data System (ADS)

Dennerl, Konrad

2010-12-01

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

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

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

Are Charge-State Distributions a Reliable Tool Describing Molecular Ensembles of Intrinsically Disordered Proteins by Native MS?

NASA Astrophysics Data System (ADS)

Natalello, Antonino; Santambrogio, Carlo; Grandori, Rita

2017-01-01

Native mass spectrometry (MS) has become a central tool of structural proteomics, but its applicability to the peculiar class of intrinsically disordered proteins (IDPs) is still object of debate. IDPs lack an ordered tridimensional structure and are characterized by high conformational plasticity. Since they represent valuable targets for cancer and neurodegeneration research, there is an urgent need of methodological advances for description of the conformational ensembles populated by these proteins in solution. However, structural rearrangements during electrospray-ionization (ESI) or after the transfer to the gas phase could affect data obtained by native ESI-MS. In particular, charge-state distributions (CSDs) are affected by protein conformation inside ESI droplets, while ion mobility (IM) reflects protein conformation in the gas phase. This review focuses on the available evidence relating IDP solution ensembles with CSDs, trying to summarize cases of apparent consistency or discrepancy. The protein-specificity of ionization patterns and their responses to ligands and buffer conditions suggests that CSDs are imprinted to protein structural features also in the case of IDPs. Nevertheless, it seems that these proteins are more easily affected by electrospray conditions, leading in some cases to rearrangements of the conformational ensembles.

Are Charge-State Distributions a Reliable Tool Describing Molecular Ensembles of Intrinsically Disordered Proteins by Native MS?

PubMed

Natalello, Antonino; Santambrogio, Carlo; Grandori, Rita

2017-01-01

Native mass spectrometry (MS) has become a central tool of structural proteomics, but its applicability to the peculiar class of intrinsically disordered proteins (IDPs) is still object of debate. IDPs lack an ordered tridimensional structure and are characterized by high conformational plasticity. Since they represent valuable targets for cancer and neurodegeneration research, there is an urgent need of methodological advances for description of the conformational ensembles populated by these proteins in solution. However, structural rearrangements during electrospray-ionization (ESI) or after the transfer to the gas phase could affect data obtained by native ESI-MS. In particular, charge-state distributions (CSDs) are affected by protein conformation inside ESI droplets, while ion mobility (IM) reflects protein conformation in the gas phase. This review focuses on the available evidence relating IDP solution ensembles with CSDs, trying to summarize cases of apparent consistency or discrepancy. The protein-specificity of ionization patterns and their responses to ligands and buffer conditions suggests that CSDs are imprinted to protein structural features also in the case of IDPs. Nevertheless, it seems that these proteins are more easily affected by electrospray conditions, leading in some cases to rearrangements of the conformational ensembles. Graphical Abstract ᅟ.

Self-assembled supramolecular system PDINH on TiO2 surface enhances hydrogen production.

PubMed

Li, Xin; Lv, Xingshuai; Zhang, Qianqian; Huang, Baibiao; Wang, Peng; Qin, Xiaoyan; Zhang, Xiaoyang; Dai, Ying

2018-09-01

Constructing organic-inorganic hybrids is one of the hopeful strategies to improve photocatalyst performance. In this study, perylene-3,4,9,10-tetracarboxylic diimide (PDINH) and commercial TiO 2 P25 are chosen as raw materials to construct a PDINH/TiO 2 organic-inorganic hybrid, which has higher photocatalytic H 2 production activity and photocurrent intensity than pure PDINH and TiO 2 , respectively. The apparent quantum efficiency for H 2 production over 0.5%PDINH/TiO 2 reaches as high as 70.69% using irradiation at 365 nm. Moreover, XRD, DRS, HRTEM, FT-IR, and XPS are used to characterize the crystal structure, optical absorption, morphology, molecular structure, and chemical bonds, as well as the elemental and chemical states of PDINH/TiO 2 organic-inorganic hybrid. The interfaces between PDINH and TiO 2 , which largely determine photocatalytic performance, is also analyzed systematically. Furthermore, charge density difference (Δρ) is used to analyze the electron-ion interactions of PDINH and TiO 2 , and reveals that substantial charge transfer occurs from PDINH to TiO 2 . Copyright © 2018. Published by Elsevier Inc.

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

Delocalization Drives Free Charge Generation in Conjugated Polymer Films

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

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

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

Delocalization Drives Free Charge Generation in Conjugated Polymer Films

DOE PAGES

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

2018-02-19

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

46 CFR 153.957 - Persons in charge of transferring liquid cargo in bulk or cleaning cargo tanks.

Code of Federal Regulations, 2014 CFR

2014-10-01

... SECURITY (CONTINUED) CERTAIN BULK DANGEROUS CARGOES SHIPS CARRYING BULK LIQUID, LIQUEFIED GAS, OR COMPRESSED GAS HAZARDOUS MATERIALS Operations Cargo Transfer Procedures § 153.957 Persons in charge of...

46 CFR 153.957 - Persons in charge of transferring liquid cargo in bulk or cleaning cargo tanks.

Code of Federal Regulations, 2010 CFR

2010-10-01

... SECURITY (CONTINUED) CERTAIN BULK DANGEROUS CARGOES SHIPS CARRYING BULK LIQUID, LIQUEFIED GAS, OR COMPRESSED GAS HAZARDOUS MATERIALS Operations Cargo Transfer Procedures § 153.957 Persons in charge of...

46 CFR 153.957 - Persons in charge of transferring liquid cargo in bulk or cleaning cargo tanks.

Code of Federal Regulations, 2013 CFR

2013-10-01

... SECURITY (CONTINUED) CERTAIN BULK DANGEROUS CARGOES SHIPS CARRYING BULK LIQUID, LIQUEFIED GAS, OR COMPRESSED GAS HAZARDOUS MATERIALS Operations Cargo Transfer Procedures § 153.957 Persons in charge of...

46 CFR 153.957 - Persons in charge of transferring liquid cargo in bulk or cleaning cargo tanks.

Code of Federal Regulations, 2012 CFR

2012-10-01

... SECURITY (CONTINUED) CERTAIN BULK DANGEROUS CARGOES SHIPS CARRYING BULK LIQUID, LIQUEFIED GAS, OR COMPRESSED GAS HAZARDOUS MATERIALS Operations Cargo Transfer Procedures § 153.957 Persons in charge of...

46 CFR 153.957 - Persons in charge of transferring liquid cargo in bulk or cleaning cargo tanks.

Code of Federal Regulations, 2011 CFR

2011-10-01

... SECURITY (CONTINUED) CERTAIN BULK DANGEROUS CARGOES SHIPS CARRYING BULK LIQUID, LIQUEFIED GAS, OR COMPRESSED GAS HAZARDOUS MATERIALS Operations Cargo Transfer Procedures § 153.957 Persons in charge of...

Polyoxometalate active charge-transfer material for mediated redox flow battery

DOEpatents

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

2017-01-17

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

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

PubMed

Bacchus-Montabonel, Marie-Christine

2014-08-21

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

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

NASA Astrophysics Data System (ADS)

Chen, Hanghui; Marianetti, Chris; Millis, Andrew

2013-03-01

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

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

PubMed Central

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

2016-01-01

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

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

PubMed

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

2017-10-01

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

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

NASA Astrophysics Data System (ADS)

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

2017-10-01

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

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

NASA Technical Reports Server (NTRS)

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

1975-01-01

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

Ferrocene-decorated nanocrystalline cellulose with charge carrier mobility.

PubMed

Eyley, Samuel; Shariki, Sara; Dale, Sara E C; Bending, Simon; Marken, Frank; Thielemans, Wim

2012-04-24

Ferrocene-decorated cellulose nanowhiskers were prepared by the grafting of ethynylferrocene onto azide functionalized cotton-derived cellulose nanowhiskers using azide-alkyne cycloaddition. Successful surface modification and retention of the crystalline morphology of the nanocrystals was confirmed by elemental analysis, inductively coupled plasma-atomic emission spectroscopy, X-ray photoelectron spectroscopy, and X-ray diffraction. The coverage with ferrocenyl is high (approximately 1.14 × 10(-3) mol g(-1) or 4.6 × 10(13) mol cm(-2) corresponding to a specific area of 61 Å(2) per ferrocene). Cyclic voltammetry measurements of films formed by deposition of ferrocene-decorated nanowhiskers showed that this small spacing of redox centers along the nanowhisker surface allowed conduction hopping of electrons. The apparent diffusion coefficient for electron (or hole) hopping via Fe(III/II) surface sites is estimated as Dapp = 10(-19) m(2)s(-1) via impedance methods, a value significantly less than nonsolvated ferrocene polymers, which would be expected as the 1,2,3-triazole ring forms a rigid linker tethering the ferrocene to the nanowhisker surface. In part, this is believed to be also due to "bottleneck" diffusion of charges across contact points where individual cellulose nanowhiskers contact each other. However, the charge-communication across the nanocrystal surface opens up the potential for use of cellulose nanocrystals as a charge percolation template for the preparation of conducting films via covalent surface modification (with applications similar to those using adsorbed conducting polymers), for use in bioelectrochemical devices to gently transfer and remove electrons without the need for a solution-soluble redox mediator, or for the fabrication of three-dimensional self-assembled conducting networks.

Atomic charge transfer-counter polarization effects determine infrared CH intensities of hydrocarbons: a quantum theory of atoms in molecules model.

PubMed

Silva, Arnaldo F; Richter, Wagner E; Meneses, Helen G C; Bruns, Roy E

2014-11-14

Atomic charge transfer-counter polarization effects determine most of the infrared fundamental CH intensities of simple hydrocarbons, methane, ethylene, ethane, propyne, cyclopropane and allene. The quantum theory of atoms in molecules/charge-charge flux-dipole flux model predicted the values of 30 CH intensities ranging from 0 to 123 km mol(-1) with a root mean square (rms) error of only 4.2 km mol(-1) without including a specific equilibrium atomic charge term. Sums of the contributions from terms involving charge flux and/or dipole flux averaged 20.3 km mol(-1), about ten times larger than the average charge contribution of 2.0 km mol(-1). The only notable exceptions are the CH stretching and bending intensities of acetylene and two of the propyne vibrations for hydrogens bound to sp hybridized carbon atoms. Calculations were carried out at four quantum levels, MP2/6-311++G(3d,3p), MP2/cc-pVTZ, QCISD/6-311++G(3d,3p) and QCISD/cc-pVTZ. The results calculated at the QCISD level are the most accurate among the four with root mean square errors of 4.7 and 5.0 km mol(-1) for the 6-311++G(3d,3p) and cc-pVTZ basis sets. These values are close to the estimated aggregate experimental error of the hydrocarbon intensities, 4.0 km mol(-1). The atomic charge transfer-counter polarization effect is much larger than the charge effect for the results of all four quantum levels. Charge transfer-counter polarization effects are expected to also be important in vibrations of more polar molecules for which equilibrium charge contributions can be large.

The generalized anomeric effect in the 1,3-thiazolidines: Evidence for both sulphur and nitrogen as electron donors. Crystal structures of various N-acylthiazolidines including mercury(II) complexes. Possible relevance to penicillin action

NASA Astrophysics Data System (ADS)

Chandrasekhar, Sosale; Chopra, Deepak; Gopalaiah, Kovuru; Guru Row, Tayur N.

2007-06-01

Evidence for the generalized anomeric effect (GAE) in the N-acyl-1,3-thiazolidines, an important structural motif in the penicillins, was sought in the crystal structures of N-(4-nitrobenzoyl)-1,3-thiazolidine and its (2:1) complex with mercuric chloride, N-acetyl-2-phenyl-1,3-thiazolidine, and the (2:1) complex of N-benzoyl-1,3-thiazolidine with mercuric bromide. An inverse relationship was generally observed between the C2- N and C2- S bond lengths of the thiazolidine ring, supporting the existence of the GAE. (Maximal bond length changes were ˜0.04 Å for C2- N3, S1- C2, and ˜0.08 Å for N3- C6.) Comparison with N-acylpyrrolidines and tetrahydrothiophenes indicates that both the nitrogen-to-sulphur and sulphur-to-nitrogen GAE's operate simultaneously in the 1,3-thiazolidines, the former being dominant. (This is analogous to the normal and exo-anomeric effects in pyranoses, and also leads to an interesting application of Baldwin's rules.) The nitrogen-to-sulphur GAE is generally enhanced in the mercury(II) complexes (presumably via coordination at the sulphur); a 'competition' between the GAE and the amide resonance of the N-acyl moiety is apparent. There is evidence for a 'push-pull' charge transfer between the thiazolidine moieties in the mercury(II) complexes, and for a 'back-donation' of charge from the bromine atoms to the thiazolidine moieties in the HgBr 2 complex. (The sulphur atom appears to be sp 2 hybridised in the mercury(II) complexes, possibly for stereoelectronic reasons.) These results are apparently relevant to the mode of action of the penicillins.

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

NASA Astrophysics Data System (ADS)

Yang, Chou-Hsun; Hsu, Chao-Ping

2013-10-01

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

Charge transfer during individual collisions in ice growing by riming

NASA Technical Reports Server (NTRS)

Avila, Eldo E.; Caranti, Giorgio M.

1991-01-01

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

Impact of concentration and species of sulfamethoxazole and ofloxacin on their adsorption kinetics on sediments.

PubMed

Wang, Peng; Zhang, Di; Zhang, Huang; Li, Hao; Ghosh, Saikat; Pan, Bo

2017-05-01

Antibiotics are used widely in human and veterinary medicine and are ubiquitous in environmental matrices worldwide. The influence of the concentration of antibiotics on adsorption kinetics is still unclear. This study used sulfamethoxazole (SMX) and ofloxacin (OFL) as adsorbates to investigate the adsorption kinetics on sediment affected by varying concentrations of antibiotics adsorbable species. At the experimental pH values, the major adsorbed species of SMX and OFL on sediment were SMX 0 and OFL + by hydrophobic interaction and electrostatic attraction, respectively. The apparent adsorption rate of SMX was not affected by the initial concentration and the pH values because the hydrophobic interactions were concentration-independent and charge-independent. However, the apparent adsorption rate of OFL significantly slowed down as the initial concentration increased. The adsorbed OFL + effectively neutralized the negative charges of the sediment, leading to a reduced adsorption rate of subsequent OFL + . The neutralization effect was greatly enhanced due to the increased OFL + with the increasing OFL concentration. Additionally, the apparent adsorption rate of OFL significantly increased at higher pH due to the reduced neutralization effect that resulted from the decreased OFL + and increased negative charges of the sediment surface. This study implied that the adsorption kinetics of antibiotics was greatly dominated by the concentration of adsorbable species rather than apparent overall concentration. Copyright © 2017 Elsevier Ltd. All rights reserved.

Charge transfer between biogenic jarosite derived Fe3+and TiO2 enhances visible light photocatalytic activity of TiO2.

PubMed

Chowdhury, Mahabubur; Shoko, Sipiwe; Cummings, Fransciuos; Fester, Veruscha; Ojumu, Tunde Victor

2017-04-01

In this work, we have shown that mining waste derived Fe 3+ can be used to enhance the photocatalytic activity of TiO 2 . This will allow us to harness a waste product from the mines, and utilize it to enhance TiO 2 photocatalytic waste water treatment efficiency. An organic linker mediated route was utilized to create a composite of TiO 2 and biogenic jarosite. Evidence of FeOTi bonding in the TiO 2 /jarosite composite was apparent from the FTIR, EFTEM, EELS and ELNEFS analysis. The as prepared material showed enhanced photocatalytic activity compared to pristine TiO 2 , biogenic jarosite and mechanically mixed sample of jarosite and TiO 2 under both simulated and natural solar irradiation. The prepared material can reduce the electrical energy consumption by 4 times compared to pristine P25 for degradation of organic pollutant in water. The material also showed good recyclability. Results obtained from sedimentation experiments showed that the larger sized jarosite material provided the surface to TiO 2 nanoparticles, which increases the settling rate of the materials. This allowed simple and efficient recovery of the catalyst from the reaction system after completion of photocatalysis. Enhanced photocatalytic activity of the composite material was due to effective charge transfer between TiO 2 and jarosite derived Fe 3+ as was shown from the EELS and ELNEFS. Generation of OH was supported by photoluminesence (PL) experiments. Copyright © 2016. Published by Elsevier B.V.

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.

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

NASA Astrophysics Data System (ADS)

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

2004-01-01

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

The study of surface acoustic wave charge transfer device

NASA Technical Reports Server (NTRS)

Papanicolaou, N.; Lin, H. C.

1978-01-01

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

Weak competing interactions control assembly of strongly bonded TCNQ ionic acceptor molecules on silver surfaces

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

Park, Changwon; Rojas, Geoffrey A.; Jeon, Seokmin

2014-09-19

The energy scales of interactions that control molecular adsorption and assembly on surfaces can vary by several orders of magnitude, yet the importance of each contributing interaction is not apparent a priori. Tetracyanoquinodimethane (TCNQ) is an archetypal electron acceptor molecule and it is a key component of organic metals. On metal surfaces, this molecule also acts as an electron acceptor, producing negatively charged adsorbates. It is therefore rather intriguing to observe attractive molecular interactions in this system that were reported previously for copper and silver surfaces. In this paper, our experiments compared TCNQ adsorption on noble metal surfaces of Ag(100)more » and Ag(111). In both cases we found net attractive interactions down to the lowest coverage. However, the morphology of the assemblies was strikingly different, with two-dimensional islands on Ag(100) and one-dimensional chains on Ag(111) surfaces. This observation suggests that the registry effect governed by the molecular interaction with the underlying lattice potential is critical in determining the dimensionality of the molecular assembly. Using first-principles density functional calculations with a van der Waals correction scheme, we revealed that the strengths of major interactions (i.e., lattice potential corrugation, intermolecular attraction, and charge-transfer-induced repulsion) are all similar in energy. The van der Waals interactions, in particular, almost double the strength of attractive interactions, making the intermolecular potential comparable in strength to the diffusion potential and promoting self-assembly. However, it is the anisotropy of local intermolecular interactions that is primarily responsible for the difference in the topology of the molecular islands on Ag(100) and Ag(111) surfaces. Finally, we anticipate that the intermolecular potential will become more attractive and dominant over the diffusion potential with increasing molecular size, providing new design strategies for the structure and charge transfer within molecular layers.« less

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

PubMed

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

2015-07-07

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

An experimental approach to determine the heat transfer coefficient in directional solidification furnaces

NASA Technical Reports Server (NTRS)

Banan, Mohsen; Gray, Ross T.; Wilcox, William R.

1992-01-01

The heat transfer coefficient between a molten charge and its surroundings in a Bridgman furnace was experimentally determined using in-situ temperature measurement. The ampoule containing an isothermal melt was suddenly moved from a higher temperature zone to a lower temperature zone. The temperature-time history was used in a lumped-capacity cooling model to evaluate the heat transfer coefficient between the charge and the furnace. The experimentally determined heat transfer coefficient was of the same order of magnitude as the theoretical value estimated by standard heat transfer calculations.

Integrated exhaust gas recirculation and charge cooling system

DOEpatents

Wu, Ko-Jen

2013-12-10

An intake system for an internal combustion engine comprises an exhaust driven turbocharger configured to deliver compressed intake charge, comprising exhaust gas from the exhaust system and ambient air, through an intake charge conduit and to cylinders of the internal combustion engine. An intake charge cooler is in fluid communication with the intake charge conduit. A cooling system, independent of the cooling system for the internal combustion engine, is in fluid communication with the intake charge cooler through a cooling system conduit. A coolant pump delivers a low temperature cooling medium from the cooling system to and through the intake charge cooler for the transfer of heat from the compressed intake charge thereto. A low temperature cooler receives the heated cooling medium through the cooling system conduit for the transfer or heat therefrom.

Epitaxial growth and electronic properties of well ordered phthalocyanine heterojunctions MnPc/F{sub 16}CoPc

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

Lindner, Susi; Mahns, Benjamin; Treske, Uwe

2014-09-07

We have prepared phthalocyanine heterojunctions out of MnPc and F{sub 16}CoPc, which were studied by means of X-ray absorption spectroscopy. This heterojunction is characterized by a charge transfer at the interface, resulting in charged MnPc{sup δ} {sup +} and F{sub 16}CoPc{sup δ} {sup −} species. Our data reveal that the molecules are well ordered and oriented parallel to the substrate surface. Furthermore, we demonstrate the filling of the Co 3d{sub z{sup 2}} orbital due to the charge transfer, which supports the explanation of the density functional theory, that the charge transfer is local and affects the metal centers only.

Solvent Dependence of Lateral Charge Transfer in a Porphyrin Monolayer

DOE PAGES

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

2016-12-19

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

Substitution effects on the absorption spectra of nitrophenolate isomers.

PubMed

Wanko, Marius; Houmøller, Jørgen; Støchkel, Kristian; Suhr Kirketerp, Maj-Britt; Petersen, Michael Åxman; Nielsen, Mogens Brøndsted; Nielsen, Steen Brøndsted; Rubio, Angel

2012-10-05

Charge-transfer excitations highly depend on the electronic coupling between the donor and acceptor groups. Nitrophenolates are simple examples of charge-transfer systems where the degree of coupling differs between ortho, meta and para isomers. Here we report the absorption spectra of the isolated anions in vacuo to avoid the complications of solvent effects. Gas-phase action spectroscopy was done with two different setups, an electrostatic ion storage ring and an accelerator mass spectrometer. The results are interpreted on the basis of CC2 quantum chemical calculations. We identified absorption maxima at 393, 532, and 399 nm for the para, meta, and ortho isomer, respectively, with the charge-transfer transition into the lowest excited singlet state. In the meta isomer, this π-π* transition is strongly redshifted and its oscillator strength reduced, which is related to the pronounced charge-transfer character, as a consequence of the topology of the conjugated π-system. Each isomer's different charge distribution in the ground state leads to a very different solvent shift, which in acetonitrile is bathochromic for the para and ortho, but hypsochromic for the meta isomer.

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

Electron-lattice interactions strongly renormalize the charge-transfer energy in the spin-chain cuprate Li 2CuO 2

DOE PAGES

Johnston, Steve; Monney, Claude; Bisogni, Valentina; ...

2016-02-17

Strongly correlated insulators are broadly divided into two classes: Mott–Hubbard insulators, where the insulating gap is driven by the Coulomb repulsion U on the transition-metal cation, and charge-transfer insulators, where the gap is driven by the charge-transfer energy Δ between the cation and the ligand anions. The relative magnitudes of U and Δ determine which class a material belongs to, and subsequently the nature of its low-energy excitations. These energy scales are typically understood through the local chemistry of the active ions. Here we show that the situation is more complex in the low-dimensional charge-transfer insulator Li 2CuO 2, wheremore » Δ has a large non-electronic component. Combining resonant inelastic X-ray scattering with detailed modelling, we determine how the elementary lattice, charge, spin and orbital excitations are entangled in this material. This results in a large lattice-driven renormalization of Δ, which significantly reshapes the fundamental electronic properties of Li 2CuO 2.« less

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

PubMed

Baumeier, Björn; Andrienko, Denis; Rohlfing, Michael

2012-08-14

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

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

DOE PAGES

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

2017-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2007-09-01

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

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.

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

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

Reslan, Randa; Lopata, Kenneth; Arntsen, Christopher

2012-12-14

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

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

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

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

2012-12-14

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

Free energy gap laws for the pulse-induced and stationary fluorescence quenching by reversible charge transfer in polar solutions.

PubMed

Khokhlova, Svetlana S; Burshtein, Anatoly I

2011-01-21

The Stern-Volmer constants for either pulse-induced or stationary fluorescence being quenched by a contact charge transfer are calculated and their free energy dependencies (the free energy gap laws) are specified. The reversibility of charge transfer is taken into account as well as spin conversion in radical ion pairs, followed by their recombination in either singlet or triplet neutral products. The natural decay of triplets as well as their impurity quenching by ionization are accounted for when estimating the fluorescence quantum yield and its free energy dependence.

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

NASA Astrophysics Data System (ADS)

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

2017-02-01

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

Molecular implementation of molecular shift register memories

NASA Technical Reports Server (NTRS)

Beratan, David N. (Inventor); Onuchic, Jose N. (Inventor)

1991-01-01

An electronic shift register memory (20) at the molecular level is described. The memory elements are based on a chain of electron transfer molecules (22) and the information is shifted by photoinduced (26) electron transfer reactions. Thus, multi-step sequences of charge transfer reactions are used to move charge with high efficiency down a molecular chain. The device integrates compositions of the invention onto a VLSI substrate (36), providing an example of a molecular electronic device which may be fabricated. Three energy level schemes, molecular implementation of these schemes, optical excitation strategies, charge amplification strategies, and error correction strategies are described.

Intramolecular Charge Transfer States in the Condensed Phase

NASA Astrophysics Data System (ADS)

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

2009-06-01

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

Charge transfer in photorefractive CdTe:Ge at different wavelengths

NASA Astrophysics Data System (ADS)

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

2001-10-01

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

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.

Structural and spectroscopic characterizations on the charge-transfer interactions of the second generation poly(propylene amine) dendrimers with iodine and picric acid acceptors

NASA Astrophysics Data System (ADS)

El-Sayed, Mohamed Y.; Refat, Moamen S.

2015-02-01

Herein, this study was focused to get a knowledge about the intermolecular charge transfer complexes between the second generation of poly(propylene amine) dendrimer (PPD2) with picric acid (PA) and iodine (I2) as π and σ-acceptors. The charge-transfer interaction of the PPD2 electron donor and the PA acceptor has been studied in CHCl3. The resulted data refereed to the formation of the new CT-complex with the general formula [(PPD2)(PA)4]. The 1:4 stoichiometry of the reaction was discussed upon the on elemental analysis and photometric titration. On the other hand, the 1:3½ iodine-PPD2 heptaiodide (I7-) charge-transfer complex has been studied spectrophotometrically in chloroform at room temperature with general formula [(PPD2)]+I7-. The electronic absorption bands of 2I2·I3- (I7-) are observed at 358 and 294 nm. Raman laser spectrum of the brown solid heptaiodide complex has two clearly vibration bands at 155 and 110 cm-1 due to symmetric stretching νs(Isbnd I) outer and inner bonds, respectively. The 1H NMR spectra and differential scanning calorimetry (DSC) data of PPD2 charge-transfer complexes were discussed.

Abnormal Magnetic Field Effects on Electrogenerated Chemiluminescence

NASA Astrophysics Data System (ADS)

Pan, Haiping; Shen, Yan; Wang, Hongfeng; He, Lei; Hu, Bin

2015-03-01

We report abnormal magnetic field effects on electrogenerated chemiluminescence (MFEECL) based on triplet emission from the Ru(bpy)3Cl2-TPrA electrochemical system: the appearance of MFEECL after magnetic field ceases. In early studies the normal MFEECL have been observed from electrochemical systems during the application of magnetic field. Here, the abnormal MFEECL suggest that the activated charge-transfer [Ru(bpy)33+ … TPrA•] complexes may become magnetized in magnetic field and experience a long magnetic relaxation after removing magnetic field. Our analysis indicates that the magnetic relaxation can gradually increase the density of charge-transfer complexes within reaction region due to decayed magnetic interactions, leading to a positive component in the abnormal MFEECL. On the other hand, the magnetic relaxation facilitates an inverse conversion from triplets to singlets within charge-transfer complexes. The inverse triplet --> singlet conversion reduces the density of triplet light-emitting states through charge-transfer complexes and gives rise to a negative component in the abnormal MFEECL. The combination of positive and negative components can essentially lead to a non-monotonic profile in the abnormal MFEECL after ceasing magnetic field. Nevertheless, our experimental studies may reveal un-usual magnetic behaviors with long magnetic relaxation from the activated charge-transfer [Ru(bpy)33+ … TPrA•] complexes in solution at room temperature.

Charging of Proteins in Native Mass Spectrometry

DOE PAGES

Susa, Anna C.; Xia, Zijie; Tang, Henry Y. H.; ...

2016-10-12

Factors that influence the charging of protein ions formed by electrospray ionization from aqueous solutions in which proteins have native structures and function were investigated. Protein ions ranging in molecular weight from 12.3 to 79.7 kDa and pI values from 5.4 to 9.6 were formed from different solutions and reacted with volatile bases of gas-phase basicities higher than that of ammonia in the cell of a Fourier-transform ion cyclotron resonance mass spectrometer. The charge-state distribution of cytochrome c ions formed from aqueous ammonium or potassium acetate is the same. Moreover, ions formed from these two solutions do not undergo protonmore » transfer to 2-fluoropyridine, which is 8 kcal/mol more basic than ammonia. These results provide compelling evidence that proton transfer between ammonia and protein ions does not limit protein ion charge in native electrospray ionization. Both circular dichroism and ion mobility measurements indicate that there are differences in conformations of proteins in pure water and aqueous ammonium acetate, and these differences can account for the difference in the extent of charging and proton-transfer reactivities of protein ions formed from these solutions. The extent of proton transfer of the protein ions with higher gas-phase basicity bases trends with how closely the protein ions are charged to the value predicted by the Rayleigh limit for spherical water droplets approximately the same size as the proteins. These results indicate that droplet charge limits protein ion charge in native mass spectrometry and are consistent with these ions being formed by the charged residue mechanism.« less

Charging of Proteins in Native Mass Spectrometry

NASA Astrophysics Data System (ADS)

Susa, Anna C.; Xia, Zijie; Tang, Henry Y. H.; Tainer, John A.; Williams, Evan R.

2017-02-01

Factors that influence the charging of protein ions formed by electrospray ionization from aqueous solutions in which proteins have native structures and function were investigated. Protein ions ranging in molecular weight from 12.3 to 79.7 kDa and pI values from 5.4 to 9.6 were formed from different solutions and reacted with volatile bases of gas-phase basicities higher than that of ammonia in the cell of a Fourier-transform ion cyclotron resonance mass spectrometer. The charge-state distribution of cytochrome c ions formed from aqueous ammonium or potassium acetate is the same. Moreover, ions formed from these two solutions do not undergo proton transfer to 2-fluoropyridine, which is 8 kcal/mol more basic than ammonia. These results provide compelling evidence that proton transfer between ammonia and protein ions does not limit protein ion charge in native electrospray ionization. Both circular dichroism and ion mobility measurements indicate that there are differences in conformations of proteins in pure water and aqueous ammonium acetate, and these differences can account for the difference in the extent of charging and proton-transfer reactivities of protein ions formed from these solutions. The extent of proton transfer of the protein ions with higher gas-phase basicity bases trends with how closely the protein ions are charged to the value predicted by the Rayleigh limit for spherical water droplets approximately the same size as the proteins. These results indicate that droplet charge limits protein ion charge in native mass spectrometry and are consistent with these ions being formed by the charged residue mechanism.

Larry car for a coking oven battery

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

Corry, D.B.

A larry car (3) for transporting a charge of pre-heated coal along the top of a battery of coke ovens, from a storage installation including a group of metering bins (1) at one or more filling stations above the battery, to a corresponding group of charge holes for the oven chamber to be charged, the car including a corresponding group of coal transfer hoppers (4) each having valved inlet and discharge apertures (5,21), a sealed connection (2) between each metering bin and transfer hopper, an inert gas reservoir (10) connectable via a valved manifold (13,14) to each transfer hopper, amore » valved connection (7,8,9) for charging the reservoir, and a valved connection (15,16,17) to permit dusty gas to be displaced into the storage bunkers, and control means for the various valved connections to maintain continuous isolation of the interior of each transfer hopper from the atmosphere, to permit dust-laden gases to escape into the storage installation, and to cause inert medium to displace coal discharged from the transfer hoppers.« less

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

PubMed

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

2014-06-11

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

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.

Mediated Electron Transfer at Vertically Aligned Single-Walled Carbon Nanotube Electrodes During Detection of DNA Hybridization.

PubMed

Wallen, Rachel; Gokarn, Nirmal; Bercea, Priscila; Grzincic, Elissa; Bandyopadhyay, Krisanu

2015-12-01

Vertically aligned single-walled carbon nanotube (VASWCNT) assemblies are generated on cysteamine and 2-mercaptoethanol (2-ME)-functionalized gold surfaces through amide bond formation between carboxylic groups generated at the end of acid-shortened single-walled carbon nanotubes (SWCNTs) and amine groups present on the gold surfaces. Atomic force microscopy (AFM) imaging confirms the vertical alignment mode of SWCNT attachment through significant changes in surface roughness compared to bare gold surfaces and the lack of any horizontally aligned SWCNTs present. These SWCNT assemblies are further modified with an amine-terminated single-stranded probe-DNA. Subsequent hybridization of the surface-bound probe-DNA in the presence of complementary strands in solution is followed using impedance measurements in the presence of Fe(CN)6 (3-/4-) as the redox probe in solution, which show changes in the interfacial electrochemical properties, specifically the charge-transfer resistance, due to hybridization. In addition, hybridization of the probe-DNA is also compared when it is attached directly to the gold surfaces without any intermediary SWCNTs. Contrary to our expectations, impedance measurements show a decrease in charge-transfer resistance with time due to hybridization with 300 nM complementary DNA in solution with the probe-DNA attached to SWCNTs. In contrast, an increase in charge-transfer resistance is observed with time during hybridization when the probe-DNA is attached directly to the gold surfaces. The decrease in charge-transfer resistance during hybridization in the presence of VASWCNTs indicates an enhancement in the electron transfer process of the redox probe at the VASWCNT-modified electrode. The results suggest that VASWCNTs are acting as mediators of electron transfer, which facilitate the charge transfer of the redox probe at the electrode-solution interface.

Mediated Electron Transfer at Vertically Aligned Single-Walled Carbon Nanotube Electrodes During Detection of DNA Hybridization

NASA Astrophysics Data System (ADS)

Wallen, Rachel; Gokarn, Nirmal; Bercea, Priscila; Grzincic, Elissa; Bandyopadhyay, Krisanu

2015-06-01

Vertically aligned single-walled carbon nanotube (VASWCNT) assemblies are generated on cysteamine and 2-mercaptoethanol (2-ME)-functionalized gold surfaces through amide bond formation between carboxylic groups generated at the end of acid-shortened single-walled carbon nanotubes (SWCNTs) and amine groups present on the gold surfaces. Atomic force microscopy (AFM) imaging confirms the vertical alignment mode of SWCNT attachment through significant changes in surface roughness compared to bare gold surfaces and the lack of any horizontally aligned SWCNTs present. These SWCNT assemblies are further modified with an amine-terminated single-stranded probe-DNA. Subsequent hybridization of the surface-bound probe-DNA in the presence of complementary strands in solution is followed using impedance measurements in the presence of Fe(CN)6 3-/4- as the redox probe in solution, which show changes in the interfacial electrochemical properties, specifically the charge-transfer resistance, due to hybridization. In addition, hybridization of the probe-DNA is also compared when it is attached directly to the gold surfaces without any intermediary SWCNTs. Contrary to our expectations, impedance measurements show a decrease in charge-transfer resistance with time due to hybridization with 300 nM complementary DNA in solution with the probe-DNA attached to SWCNTs. In contrast, an increase in charge-transfer resistance is observed with time during hybridization when the probe-DNA is attached directly to the gold surfaces. The decrease in charge-transfer resistance during hybridization in the presence of VASWCNTs indicates an enhancement in the electron transfer process of the redox probe at the VASWCNT-modified electrode. The results suggest that VASWCNTs are acting as mediators of electron transfer, which facilitate the charge transfer of the redox probe at the electrode-solution interface.

Dependence of triboelectric charging behavior on material microstructure

NASA Astrophysics Data System (ADS)

Wang, Andrew E.; Gil, Phwey S.; Holonga, Moses; Yavuz, Zelal; Baytekin, H. Tarik; Sankaran, R. Mohan; Lacks, Daniel J.

2017-08-01

We demonstrate that differences in the microstructure of chemically identical materials can lead to distinct triboelectric charging behavior. Contact charging experiments are carried out between strained and unstrained polytetrafluoroethylene samples. Whereas charge transfer is random between samples of identical strain, when one of the samples is strained, systematic charge transfer occurs. No significant changes in the molecular-level structure of the polymer are observed by XRD and micro-Raman spectroscopy after deformation. However, the strained surfaces are found to exhibit void and craze formation spanning the nano- to micrometer length scales by molecular dynamics simulations, SEM, UV-vis spectroscopy, and naked-eye observations. This suggests that material microstructure (voids and crazes) can govern the triboelectric charging behavior of materials.

Spacecraft Charging in Geostationary Transfer Orbit

NASA Technical Reports Server (NTRS)

Parker, Linda Neergaard; Minow, Joseph I.

2014-01-01

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

Electrostatic Charging and Particle Interactions in Microscopic Insulating Grains

NASA Astrophysics Data System (ADS)

Lee, Victor

In this thesis, we experimentally investigate the electrostatic charging as well as the particle interactions in microscopic insulating grains. First, by tracking individual grains accelerated in an electric field, we quantitatively demonstrate that tribocharging of same-material grains depends on particle size. Large grains tend to charge positively, and small ones tend to charge negatively. Theories based on the transfer of trapped electrons can explain this tendency but have not been validated. Here we show that the number of trapped electrons, measured independently by a thermoluminescence technique, is orders of magnitude too small to be responsible for the amount of charge transferred. This result reveals that trapped electrons are not responsible for same-material tribocharging of dielectric particles. Second, same-material tribocharging in grains can result in important long-range electrostatic interactions. However, how these electrostatic interactions contribute to particle clustering remains elusive, primarily due to the lack of direct, detailed observations. Using a high-speed camera that falls with a stream charged grains, we observe for the first time how charged grains can undergo attractive as well as repulsive Kepler-like orbits. Charged particles can be captured in their mutual electrostatic potential and form clusters via multiple bounces. Dielectric polarization effects are directly observed, which lead to additional attractive forces and stabilize "molecule-like" arrangements of charged particles. Third, we have developed a new method to study the charge transfer of microscopic particles based on acoustic levitation techniques. This method allows us to narrow the complex problem of many-particle charging down to precise charge measurements of a single sub-millimeter particle colliding with a target plate. By simply attaching nonpolar groups onto glass surfaces, we show that the contact charging of a particle is highly dependent on hydrophobicity. Charging between a hydrophilic and a hydrophobic surface is enhanced in a basic atmosphere and suppressed in an acidic one. Moreover, hydrophobicity is also found to play a key role in particle charging driven by an external electric field. These results strongly support the idea that aqueous-ion transfer is responsible for the particle contact charging phenomenon.

Negative kinetic temperature effect on the hydride transfer from NADH analogue BNAH to the radical cation of N-benzylphenothiazine in acetonitrile.

PubMed

Zhu, Xiao-Qing; Zhang, Jian-Yu; Cheng, Jin-Pei

2006-09-01

The reaction rates of 1-(p-substituted benzyl)-1,4-dihydronicotinamide (G-BNAH) with N-benzylphenothiazine radical cation (PTZ(*+)) in acetonitrile were determined. The results show that the reaction rates (k(obs)) decreased from 2.80 x 10(7) to 2.16 x 10(7) M(-1) s(-1) for G = H as the reaction temperature increased from 298 to 318 K. The activation enthalpies of the reactions were estimated according to Eyring equation to give negative values (-3.4 to -2.9 kcal/mol). Investigation of the reaction intermediate shows that the charge-transfer complex (CT-complex) between G-BNAH and PTZ(*+) was formed in front of the hydride transfer from G-BNAH to PTZ(*+). The formation enthalpy of the CT-complex was estimated by using the Benesi-Hildebrand equation to give the values from -6.4 to -6.0 kcal/mol when the substituent G in G-BNAH changes from CH(3)O to Br. Detailed thermodynamic analyses on each elementary step in the possible reaction pathways suggest that the hydride transfer from G-BNAH to PTZ(*+) occurs by a concerted hydride transfer via a CT-complex. The effective charge distribution on the pyridine ring in G-BNAH at the various stages-the reactant G-BNAH, the charge-transfer complex, the transition-state, and the product G-BNA(+)-was estimated by using the method of Hammett-type linear free energy analysis, and the results show that the pyridine ring carries relative effective positive charges of 0.35 in the CT-complex and 0.45 in the transition state, respectively, which indicates that the concerted hydride transfer from G-BNAH to PTZ(*+) was practically performed by the initial charge (-0.35) transfer from G-BNAH to PTZ(*+) and then followed by the transfer of hydrogen atom with partial negative charge (-0.65). It is evident that the present work would be helpful in understanding the nature of the negative temperature effect, especially on the reaction of NADH coenzyme with the drug phenothiazine in vivo.

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

PubMed Central

Ni, Yang

2018-01-01

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

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

PubMed

Ni, Yang

2018-02-14

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

Large Ice Crystal Charge Transfer Studies

DTIC Science & Technology

1988-10-28

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

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.

Understanding How Isotopes Affect Charge Transfer in P3HT/PCBM: A Quantum Trajectory-Electronic Structure Study with Nonlinear Quantum Corrections

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

Wang, Lei; Jakowski, Jacek; Garashchuk, Sophya

The experimentally observed effect of selective deuterium substitution on the open circuit voltage for a blend of poly(3-hexylthiophene)(P3HT) and [6,6]-phenyl-C 61- butyric acid methyl ester (PCBM) (Nat. Commun. 5:3180, 2014) is explored using a 221-atom model of a polymer-wrapped PCBM molecule. We describe the protonic and deuteronic wavefunctions for the H/D isotopologues of the hexyl side chains within a Quantum Trajectory/Electronic Structure approach where the dynamics is performed with newly developed nonlinear corrections to the quantum forces, necessary to describe the nuclear wavefunctions; the classical forces are generated with a Density Functional Tight Binding method. We used the resulting protonicmore » and deuteronic time-dependent wavefunctions to assess the effects of isotopic substitution (deuteration) on the energy gaps relevant to the charge transfer for the donor and acceptor electronic states. Furthermore, while the isotope effect on the electronic energy levels is found negligible, the quantum-induced fluctuations of the energy gap between the charge transfer and charge separated states due to nuclear wavefunctions may account for experimental trends by promoting charge transfer in P3HT/PCBM and increasing charge recombination on the donor in the deuterium substituted P3HT/PCBM.« less

Understanding How Isotopes Affect Charge Transfer in P3HT/PCBM: A Quantum Trajectory-Electronic Structure Study with Nonlinear Quantum Corrections

DOE PAGES

Wang, Lei; Jakowski, Jacek; Garashchuk, Sophya; ...

2016-08-09

The experimentally observed effect of selective deuterium substitution on the open circuit voltage for a blend of poly(3-hexylthiophene)(P3HT) and [6,6]-phenyl-C 61- butyric acid methyl ester (PCBM) (Nat. Commun. 5:3180, 2014) is explored using a 221-atom model of a polymer-wrapped PCBM molecule. We describe the protonic and deuteronic wavefunctions for the H/D isotopologues of the hexyl side chains within a Quantum Trajectory/Electronic Structure approach where the dynamics is performed with newly developed nonlinear corrections to the quantum forces, necessary to describe the nuclear wavefunctions; the classical forces are generated with a Density Functional Tight Binding method. We used the resulting protonicmore » and deuteronic time-dependent wavefunctions to assess the effects of isotopic substitution (deuteration) on the energy gaps relevant to the charge transfer for the donor and acceptor electronic states. Furthermore, while the isotope effect on the electronic energy levels is found negligible, the quantum-induced fluctuations of the energy gap between the charge transfer and charge separated states due to nuclear wavefunctions may account for experimental trends by promoting charge transfer in P3HT/PCBM and increasing charge recombination on the donor in the deuterium substituted P3HT/PCBM.« less

Charge transfer complex of some nervous and brain drugs - Part 1: Synthesis, spectroscopic, analytical and biological studies on the reaction between haloperidol antipsychotic drugs with π-acceptors

NASA Astrophysics Data System (ADS)

El-Habeeb, Abeer A.; Al-Saif, Foziah A.; Refat, Moamen S.

2013-02-01

Donor-acceptor interactions between the electron donor haloperidol (HPL) and π-acceptors like 7,7,8,8-tetracyanoquinodimethane (TCNQ) and picric acid (PA) have been studied spectrophotometrically in CH3OH solvent. The donor-acceptor (charge transfer complexes) were discussed in terms of formation constant (KCT), molar extinction coefficient (ɛCT), standard free energy (ΔGo), oscillator strength (ƒ), transition dipole moment (μ), resonance energy (RN) and ionization potential (ID). The stoichiometry of these complexes was found to be 1:1 M ratio and having the formulas [(HPL)(TCNQ)] and [(HPL)(PA)], respectively. The charge transfer interaction was successfully applied to determine of HPL drug using mentioned common π-acceptors also, the results obtained herein are satisfactory for estimation of HPL compound in the pharmaceutical form. The formed solid charge-transfer complexes were also isolated and characterized using elemental analysis, conductivity, (infrared, Raman, and 1H NMR) spectra and X-ray powder diffraction (XRD). The experimental data of elemental analyses are in agreement with calculated data. The infrared spectra of both HPL complexes are confirming the participation of sbnd OH of 4-hydroxy-1-piperidyl moiety in the donor-acceptor chelation. The morphological surface of the resulted charge transfer complexes were investigated using scanning electron microscopy (SEM). The thermogravimetric analysis (TG/DTG) and differential scanning calorimetry (DSC) techniques were performed to give knowledge about the thermal stability behavior of the synthesized charge transfer complexes. Thermodynamic parameters were computed from the thermal decomposition data. These complexes were also tested for their antimicrobial activity against six different microorganisms, and the results were compared with the parent drug.

DFT and TD-DFT computation of charge transfer complex between o-phenylenediamine and 3,5-dinitrosalicylic acid

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

Afroz, Ziya; Zulkarnain,; Ahmad, Afaq, E-mail: afaqahmad3@gmail.com

2016-05-23

DFT and TD-DFT studies of o-phenylenediamine (PDA), 3,5-dinitrosalicylic acid (DNSA) and their charge transfer complex have been carried out at B3LYP/6-311G(d,p) level of theory. Molecular geometry and various other molecular properties like natural atomic charges, ionization potential, electron affinity, band gap, natural bond orbital (NBO) and frontier molecular analysis have been presented at same level of theory. Frontier molecular orbital and natural bond orbital analysis show the charge delocalization from PDA to DNSA.

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

NASA Astrophysics Data System (ADS)

Gisslén, Linus; Scholz, Reinhard

2009-09-01

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

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

DOE PAGES

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

2016-10-18

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

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

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

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

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

Ab Initio Simulation of Charge Transfer at the Semiconductor Quantum Dot/TiO 2 Interface in Quantum Dot-Sensitized Solar Cells

DOE PAGES

Xin, Xukai; Li, Bo; Jung, Jaehan; ...

2014-07-24

Quantum dot-sensitized solar cells (QDSSCs) have emerged as a promising solar architecture for next-generation solar cells. The QDSSCs exhibit a remarkably fast electron transfer from the quantum dot (QD) donor to the TiO 2 acceptor with size quantization properties of QDs that allows for the modulation of band energies to control photoresponse and photoconversion efficiency of solar cells. In order to understand the mechanisms that underpin this rapid charge transfer, the electronic properties of CdSe and PbSe QDs with different sizes on the TiO 2 substrate are simulated using a rigorous ab initio density functional method. Our method capitalizes onmore » localized orbital basis set, which is computationally less intensive. Quite intriguingly, a remarkable set of electron bridging states between QDs and TiO 2 occurring via the strong bonding between the conduction bands of QDs and TiO 2 is revealed. Such bridging states account for the fast adiabatic charge transfer from the QD donor to the TiO 2 acceptor, and may be a general feature for strongly coupled donor/acceptor systems. All the QDs/TiO 2 systems exhibit type II band alignments, with conduction band offsets that increase with the decrease in QD size. This facilitates the charge transfer from QDs donors to TiO 2 acceptors and explains the dependence of the increased charge transfer rate with the decreased QD size.« less

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

NASA Astrophysics Data System (ADS)

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

2017-01-01

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

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

NASA Astrophysics Data System (ADS)

Bai, Peng; Bazant, Martin Z.

2014-04-01

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

Charge states of ions, and mechanisms of charge ordering transitions

NASA Astrophysics Data System (ADS)

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

2014-07-01

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

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

NASA Astrophysics Data System (ADS)

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

2016-10-01

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

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

PubMed

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

2014-08-20

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

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

NASA Astrophysics Data System (ADS)

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

2014-03-01

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

Charge transfer in photorechargeable composite films of TiO2 and polyaniline

NASA Astrophysics Data System (ADS)

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

2015-07-01

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

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

PubMed Central

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

2012-01-01

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

Competing charge transfer pathways at the photosystem II-electrode interface

PubMed Central

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

2016-01-01

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

Spectrophotometric and spectroscopic studies of charge transfer complex of 1-Naphthylamine as an electron donor with picric acid as an electron acceptor in different polar solvents

NASA Astrophysics Data System (ADS)

Singh, Neeti; Ahmad, Afaq

2010-08-01

The charge transfer complex of 1-Naphthylamine as a donor with π-acceptor picric acid has been studied spectrophotometrically in different solvents at room temperature. The results indicate that the formation of charge transfer complex is high in less polar solvent. The stoichiometry of the complex was found to be 1:1 by straight line method. The data are analysed in terms of formation constant ( KCT), molar extinction coefficient ( ɛCT), standard free energy (Δ G o), oscillator strength ( ƒ), transition dipole moment ( μ EN), resonance energy ( R N) and ionization potential ( I D). It is concluded that the formation constant ( KCT) of the complex is found to be depends upon the nature of both electron acceptor and donor and also on the polarity of solvents. Further the charge transfer molecular complex between picric acid and 1-Naphthylamine is stabilized by hydrogen bonding.

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

PEDOT-CNT coated electrodes stimulate retinal neurons at low voltage amplitudes and low charge densities

NASA Astrophysics Data System (ADS)

Samba, R.; Herrmann, T.; Zeck, G.

2015-02-01

Objective. The aim of this study was to compare two different microelectrode materials—the conductive polymer composite poly-3,4-ethylenedioxythiophene (PEDOT)-carbon nanotube(CNT) and titanium nitride (TiN)—at activating spikes in retinal ganglion cells in whole mount rat retina through stimulation of the local retinal network. Stimulation efficacy of the microelectrodes was analyzed by comparing voltage, current and transferred charge at stimulation threshold. Approach. Retinal ganglion cell spikes were recorded by a central electrode (30 μm diameter) in the planar grid of an electrode array. Extracellular stimulation (monophasic, cathodic, 0.1-1.0 ms) of the retinal network was performed using constant voltage pulses applied to the eight surrounding electrodes. The stimulation electrodes were equally spaced on the four sides of a square (400 × 400 μm). Threshold voltage was determined as the pulse amplitude required to evoke network-mediated ganglion cell spiking in a defined post stimulus time window in 50% of identical stimulus repetitions. For the two electrode materials threshold voltage, transferred charge at threshold, maximum current and the residual current at the end of the pulse were compared. Main results. Stimulation of retinal interneurons using PEDOT-CNT electrodes is achieved with lower stimulation voltage and requires lower charge transfer as compared to TiN. The key parameter for effective stimulation is a constant current over at least 0.5 ms, which is obtained by PEDOT-CNT electrodes at lower stimulation voltage due to its faradaic charge transfer mechanism. Significance. In neuroprosthetic implants, PEDOT-CNT may allow for smaller electrodes, effective stimulation in a safe voltage regime and lower energy-consumption. Our study also indicates, that the charge transferred at threshold or the charge injection capacity per se does not determine stimulation efficacy.

Influence of mass transfer resistance on overall nitrate removal rate in upflow sludge bed reactors.

PubMed

Ting, Wen-Huei; Huang, Ju-Sheng

2006-09-01

A kinetic model with intrinsic reaction kinetics and a simplified model with apparent reaction kinetics for denitrification in upflow sludge bed (USB) reactors were proposed. USB-reactor performance data with and without sludge wasting were also obtained for model verification. An independent batch study showed that the apparent kinetic constants k' did not differ from the intrinsic k but the apparent Ks' was significantly larger than the intrinsic Ks suggesting that the intra-granule mass transfer resistance can be modeled by changes in Ks. Calculations of the overall effectiveness factor, Thiele modulus, and Biot number combined with parametric sensitivity analysis showed that the influence of internal mass transfer resistance on the overall nitrate removal rate in USB reactors is more significant than the external mass transfer resistance. The simulated residual nitrate concentrations using the simplified model were in good agreement with the experimental data; the simulated results using the simplified model were also close to those using the kinetic model. Accordingly, the simplified model adequately described the overall nitrate removal rate and can be used for process design.

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

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

Yukihira, Nao; Sugai, Yuko; Fujiwara, Masazumi

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

Predicting apparent singlet oxygen quantum yields of dissolved black carbon and humic substances using spectroscopic indices.

PubMed

Du, Ziyan; He, Yingsheng; Fan, Jianing; Fu, Heyun; Zheng, Shourong; Xu, Zhaoyi; Qu, Xiaolei; Kong, Ao; Zhu, Dongqiang

2018-03-01

Dissolved black carbon (DBC) is ubiquitous in aquatic systems, being an important subgroup of the dissolved organic matter (DOM) pool. Nevertheless, its aquatic photoactivity remains largely unknown. In this study, a range of spectroscopic indices of DBC and humic substance (HS) samples were determined using UV-Vis spectroscopy, fluorescence spectroscopy, and proton nuclear magnetic resonance. DBC can be readily differentiated from HS using spectroscopic indices. It has lower average molecular weight, but higher aromaticity and lignin content. The apparent singlet oxygen quantum yield (Φ singlet oxygen ) of DBC under simulated sunlight varies from 3.46% to 6.13%, significantly higher than HS, 1.26%-3.57%, suggesting that DBC is the more photoactive component in the DOM pool. Despite drastically different formation processes and structural properties, the Φ singlet oxygen of DBC and HS can be well predicted by the same simple linear regression models using optical indices including spectral slope coefficient (S 275-295 ) and absorbance ratio (E 2 /E 3 ) which are proxies for the abundance of singlet oxygen sensitizers and for the significance of intramolecular charge transfer interactions. The regression models can be potentially used to assess the photoactivity of DOM at large scales with in situ water spectrophotometry or satellite remote sensing. Copyright © 2017 Elsevier Ltd. All rights reserved.

Development of a Simple Electron Transfer and Polarization Model and Its Application to Biological Systems.

PubMed

Diller, David J

2017-01-10

Here we present a new method for point charge calculation which we call Q ET (charges by electron transfer). The intent of this work is to develop a method that can be useful for studying charge transfer in large biological systems. It is based on the intuitive framework of the Q EQ method with the key difference being that the Q ET method tracks all pairwise electron transfers by augmenting the Q EQ pseudoenergy function with a distance dependent cost function for each electron transfer. This approach solves the key limitation of the Q EQ method which is its handling of formally charged groups. First, we parametrize the Q ET method by fitting to electrostatic potentials calculated using ab initio quantum mechanics on over 11,000 small molecules. On an external test set of over 2500 small molecules the Q ET method achieves a mean absolute error of 1.37 kcal/mol/electron when compared to the ab initio electrostatic potentials. Second, we examine the conformational dependence of the charges on over 2700 tripeptides. With the tripeptide data set, we show that the conformational effects account for approximately 0.4 kcal/mol/electron on the electrostatic potentials. Third, we test the Q ET method for its ability to reproduce the effects of polarization and electron transfer on 1000 water clusters. For the water clusters, we show that the Q ET method captures about 50% of the polarization and electron transfer effects. Finally, we examine the effects of electron transfer and polarizability on the electrostatic interaction between p38 and 94 small molecule ligands. When used in conjunction with the Generalized-Born continuum solvent model, polarization and electron transfer with the Q ET model lead to an average change of 17 kcal/mol on the calculated electrostatic component of ΔG.

Direct Observation of Individual Charges and Their Dynamics on Graphene by Low-Energy Electron Holography.

PubMed

Latychevskaia, Tatiana; Wicki, Flavio; Longchamp, Jean-Nicolas; Escher, Conrad; Fink, Hans-Werner

2016-09-14

Visualizing individual charges confined to molecules and observing their dynamics with high spatial resolution is a challenge for advancing various fields in science, ranging from mesoscopic physics to electron transfer events in biological molecules. We show here that the high sensitivity of low-energy electrons to local electric fields can be employed to directly visualize individual charged adsorbates and to study their behavior in a quantitative way. This makes electron holography a unique probing tool for directly visualizing charge distributions with a sensitivity of a fraction of an elementary charge. Moreover, spatial resolution in the nanometer range and fast data acquisition inherent to lens-less low-energy electron holography allows for direct visual inspection of charge transfer processes.

Computational Investigation of Amine–Oxygen Exciplex Formation

PubMed Central

Haupert, Levi M.; Simpson, Garth J.; Slipchenko, Lyudmila V.

2012-01-01

It has been suggested that fluorescence from amine-containing dendrimer compounds could be the result of a charge transfer between amine groups and molecular oxygen [Chu, C.-C.; Imae, T. Macromol. Rapid Commun. 2009, 30, 89.]. In this paper we employ equation-of-motion coupled cluster computational methods to study the electronic structure of an ammonia–oxygen model complex to examine this possibility. The results reveal several bound electronic states with charge transfer character with emission energies generally consistent with previous observations. However, further work involving confinement, solvent, and amine structure effects will be necessary for more rigorous examination of the charge transfer fluorescence hypothesis. PMID:21812447

Dielectric spectroscopy on organic charge-transfer salts

NASA Astrophysics Data System (ADS)

Lunkenheimer, P.; Loidl, A.

2015-09-01

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

Dielectric spectroscopy on organic charge-transfer salts.

PubMed

Lunkenheimer, P; Loidl, A

2015-09-23

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

Generalized Breit-Wigner treatment of molecular transport: Charging effects in a single decanedithiol molecule

NASA Astrophysics Data System (ADS)

Cabrera-Tinoco, Hugo Andres; Moreira, Augusto C. L.; de Melo, Celso P.

2018-05-01

We examine the relative contribution of ballistic and elastic cotunneling mechanisms to the charge transport through a single decanedithiol molecule linked to two terminal clusters of gold atoms. For this, we first introduced a conceptual model that permits a generalization of the Breit-Wigner scattering formalism where the cation, anion, and neutral forms of the molecule can participate with different probabilities of the charge transfer process, but in a simultaneous manner. We used a density functional theory treatment and considered the fixed geometry of each charge state to calculate the corresponding eigenvalues and eigenvectors of the extended system for different values of the external electric field. We have found that for the ballistic transport the HOMO and LUMO of the neutral species play a key role, while the charged states give a negligible contribution. On the other hand, an elastic cotunneling charge transfer can occur whenever a molecular orbital (MO) of the cation or anion species, even if localized in just one side of the molecule-gold clusters complex, has energy close to that of a delocalized MO of the neutral species. Under these conditions, a conduction channel is formed throughout the entire system, in a process that is controlled by the degree of resonance between the MOs involved. Our results indicate that while different charge transfer mechanisms contribute to the overall charge transport, quantum effects such as avoided-crossing situations between relevant frontier MOs can be of special importance. In these specific situations, the interchange of spatial localization of two MOs involved in the crossing can open a new channel of charge transfer that otherwise would not be available.

Typical effects of laser dazzling CCD camera

NASA Astrophysics Data System (ADS)

Zhang, Zhen; Zhang, Jianmin; Shao, Bibo; Cheng, Deyan; Ye, Xisheng; Feng, Guobin

2015-05-01

In this article, an overview of laser dazzling effect to buried channel CCD camera is given. The CCDs are sorted into staring and scanning types. The former includes the frame transfer and interline transfer types. The latter includes linear and time delay integration types. All CCDs must perform four primary tasks in generating an image, which are called charge generation, charge collection, charge transfer and charge measurement. In camera, the lenses are needed to input the optical signal to the CCD sensors, in which the techniques for erasing stray light are used. And the electron circuits are needed to process the output signal of CCD, in which many electronic techniques are used. The dazzling effects are the conjunct result of light distribution distortion and charge distribution distortion, which respectively derive from the lens and the sensor. Strictly speaking, in lens, the light distribution is not distorted. In general, the lens are so well designed and fabricated that its stray light can be neglected. But the laser is of much enough intensity to make its stray light obvious. In CCD image sensors, laser can induce a so large electrons generation. Charges transfer inefficiency and charges blooming will cause the distortion of the charge distribution. Commonly, the largest signal outputted from CCD sensor is restricted by capability of the collection well of CCD, and can't go beyond the dynamic range for the subsequent electron circuits maintaining normal work. So the signal is not distorted in the post-processing circuits. But some techniques in the circuit can make some dazzling effects present different phenomenon in final image.

Electron Transfer Dissociation of iTRAQ Labeled Peptide Ions

PubMed Central

Han, Hongling; Pappin, Darryl J.; Ross, Philip L; McLuckey, Scott A.

2009-01-01

Triply and doubly charged iTRAQ (isobaric tagging for relative and absolute quantitation) labeled peptide cations from a tryptic peptide mixture of bovine carbonic anhydrase II were subjected to electron transfer ion/ion reactions to investigate the effect of charge bearing modifications associated with iTRAQ on the fragmentation pattern. It was noted that electron transfer dissociation (ETD) of triply charged or activated ETD (ETD + supplemental collisional activation of intact electron transfer species) of doubly charged iTRAQ tagged peptide ions yielded extensive sequence information, in analogy with ETD of unmodified peptide ions. That is, addition of the fixed charge iTRAQ tag showed relatively little deleterious effect on the ETD performance of the modified peptides. ETD of the triply charged iTRAQ labeled peptide ions followed by collision-induced dissociation (CID) of the product ion at m/z 162 yielded the reporter ion at m/z 116, which is the reporter ion used for quantitation via CID of the same precursor ions. The reporter ion formed via the two-step activation process is expected to provide quantitative information similar to that directly produced from CID. A 103 Da neutral loss species observed in the ETD spectra of all the triply and doubly charged iTRAQ labeled peptide ions is unique to the 116 Da iTRAQ reagent, which implies that this process also has potential for quantitation of peptides/proteins. Therefore, ETD with or without supplemental collisional activation, depending on the precursor ion charge state, has the potential to directly identify and quantify the peptides/proteins simultaneously using existing iTRAQ reagents. PMID:18646790

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

Susa, Anna C.; Xia, Zijie; Tang, Henry Y. H.

Factors that influence the charging of protein ions formed by electrospray ionization from aqueous solutions in which proteins have native structures and function were investigated. Protein ions ranging in molecular weight from 12.3 to 79.7 kDa and pI values from 5.4 to 9.6 were formed from different solutions and reacted with volatile bases of gas-phase basicities higher than that of ammonia in the cell of a Fourier-transform ion cyclotron resonance mass spectrometer. The charge-state distribution of cytochrome c ions formed from aqueous ammonium or potassium acetate is the same. Moreover, ions formed from these two solutions do not undergo protonmore » transfer to 2-fluoropyridine, which is 8 kcal/mol more basic than ammonia. These results provide compelling evidence that proton transfer between ammonia and protein ions does not limit protein ion charge in native electrospray ionization. Both circular dichroism and ion mobility measurements indicate that there are differences in conformations of proteins in pure water and aqueous ammonium acetate, and these differences can account for the difference in the extent of charging and proton-transfer reactivities of protein ions formed from these solutions. The extent of proton transfer of the protein ions with higher gas-phase basicity bases trends with how closely the protein ions are charged to the value predicted by the Rayleigh limit for spherical water droplets approximately the same size as the proteins. These results indicate that droplet charge limits protein ion charge in native mass spectrometry and are consistent with these ions being formed by the charged residue mechanism.« less

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

PubMed

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

2014-01-01

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

Analysis of pulsed injection for microgravity receiver tank chilldown

NASA Astrophysics Data System (ADS)

Honkonen, Scott C.; Pietrzyk, Joe R.; Schuster, John R.

The dominant heat transfer mechanism during the hold phase of a tank chilldown cycle in a low-gravity environment is due to fluid motion persistence following the charge. As compared to the single-charge per vent cycle case, pulsed injection maintains fluid motion and the associated high wall heat transfer coefficients during the hold phase. As a result, the pulsed injection procedure appears to be an attractive method for reducing the time and liquid mass required to chill a tank. However, for the representative conditions considered, no significant benefit can be realized by using pulsed injection as compared to the single-charge case. A numerical model of the charge/hold/vent process was used to evaluate the pulsed injection procedure for tank chilldown in microgravity. Pulsed injection results in higher average wall heat transfer coefficients during the hold, as compared to the single-charge case. However, these high levels were not coincident with the maximum wall-to-fluid temperature differences, as in the single-charge case. For representative conditions investigated, the charge/hold/vent process is very efficient. A slightly shorter chilldown time was realized by increasing the number of pulses.

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

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.

Effect of Molecular Coupling on Ultrafast Electron-Transfer and Charge-Recombination Dynamics in a Wide-Gap ZnS Nanoaggregate Sensitized by Triphenyl Methane Dyes.

PubMed

Debnath, Tushar; Maity, Partha; Dana, Jayanta; Ghosh, Hirendra N

2016-03-03

Wide-band-gap ZnS nanocrystals (NCs) were synthesized, and after sensitizing the NCs with series of triphenyl methane (TPM) dyes, ultrafast charge-transfer dynamics was demonstrated. HRTEM images of ZnS NCs show the formation of aggregate crystals with a flower-like structure. Exciton absorption and lumimescence, due to quantum confinement of the ZnS NCs, appear at approximately 310 and 340 nm, respectively. Interestingly, all the TPM dyes (pyrogallol red, bromopyrogallol red, and aurin tricarboxylic acid) form charge-transfer complexes with the ZnS NCs, with the appearance of a red-shifted band. Electron injection from the photoexcited TPM dyes into the conduction band of the ZnS NCs is shown to be a thermodynamically viable process, as confirmed by steady-state and time-resolved emission studies. To unravel charge-transfer (both electron injection and charge recombination) dynamics and the effect of molecular coupling, femtosecond transient absorption studies were carried out in TPM-sensitized ZnS NCs. The electron-injection dynamics is pulse-width-limited in all the ZnS/TPM dye systems, however, the back electron transfer differs, depending on the molecular coupling of the sensitizers (TPM dyes). The detailed mechanisms for the above-mentioned processes are discussed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structural and spectroscopic characterizations on the charge-transfer interactions of the second generation poly(propylene amine) dendrimers with iodine and picric acid acceptors.

PubMed

El-Sayed, Mohamed Y; Refat, Moamen S

2015-02-25

Herein, this study was focused to get a knowledge about the intermolecular charge transfer complexes between the second generation of poly(propylene amine) dendrimer (PPD2) with picric acid (PA) and iodine (I2) as π and σ-acceptors. The charge-transfer interaction of the PPD2 electron donor and the PA acceptor has been studied in CHCl3. The resulted data refereed to the formation of the new CT-complex with the general formula [(PPD2)(PA)4]. The 1:4 stoichiometry of the reaction was discussed upon the on elemental analysis and photometric titration. On the other hand, the 1:3½ iodine-PPD2 heptaiodide (I7(-)) charge-transfer complex has been studied spectrophotometrically in chloroform at room temperature with general formula [(PPD2)](+)I7(-). The electronic absorption bands of 2I2·I3(-) (I7(-)) are observed at 358 and 294 nm. Raman laser spectrum of the brown solid heptaiodide complex has two clearly vibration bands at 155 and 110 cm(-1) due to symmetric stretching νs(II) outer and inner bonds, respectively. The (1)H NMR spectra and differential scanning calorimetry (DSC) data of PPD2 charge-transfer complexes were discussed. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

Molecular layers of ZnPc and FePc on Au(111) surface: Charge transfer and chemical interaction

NASA Astrophysics Data System (ADS)

Ahmadi, Sareh; Shariati, M. Nina; Yu, Shun; Göthelid, Mats

2012-08-01

We have studied zinc phthalocyanine (ZnPc) and iron phthalocyanine (FePc) thick films and monolayers on Au(111) using photoelectron spectroscopy and x-ray absorption spectroscopy. Both molecules are adsorbed flat on the surface at monolayer. ZnPc keeps this orientation in all investigated coverages, whereas FePc molecules stand up in the thick film. The stronger inter-molecular interaction of FePc molecules leads to change of orientation, as well as higher conductivity in FePc layer in comparison with ZnPc, which is reflected in thickness-dependent differences in core-level shifts. Work function changes indicate that both molecules donate charge to Au; through the π-system. However, the Fe3d derived lowest unoccupied molecular orbital receives charge from the substrate when forming an interface state at the Fermi level. Thus, the central atom plays an important role in mediating the charge, but the charge transfer as a whole is a balance between the two different charge transfer channels; π-system and the central atom.

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

NASA Astrophysics Data System (ADS)

Le, Xuan Que; Nguyen, Phu Thuy

2002-12-01

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

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

DOE PAGES

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

2015-09-15

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

Resolving the excited state equilibrium of peridinin in solution.

PubMed

Papagiannakis, Emmanouil; Larsen, Delmar S; van Stokkum, Ivo H M; Vengris, Mikas; Hiller, Roger G; van Grondelle, Rienk

2004-12-14

The carotenoid peridinin is abundant in the biosphere, as it is the main pigment bound by the light-harvesting complexes of dinoflagellates, where it collects blue and green sunlight and transfers energy to chlorophyll a with high efficiency. Its molecular structure is particularly complex, giving rise to an intricate excited state manifold, which includes a state with charge-transfer character. To disentangle the excited states of peridinin and understand their function in vivo, we applied dispersed pump-probe and pump-dump-probe spectroscopy. The preferential depletion of population from the intramolecular charge transfer state by the dump pulse demonstrates that the S(1) and this charge transfer state are distinct entities. The ensuing dump-induced dynamics illustrates the equilibration of the two states which occurs on the time scale of a few picoseconds. Additionally, the dump pulse populates a short-lived ground state intermediate, which is suggestive of a complex relaxation pathway, probably including structural reorientation or solvation of the ground state. These findings indicate that the unique intramolecular charge transfer state of peridinin is an efficient energy donor to chlorophyll a in the peridinin-chlorophyll-protein complex and thus plays a significant role in global light harvesting.

Probing the effect of charge transfer enhancement in off resonance mode SERS via conjugation of the probe dye between silver nanoparticles and metal substrates.

PubMed

Selvakannan, Pr; Ramanathan, Rajesh; Plowman, Blake J; Sabri, Ylias M; Daima, Hemant K; O'Mullane, Anthony P; Bansal, Vipul; Bhargava, Suresh K

2013-08-21

The charge transfer-mediated surface enhanced Raman scattering (SERS) of crystal violet (CV) molecules that were chemically conjugated between partially polarized silver nanoparticles and optically smooth gold and silver substrates has been studied under off-resonant conditions. Tyrosine molecules were used as a reducing agent to convert silver ions into silver nanoparticles where oxidised tyrosine caps the silver nanoparticle surface with its semiquinone group. This binding through the quinone group facilitates charge transfer and results in partially oxidised silver. This establishes a chemical link between the silver nanoparticles and the CV molecules, where the positively charged central carbon of CV molecules can bind to the terminal carboxylate anion of the oxidised tyrosine molecules. After drop casting Ag nanoparticles bound with CV molecules it was found that the free terminal amine groups tend to bind with the underlying substrates. Significantly, only those CV molecules that were chemically conjugated between the partially polarised silver nanoparticles and the underlying gold or silver substrates were found to show SERS under off-resonant conditions. The importance of partial charge transfer at the nanoparticle/capping agent interface and the resultant conjugation of CV molecules to off resonant SERS effects was confirmed by using gold nanoparticles prepared in a similar manner. In this case the capping agent binds to the nanoparticle through the amine group which does not facilitate charge transfer from the gold nanoparticle and under these conditions SERS enhancement in the sandwich configuration was not observed.

Charging system using solar panels and a highly resonant wireless power transfer model for small UAS applications

NASA Astrophysics Data System (ADS)

Hallman, Sydney N.; Huck, Robert C.; Sluss, James J.

2016-05-01

The use of a wireless charging system for small, unmanned aircraft system applications is useful for both military and commercial consumers. An efficient way to keep the aircraft's batteries charged without interrupting flight would be highly marketable. While the general concepts behind highly resonant wireless power transfer are discussed in a few publications, the details behind the system designs are not available even in academic journals, especially in relation to avionics. Combining a highly resonant charging system with a solar panel charging system can produce enough power to extend the flight time of a small, unmanned aircraft system without interruption. This paper provides an overview of a few of the wireless-charging technologies currently available and outlines a preliminary design for an aircraft-mounted battery charging system.

Simple Model for the Benzene Hexafluorobenzene Interaction

DOE PAGES

Tillack, Andreas F.; Robinson, Bruce H.

2017-06-05

While the experimental intermolecular distance distribution functions of pure benzene and pure hexafluorobenzene are well described by transferable all-atom force fields, the interaction between the two molecules (in a 1:1 mixture) is not well simulated. We demonstrate that the parameters of the transferable force fields are adequate to describe the intermolecular distance distribution if the charges are replaced by a set of charges that are not located at the atoms. Here, the simplest model that well describes the experimental distance distribution, between benzene and hexafluorobenzene, is that of a single ellipsoid for each molecule, representing the van der Waals interactions,more » and a set of three point charges (on the axis perpendicular to the arene plane) which give the same quadrupole moment as do the all atom charges from the transferable force fields.« less

Plasmon enhanced heterogeneous electron transfer with continuous band energy model

NASA Astrophysics Data System (ADS)

Zhao, Dandan; Niu, Lu; Wang, Luxia

2017-08-01

Photoinduced charge injection from a perylene dye molecule into the conduction band of a TiO2 system decorated by a metal nanoparticles (MNP) is studied theoretically. Utilizing the density matrix theory the charge transfer dynamics is analyzed. The continuous behavior of the TiO2 conduction band is accounted for by a Legendre polynomials expansion. The simulations consider optical excitation of the dye molecule coupled to the MNP and the subsequent electron injection into the TiO2 semiconductor. Due to the energy transfer coupling between the molecule and the MNP optical excitation and subsequent charge injection into semiconductor is strongly enhanced. The respective enhancement factor can reach values larger than 103. Effects of pulse duration, coupling strength and energetic resonances are also analyzed. The whole approach offers an efficient way to increase charge injection in dye-sensitized solar cells.

Constructing diabatic states from adiabatic states: Extending generalized Mulliken-Hush to multiple charge centers with Boys localization

NASA Astrophysics Data System (ADS)

Subotnik, Joseph E.; Yeganeh, Sina; Cave, Robert J.; Ratner, Mark A.

2008-12-01

This article shows that, although Boys localization is usually applied to single-electron orbitals, the Boys method itself can be applied to many electron molecular states. For the two-state charge-transfer problem, we show analytically that Boys localization yields the same charge-localized diabatic states as those found by generalized Mulliken-Hush theory. We suggest that for future work in electron transfer, where systems have more than two charge centers, one may benefit by using a variant of Boys localization to construct diabatic potential energy surfaces and extract electronic coupling matrix elements. We discuss two chemical examples of Boys localization and propose a generalization of the Boys algorithm for creating diabatic states with localized spin density that should be useful for Dexter triplet-triplet energy transfer.

Constructing diabatic states from adiabatic states: extending generalized Mulliken-Hush to multiple charge centers with boys localization.

PubMed

Subotnik, Joseph E; Yeganeh, Sina; Cave, Robert J; Ratner, Mark A

2008-12-28

This article shows that, although Boys localization is usually applied to single-electron orbitals, the Boys method itself can be applied to many electron molecular states. For the two-state charge-transfer problem, we show analytically that Boys localization yields the same charge-localized diabatic states as those found by generalized Mulliken-Hush theory. We suggest that for future work in electron transfer, where systems have more than two charge centers, one may benefit by using a variant of Boys localization to construct diabatic potential energy surfaces and extract electronic coupling matrix elements. We discuss two chemical examples of Boys localization and propose a generalization of the Boys algorithm for creating diabatic states with localized spin density that should be useful for Dexter triplet-triplet energy transfer.

Simple Model for the Benzene Hexafluorobenzene Interaction

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

Tillack, Andreas F.; Robinson, Bruce H.

While the experimental intermolecular distance distribution functions of pure benzene and pure hexafluorobenzene are well described by transferable all-atom force fields, the interaction between the two molecules (in a 1:1 mixture) is not well simulated. We demonstrate that the parameters of the transferable force fields are adequate to describe the intermolecular distance distribution if the charges are replaced by a set of charges that are not located at the atoms. Here, the simplest model that well describes the experimental distance distribution, between benzene and hexafluorobenzene, is that of a single ellipsoid for each molecule, representing the van der Waals interactions,more » and a set of three point charges (on the axis perpendicular to the arene plane) which give the same quadrupole moment as do the all atom charges from the transferable force fields.« less

Do fluorescence and transient absorption probe the same intramolecular charge transfer state of 4-(dimethylamino)benzonitrile?

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

Gustavsson, Thomas; Coto, Pedro B.; Serrano-Andres, Luis

2009-07-21

We present here the results of time-resolved absorption and emission experiments for 4-(dimethylamino)benzonitrile in solution, which suggest that the fluorescent intramolecular charge transfer (ICT) state may differ from the twisted ICT (TICT) state observed in transient absorption.

Correlating electronic and vibrational motions in charge transfer systems

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

Khalil, Munira

2014-06-27

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

Active pixel sensor with intra-pixel charge transfer

NASA Technical Reports Server (NTRS)

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

1995-01-01

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

Active pixel sensor with intra-pixel charge transfer

NASA Technical Reports Server (NTRS)

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

2003-01-01

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

Active pixel sensor with intra-pixel charge transfer

NASA Technical Reports Server (NTRS)

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

2004-01-01

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

Rational design of viscosity reducing mutants of a monoclonal antibody: Hydrophobic versus electrostatic inter-molecular interactions

PubMed Central

Nichols, Pilarin; Li, Li; Kumar, Sandeep; Buck, Patrick M; Singh, Satish K; Goswami, Sumit; Balthazor, Bryan; Conley, Tami R; Sek, David; Allen, Martin J

2015-01-01

High viscosity of monoclonal antibody formulations at concentrations ≥100 mg/mL can impede their development as products suitable for subcutaneous delivery. The effects of hydrophobic and electrostatic intermolecular interactions on the solution behavior of MAB 1, which becomes unacceptably viscous at high concentrations, was studied by testing 5 single point mutants. The mutations were designed to reduce viscosity by disrupting either an aggregation prone region (APR), which also participates in 2 hydrophobic surface patches, or a negatively charged surface patch in the variable region. The disruption of an APR that lies at the interface of light and heavy chain variable domains, VH and VL, via L45K mutation destabilized MAB 1 and abolished antigen binding. However, mutation at the preceding residue (V44K), which also lies in the same APR, increased apparent solubility and reduced viscosity of MAB 1 without sacrificing antigen binding or thermal stability. Neutralizing the negatively charged surface patch (E59Y) also increased apparent solubility and reduced viscosity of MAB 1, but charge reversal at the same position (E59K/R) caused destabilization, decreased solubility and led to difficulties in sample manipulation that precluded their viscosity measurements at high concentrations. Both V44K and E59Y mutations showed similar increase in apparent solubility. However, the viscosity profile of E59Y was considerably better than that of the V44K, providing evidence that inter-molecular interactions in MAB 1 are electrostatically driven. In conclusion, neutralizing negatively charged surface patches may be more beneficial toward reducing viscosity of highly concentrated antibody solutions than charge reversal or aggregation prone motif disruption. PMID:25559441

Rational design of viscosity reducing mutants of a monoclonal antibody: hydrophobic versus electrostatic inter-molecular interactions.

PubMed

Nichols, Pilarin; Li, Li; Kumar, Sandeep; Buck, Patrick M; Singh, Satish K; Goswami, Sumit; Balthazor, Bryan; Conley, Tami R; Sek, David; Allen, Martin J

2015-01-01

High viscosity of monoclonal antibody formulations at concentrations ≥100 mg/mL can impede their development as products suitable for subcutaneous delivery. The effects of hydrophobic and electrostatic intermolecular interactions on the solution behavior of MAB 1, which becomes unacceptably viscous at high concentrations, was studied by testing 5 single point mutants. The mutations were designed to reduce viscosity by disrupting either an aggregation prone region (APR), which also participates in 2 hydrophobic surface patches, or a negatively charged surface patch in the variable region. The disruption of an APR that lies at the interface of light and heavy chain variable domains, VH and VL, via L45K mutation destabilized MAB 1 and abolished antigen binding. However, mutation at the preceding residue (V44K), which also lies in the same APR, increased apparent solubility and reduced viscosity of MAB 1 without sacrificing antigen binding or thermal stability. Neutralizing the negatively charged surface patch (E59Y) also increased apparent solubility and reduced viscosity of MAB 1, but charge reversal at the same position (E59K/R) caused destabilization, decreased solubility and led to difficulties in sample manipulation that precluded their viscosity measurements at high concentrations. Both V44K and E59Y mutations showed similar increase in apparent solubility. However, the viscosity profile of E59Y was considerably better than that of the V44K, providing evidence that inter-molecular interactions in MAB 1 are electrostatically driven. In conclusion, neutralizing negatively charged surface patches may be more beneficial toward reducing viscosity of highly concentrated antibody solutions than charge reversal or aggregation prone motif disruption.

Wireless Power Transfer

ScienceCinema

None

2018-01-16

Wireless Power Transfer is an innovative approach using magnetic resonance coupling of air core transformers designed for today's growing plug-in electric vehicle market. This technology can provide a convenient, safe and flexible means to charge electric vehicles under stationary and dynamic conditions. Plug-in Electric Vehicles (PEV) are burdened by the need for cable and plug charger, galvanic isolation of the on-board electronics, bulk and cost of this charger and the large energy storage system (ESS) packs needed. With a system where you have to physically plug in there are a number of occasions where the owner could very well forget to charge the vehicle. For stationary applications (like charging of a PHEV at home), ORNL's innovative wireless power transfer technology adds a convenience factor compared to actually plugging in which will mean that the vehicle will have a full charge every morning. Electric vehicle charging must be safe, compact and efficient in order to be convenient for customers. By reconfiguring the transformer and altering the resonance frequency, energy is transferred to the battery with lower energy losses and with fewer demands on the primary circuit by the rest of the transformer system. The ORNL discovery shows that sufficient power for the battery can be transferred from the primary to secondary circuits without significant energy losses if the operating frequency is set at 50% to 95% of the resonance frequency of the circuit. The electrical power is then transmitted to the chargeable battery, which is electrically coupled to the secondary circuit through the air core transformer. Some advantages include: Reduced energy losses during transfer of energy to the battery; A charge potential that is relatively unaffected by up to 25% misalignment of vehicle; and Other receiving components draw less power from the primary circuit. These advantages allow wireless power technology applications to expand at the workplace and beyond as the demand for EV rises. For vehicles that operate over a fixed route such as busses and shuttle vehicles, Wireless Power Transfer (WPT) means that a smaller battery pack can be used. In the traditional system, the battery pack is designed to accommodate the needs of the entire route or shift. With WPT the battery can be downsized because it can be charged when the vehicle stops on its route (a rental car shuttle bus, for example, can charge when it waits in the terminal and again when it waits at the rental car place. Thus the battery only needs enough charge to get to the next stop. This decrease in battery size means significant cost savings to electrify the vehicle. This technology enables efficient "opportunity charging stations" for predefined routes and planned stops reducing down time. Charging can occur in minutes. This improvement also eliminates the harmful emissions that occur in garages while buses are at idle during charging. In larger cities, dynamic charging offers an even greater impact utilizing existing infrastructure. As vehicles travel along busy freeways and interstate systems, wireless charging can occur while the vehicle is in motion. With this technology a vehicle essentially has unlimited electric range while using a relatively small battery pack. In-motion charging stations use vehicle sensors to alert the driver. Traveling at normal speeds, sensors establish in-motion charging. WPT transmit pads sequentially energize to the negotiated power level based on vehicle speed and its requested charging energy. Lower power when vehicle speed is slow and much higher power for faster moving vehicles. Vehicle to Infrastructure communications (V2I) coordinates WPT charging level according to on-board battery pack state-of-charge. V2I activates the roadway transmit pads placing them in standby mode and negotiates charging fee based on prevailing grid rate and vehicle energy demand. Dynamic charging would allow electricity to supply a very large fraction of the energy for the transportation sector and reduce greatly petroleum consumption. Previously worrisome traffic delays now provide longer periods of charge while passing over in-motion chargers. Inclement weather such as rain and snow do not affect the charging capability. At ORNL, we are working to develop the robust nature of wireless power technology to provide a convenient, safe and flexible means to charge electric vehicles under stationary and dynamic conditions.

Wireless Power Transfer

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

None

2013-07-22

Wireless Power Transfer is an innovative approach using magnetic resonance coupling of air core transformers designed for today's growing plug-in electric vehicle market. This technology can provide a convenient, safe and flexible means to charge electric vehicles under stationary and dynamic conditions. Plug-in Electric Vehicles (PEV) are burdened by the need for cable and plug charger, galvanic isolation of the on-board electronics, bulk and cost of this charger and the large energy storage system (ESS) packs needed. With a system where you have to physically plug in there are a number of occasions where the owner could very well forgetmore » to charge the vehicle. For stationary applications (like charging of a PHEV at home), ORNL's innovative wireless power transfer technology adds a convenience factor compared to actually plugging in which will mean that the vehicle will have a full charge every morning. Electric vehicle charging must be safe, compact and efficient in order to be convenient for customers. By reconfiguring the transformer and altering the resonance frequency, energy is transferred to the battery with lower energy losses and with fewer demands on the primary circuit by the rest of the transformer system. The ORNL discovery shows that sufficient power for the battery can be transferred from the primary to secondary circuits without significant energy losses if the operating frequency is set at 50% to 95% of the resonance frequency of the circuit. The electrical power is then transmitted to the chargeable battery, which is electrically coupled to the secondary circuit through the air core transformer. Some advantages include: Reduced energy losses during transfer of energy to the battery; A charge potential that is relatively unaffected by up to 25% misalignment of vehicle; and Other receiving components draw less power from the primary circuit. These advantages allow wireless power technology applications to expand at the workplace and beyond as the demand for EV rises. For vehicles that operate over a fixed route such as busses and shuttle vehicles, Wireless Power Transfer (WPT) means that a smaller battery pack can be used. In the traditional system, the battery pack is designed to accommodate the needs of the entire route or shift. With WPT the battery can be downsized because it can be charged when the vehicle stops on its route (a rental car shuttle bus, for example, can charge when it waits in the terminal and again when it waits at the rental car place. Thus the battery only needs enough charge to get to the next stop. This decrease in battery size means significant cost savings to electrify the vehicle. This technology enables efficient "opportunity charging stations" for predefined routes and planned stops reducing down time. Charging can occur in minutes. This improvement also eliminates the harmful emissions that occur in garages while buses are at idle during charging. In larger cities, dynamic charging offers an even greater impact utilizing existing infrastructure. As vehicles travel along busy freeways and interstate systems, wireless charging can occur while the vehicle is in motion. With this technology a vehicle essentially has unlimited electric range while using a relatively small battery pack. In-motion charging stations use vehicle sensors to alert the driver. Traveling at normal speeds, sensors establish in-motion charging. WPT transmit pads sequentially energize to the negotiated power level based on vehicle speed and its requested charging energy. Lower power when vehicle speed is slow and much higher power for faster moving vehicles. Vehicle to Infrastructure communications (V2I) coordinates WPT charging level according to on-board battery pack state-of-charge. V2I activates the roadway transmit pads placing them in standby mode and negotiates charging fee based on prevailing grid rate and vehicle energy demand. Dynamic charging would allow electricity to supply a very large fraction of the energy for the transportation sector and reduce greatly petroleum consumption. Previously worrisome traffic delays now provide longer periods of charge while passing over in-motion chargers. Inclement weather such as rain and snow do not affect the charging capability. At ORNL, we are working to develop the robust nature of wireless power technology to provide a convenient, safe and flexible means to charge electric vehicles under stationary and dynamic conditions.« less

Collapse of charged scalar field in dilaton gravity

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

Borkowska, Anna; Rogatko, Marek; Moderski, Rafal

2011-04-15

We elaborated the gravitational collapse of a self-gravitating complex charged scalar field in the context of the low-energy limit of the string theory, the so-called dilaton gravity. We begin with the regular spacetime and follow the evolution through the formation of an apparent horizon and the final central singularity.

Engineering interfacial photo-induced charge transfer based on nanobamboo array architecture for efficient solar-to-chemical energy conversion.

PubMed

Wang, Xiaotian; Liow, Chihao; Bisht, Ankit; Liu, Xinfeng; Sum, Tze Chien; Chen, Xiaodong; Li, Shuzhou

2015-04-01

Engineering interfacial photo-induced charge transfer for highly synergistic photocatalysis is successfully realized based on nanobamboo array architecture. Programmable assemblies of various components and heterogeneous interfaces, and, in turn, engineering of the energy band structure along the charge transport pathways, play a critical role in generating excellent synergistic effects of multiple components for promoting photocatalytic efficiency. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed Central

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

2015-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2016-05-01

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

Mechanistic insights into the photoinduced charge carrier dynamics of BiOBr/CdS nanosheet heterojunctions for photovoltaic application.

PubMed

Jia, Huimin; Zhang, Beibei; He, Weiwei; Xiang, Yong; Zheng, Zhi

2017-03-02

The rational design of high performance hetero-structure photovoltaic devices requires a full understanding of the photoinduced charge transfer mechanism and kinetics at the interface of heterojunctions. In this paper, we intelligently fabricated p-BiOBr/n-CdS heterojunctions with perfect nanosheet arrays by using a facile successive ionic layer adsorption and reaction and chemical bath deposition methods at low temperature. A BiOBr/CdS heterojunction based solar cell has been fabricated which exhibited enhanced photovoltaic responses. Assisted by the surface photovoltage (SPV), transient photovoltage (TPV) and Kelvin probe technique, the photoinduced charge transfer dynamics on the BiOBr nanosheet and p-BiOBr/n-CdS interface were systematically investigated. It was found that the BiOBr/CdS nanosheet array heterojunctions were more efficient in facilitating charge carrier separation than both bare BiOBr and CdS films. The mechanism underlying the photoinduced charge carrier transfer behaviour was unravelled by allying the energy band of BiOBr/CdS p-n junctions from both the interfacial electric field and surface electric field. In addition, the CdS loading thickness in the p-BiOBr/n-CdS heterojunction and the incident wavelength affected greatly the transfer behavior of photoinduced charges, which was of great value for design of photovoltaic devices.

Adsorption of benzene, toluene, and xylene by two tetramethylammonium-smectites having different charge densities

USGS Publications Warehouse

Lee, Jiunn-Fwu; Mortland, Max M.; Chiou, Cary T.; Kite, Daniel E.; Boyd, Stephen A.

1990-01-01

A high-charge smectite from Arizona [cation-exchange capacity (CEC) = 120 meq/100 g] and a low-charge smectite from Wyoming (CEC = 90 meq/100 g) were used to prepare homoionic tetramethylammonium (TMA)-clay complexes. The adsorption of benzene, toluene, and o-xylene as vapors by the dry TMA-clays and as solutes from water by the wet TMA-clays was studied. The adsorption of the organic vapors by the dry TMA-smectite samples was strong and apparently consisted of interactions with both the aluminosilicate mineral surfaces and the TMA exchange ions in the interlayers. In the adsorption of organic vapors, the closer packing of TMA ions in the dry high-charge TMA-smectite, compared with the dry low-charge TMA-smectite, resulted in a somewhat higher degree of shape-selective adsorption of benzene, toluene, and xylene. In the presence of water, the adsorption capacities of both samples for the aromatic compounds were significantly reduced, although the uptake of benzene from water by the low-charge TMA-smectite was still substantial. This lower sorption capacity was accompanied by increased shape-selectivity for the aromatic compounds. The reduction in uptake and increased selectivity was much more pronounced for the water-saturated, high-charge TMA-smectite than for the low-charge TMA-smectite. Hydration of the TMA exchange ions and/or the mineral surfaces apparently reduced the accessibility of the aromatic molecules to interlamellar regions. The resulting water-induced sieving effect was greater for the high-charge TMA-smectite due to the higher density of exchanged TMA-ions. The low-charge Wyoming TMA-smectite was a highly effective adsorbent for removing benzene from water and may be useful for purifying benzene-contaminated water.

Columnar mesophases of hexabenzocoronene derivatives. II. Charge carrier mobility

NASA Astrophysics Data System (ADS)

Kirkpatrick, James; Marcon, Valentina; Kremer, Kurt; Nelson, Jenny; Andrienko, Denis

2008-09-01

Combining atomistic molecular dynamic simulations, Marcus-Hush theory description of charge transport rates, and master equation description of charge dynamics, we correlate the temperature-driven change of the mesophase structure with the change of charge carrier mobilities in columnar phases of hexabenzocoronene derivatives. The time dependence of fluctuations in transfer integrals shows that static disorder is predominant in determining charge transport characteristics. Both site energies and transfer integrals are distributed because of disorder in the molecular arrangement. It is shown that the contributions to the site energies from polarization and electrostatic effects are of opposite sign for positive charges. We look at three mesophases of hexabenzocoronene: herringbone, discotic, and columnar disordered. All results are compared to time resolved microwave conductivity data and show excellent agreement with no fitting parameters.

Columnar mesophases of hexabenzocoronene derivatives. II. Charge carrier mobility.

PubMed

Kirkpatrick, James; Marcon, Valentina; Kremer, Kurt; Nelson, Jenny; Andrienko, Denis

2008-09-07

Combining atomistic molecular dynamic simulations, Marcus-Hush theory description of charge transport rates, and master equation description of charge dynamics, we correlate the temperature-driven change of the mesophase structure with the change of charge carrier mobilities in columnar phases of hexabenzocoronene derivatives. The time dependence of fluctuations in transfer integrals shows that static disorder is predominant in determining charge transport characteristics. Both site energies and transfer integrals are distributed because of disorder in the molecular arrangement. It is shown that the contributions to the site energies from polarization and electrostatic effects are of opposite sign for positive charges. We look at three mesophases of hexabenzocoronene: herringbone, discotic, and columnar disordered. All results are compared to time resolved microwave conductivity data and show excellent agreement with no fitting parameters.

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.

Spectrophotometric Determination of Distigmine Bromide, Cyclopentolate HCl, Diaveridine HCl and Tetrahydrozoline HCl via Charge Transfer Complex Formation with TCNQ and TCNE Reagents.

PubMed

Mohamed, Gehad Genidy; Rizk, Mahmoud Sabry; Zaky Frag, Eman Yousry

2015-01-01

The purpose of this investigation was directed to propose sensitive, accurate and reproducible methods of analysis that can be applied to determine distigmine bromide (DTB), cyclopentolate hydrochloride (CPHC), diaveridine hydrochloride (DVHC) and tetrahydrozoline hydrochloride (THHC) drugs in pure form and pharmaceutical preparations via charge-transfer complex formation with 7,7,8,8-tetracyanoquinodimethane (TCNQ) and tetracyanoethylene (TCNE) reagents. Spectrophotometric method involve the addition a known excess of TCNQ or TCNE reagents to DTB, CPHC, DVHC and THHC drugs in acetonitrile, followed by the measurement of the absorbance of the CT complexes at the selected wavelength. The reaction stoichiometry is found to be 1:1 [drug]: [TCNQ or TCNE]. The absorbance is found to increase linearly with concentration of the drugs under investigation which is corroborated by the correlation coefficients of 0.9954-0.9981. The system obeys Beer's law for 6-400, 20-500, 1-180 and 60-560 µg mL(-1) and 80-600, 10-300, 1-60 and 80-640 µg mL(-1) for DTB, CPHC, DVHC and THHC drugs using TCNQ and TCNE reagents, respectively. The apparent molar absorptivity, sandell sensitivity, the limits of detection and quantification are also reported for the spectrophotometric method. Intra- and inter-day precision and accuracy of the method were evaluated as per ICH guidelines. The method was successfully applied to the assay of DTB, CPHC, DVHC and THHC drugs in formulations and the results were compared with those of a reference method by applying Student's t and F-tests. No interference was observed from common pharmaceutical excipients.

Spectrophotometric Determination of Distigmine Bromide, Cyclopentolate HCl, Diaveridine HCl and Tetrahydrozoline HCl via Charge Transfer Complex Formation with TCNQ and TCNE Reagents

PubMed Central

Mohamed, Gehad Genidy; Rizk, Mahmoud Sabry; Zaky Frag, Eman Yousry

2015-01-01

The purpose of this investigation was directed to propose sensitive, accurate and reproducible methods of analysis that can be applied to determine distigmine bromide (DTB), cyclopentolate hydrochloride (CPHC), diaveridine hydrochloride (DVHC) and tetrahydrozoline hydrochloride (THHC) drugs in pure form and pharmaceutical preparations via charge-transfer complex formation with 7,7,8,8-tetracyanoquinodimethane (TCNQ) and tetracyanoethylene (TCNE) reagents. Spectrophotometric method involve the addition a known excess of TCNQ or TCNE reagents to DTB, CPHC, DVHC and THHC drugs in acetonitrile, followed by the measurement of the absorbance of the CT complexes at the selected wavelength. The reaction stoichiometry is found to be 1:1 [drug]: [TCNQ or TCNE]. The absorbance is found to increase linearly with concentration of the drugs under investigation which is corroborated by the correlation coefficients of 0.9954-0.9981. The system obeys Beer’s law for 6-400, 20-500, 1-180 and 60-560 µg mL-1 and 80-600, 10-300, 1-60 and 80-640 µg mL-1 for DTB, CPHC, DVHC and THHC drugs using TCNQ and TCNE reagents, respectively. The apparent molar absorptivity, sandell sensitivity, the limits of detection and quantification are also reported for the spectrophotometric method. Intra- and inter-day precision and accuracy of the method were evaluated as per ICH guidelines. The method was successfully applied to the assay of DTB, CPHC, DVHC and THHC drugs in formulations and the results were compared with those of a reference method by applying Student’s t and F-tests. No interference was observed from common pharmaceutical excipients. PMID:26330858

Quasiparticles and charge transfer at the two surfaces of the honeycomb iridate Na2IrO3

NASA Astrophysics Data System (ADS)

Moreschini, L.; Lo Vecchio, I.; Breznay, N. P.; Moser, S.; Ulstrup, S.; Koch, R.; Wirjo, J.; Jozwiak, C.; Kim, K. S.; Rotenberg, E.; Bostwick, A.; Analytis, J. G.; Lanzara, A.

2017-10-01

Direct experimental investigations of the low-energy electronic structure of the Na2IrO3 iridate insulator are sparse and draw two conflicting pictures. One relies on flat bands and a clear gap, the other involves dispersive states approaching the Fermi level, pointing to surface metallicity. Here, by a combination of angle-resolved photoemission, photoemission electron microscopy, and x-ray absorption, we show that the correct picture is more complex and involves an anomalous band, arising from charge transfer from Na atoms to Ir-derived states. Bulk quasiparticles do exist, but in one of the two possible surface terminations the charge transfer is smaller and they remain elusive.

An ab initio study of ion induced charge transfer dynamics in collision of carbon ions with thymine.

PubMed

Bacchus-Montabonel, Marie-Christine; Tergiman, Yvette Suzanne

2011-05-28

Charge transfer in collisions of carbon ions on a thymine target has been studied theoretically in a wide collision range by means of ab initio quantum chemistry molecular methods. The process appears markedly anisotropic in the whole energy domain, significantly favoured in the perpendicular orientation. A specific decrease of the charge transfer cross sections at low collision energies may be pointed out and could induce an enhancement of the complementary fragmentation processes for collision energies down to about 10 eV, as observed for the low-electron fragmentation process. Such feature may be of important interest in ion-induced biomolecular radiation damage. This journal is © the Owner Societies 2011

Effect of Viscosity and Polar Properties of Solvent on Dynamics of Photoinduced Charge Transfer in BTA-1 Cation — Derivative of Thioflavin T

NASA Astrophysics Data System (ADS)

Gogoleva, S. D.; Stsiapura, V. I.

2018-05-01

It was found that the spectral and fluorescent properties of BTA-1C cation in protic and aprotic solvents differ. It was shown that for solutions in long-chain alcohols viscosity is the main factor that determines the dynamics of intramolecular charge transfer in the excited state of the BTA-1C molecule. In the case of aprotic solvents a correlation was found between the rate constant of twisted intramolecular charge transfer (TICT) during rotation of fragments of the molecule in relation to each other in the excited state and the solvent relaxation rate: k TICT 1/τ S .

Modelling charge transfer reactions with the frozen density embedding formalism.

PubMed

Pavanello, Michele; Neugebauer, Johannes

2011-12-21

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

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

NASA Astrophysics Data System (ADS)

Xu, Zhicheng; Bai, Guan; Dong, Chuan

2005-12-01

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

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

PubMed

Xu, Zhicheng; Bai, Guan; Dong, Chuan

2005-12-01

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

Computational study of interfacial charge transfer complexes of 2-anthroic acid adsorbed on a titania nanocluster for direct injection solar cells

NASA Astrophysics Data System (ADS)

Manzhos, Sergei; Kotsis, Konstantinos

2016-09-01

Adsorption and light absorption properties of interfacial charge transfer complexes of 2-anthroic acid and titania, promising for direct-injection solar cells, are studied ab initio. The formation of interfacial charge transfer bands is observed. The intensity of visible absorption is relatively low, highlighting a key challenge facing direct injection cells. We show that the popular strategy of using a lower level of theory for geometry optimization followed by single point calculations of adsorption or optical properties introduces significant errors which have been underappreciated: by up to 3 eV in adsorption energies, by up to 5 times in light absorption intensity.

Origin of attraction in p-benzoquinone complexes with benzene and p-hydroquinone.

PubMed

Tsuzuki, Seiji; Uchimaru, Tadafumi; Ono, Taizo

2017-08-30

The origin of the attraction in charge-transfer complexes (a p-hydroquinone-p-benzoquinone complex and benzene complexes with benzoquinone, tetracyanoethylene and Br 2 ) was analyzed using distributed multipole analysis and symmetry-adapted perturbation theory. Both methods show that the dispersion interactions are the primary source of the attraction in these charge-transfer complexes followed by the electrostatic interactions. The natures of the intermolecular interactions in these complexes are close to the π/π interactions of neutral aromatic molecules. The electrostatic interactions play important roles in determining the magnitude of the attraction. The contribution of charge-transfer interactions to the attraction is not large compared with the dispersion interactions in these complexes.

Theoretical studies of optics and charge transport in organic conducting oligomers and polymers: Rational design of improved transparent and conducting polymers

NASA Astrophysics Data System (ADS)

Hutchison, Geoffrey Rogers

Theoretical studies on a variety of oligo- and polyheterocycles elucidate their optical and charge transport properties, suggesting new, improved transparent conductive polymers. First-principles calculations provide accurate methodologies for predicting both optical band gaps of neutral and cationic oligomers and intrinsic charge transfer rates. Multidimensional analysis reveals important motifs in chemical tailorability of oligoheterocycle optical and charge transport properties. The results suggest new directions for design of novel materials. Using both finite oligomer and infinite polymer calculations, the optical band gaps in polyheterocycles follow a modified particle-in-a-box formalism, scaling approximately as 1/N (where N is the number of monomer units) in short chains, saturating for long chains. Calculations demonstrate that band structure changes upon heteroatom substitution, (e.g., from polythiophene to polypyrrole) derive from heteroatom electron affinity. Further investigation of chemical variability in substituted oligoheterocycles using multidimensional statistics reveals the interplay between heteroatom and substituent in correlations between structure and redox/optical properties of neutral and cationic species. A linear correlation between band gaps of neutral and cationic species upon oxidation of conjugated oligomers, shows redshifts of optical absorption for most species and blueshifts for small band gap species. Interstrand charge-transport studies focus on two contributors to hopping-style charge transfer rates: internal reorganization energy and the electronic coupling matrix element. Statistical analysis of chemical variability of reorganization energies in oligoheterocycles proves the importance of reorganization energy in determining intrinsic charge transfer rates (e.g., charge mobility in unsubstituted oligothiophenes). Computed bandwidths across several oligothiophene crystal packing motifs show similar electron and hole bandwidths, and show that well-known tilted and herringbone motifs in oligothiophenes are driven by electrostatic repulsion. Tilted stacks exhibit intrinsic charge-transfer rates smaller than cofacial stacks, but with lower packing energy. Given similar electron and hole bandwidths, a charge injection model explains substitution-modulated majority carrier changes in n- and p-type oligothiophene field-effect transistors.

Fast charging nickel-metal hydride traction batteries

NASA Astrophysics Data System (ADS)

Yang, Xiao Guang; Liaw, Bor Yann

This paper describes the fast charge ability, or "fast rechargeability", of nominal 85 Ah Ni-MH modules under various fast charge conditions, including constant current (CC); typically 1-3C, and constant power (CP) regimes. Our tests revealed that there is no apparent difference between CC and CP fast charge regimes with respect to charge efficiency and time. Following the USABC Electric Vehicle Battery Test Procedures Manual (Revision 2, 1996), we demonstrated that we were able to return 40% state of charge (SOC) from 60% depth of discharge (DOD) to 20% DOD within 15 min. Most importantly, we found that the internal pressure of the cell is the most critical parameter in the control of the fast charge process and the safe operation of the modules.

Designing a biocidal reverse osmosis membrane coating: Synthesis and biofouling properties

DOE PAGES

Hibbs, Michael R.; McGrath, Lucas K.; Kang, Seoktae; ...

2015-12-04

In this study, a biocidal coating was developed in order to reduce biofouling on a reverse osmosis (RO) membrane using a quaternary ammonium (QA) functionalized polymer. The synthesis of a series of polysulfone (PS) ionomers with QA groups is described, and a method for spraying these QA ionomers as an alcoholic solution, which dried into water insoluble coatings. Contact angle and streaming potential were used to analyze the coating's hydrophilicity and surface charge. Both PS-QA1 and the commercial RO membrane had an apparent contact angle of 68° that increased to 126° for PS-QA12 corresponding to alkyl chain length. A negativelymore » charged particle-probe was used to measure coated and uncoated RO membrane interaction forces. Measured interaction forces correlated strongly with the length of alkyl chains or hydrophobicity of the coated surfaces. Uncoated RO membranes and ones coated with PS-QA were exposed to suspensions of Escherichia coli cells. All four PS-QA coatings showed significant biotoxicity and killed 100% of the E. coli cells, but uncoated RO membranes had metabolically active biofilms. However, coatings tested in a RO crossflow system showed a flux reduction that is attributed to mass transfer resistance due to excessively thick films.« less

Designing a biocidal reverse osmosis membrane coating: Synthesis and biofouling properties

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

Hibbs, Michael R.; McGrath, Lucas K.; Kang, Seoktae

In this study, a biocidal coating was developed in order to reduce biofouling on a reverse osmosis (RO) membrane using a quaternary ammonium (QA) functionalized polymer. The synthesis of a series of polysulfone (PS) ionomers with QA groups is described, and a method for spraying these QA ionomers as an alcoholic solution, which dried into water insoluble coatings. Contact angle and streaming potential were used to analyze the coating's hydrophilicity and surface charge. Both PS-QA1 and the commercial RO membrane had an apparent contact angle of 68° that increased to 126° for PS-QA12 corresponding to alkyl chain length. A negativelymore » charged particle-probe was used to measure coated and uncoated RO membrane interaction forces. Measured interaction forces correlated strongly with the length of alkyl chains or hydrophobicity of the coated surfaces. Uncoated RO membranes and ones coated with PS-QA were exposed to suspensions of Escherichia coli cells. All four PS-QA coatings showed significant biotoxicity and killed 100% of the E. coli cells, but uncoated RO membranes had metabolically active biofilms. However, coatings tested in a RO crossflow system showed a flux reduction that is attributed to mass transfer resistance due to excessively thick films.« less

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

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

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

1992-01-09

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

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

PubMed

Sirjoosingh, Andrew; Hammes-Schiffer, Sharon

2011-03-24

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

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

PubMed

Li, Guangqi; Govind, Niranjan; Ratner, Mark A; Cramer, Christopher J; Gagliardi, Laura

2015-12-17

The mechanism of charge transfer has been observed to change from tunneling to hopping with increasing numbers of DNA base pairs in polynucleotides and with the length of molecular wires. The aim of this paper is to investigate this transition by examining the population dynamics using a tight-binding Hamiltonian with model parameters to describe a linear donor-bridge-acceptor (D-B-A) system. The model includes a primary vibration and an electron-vibration coupling at each site. A further coupling of the primary vibration with a secondary phonon bath allows the system to dissipate energy to the environment and reach a steady state. We apply the quantum master equation (QME) approach, based on second-order perturbation theory in a quantum dissipative system, to examine the dynamical processes involved in charge-transfer and follow the population transfer rate at the acceptor, ka, to shed light on the transition from tunneling to hopping. With a small tunneling parameter, V, the on-site population tends to localize and form polarons, and the hopping mechanism dominates the transfer process. With increasing V, the population tends to be delocalized and the tunneling mechanism dominates. The competition between incoherent hopping and coherent tunneling governs the mechanism of charge transfer. By varying V and the total number of sites, we also examine the onset of the transition from tunneling to hopping with increasing length.

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

USGS Publications Warehouse

Sherman, David M.

1987-01-01

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

Investigating Wireless Power Transfer

ERIC Educational Resources Information Center

St. John, Stuart A.

2017-01-01

Understanding Physics is a great end in itself, but is also crucial to keep pace with developments in modern technology. Wireless power transfer, known to many only as a means to charge electric toothbrushes, will soon be commonplace in charging phones, electric cars and implanted medical devices. This article outlines how to produce and use a…

Charge transfer polarisation wave in high Tc oxides and superconductive pairing

NASA Technical Reports Server (NTRS)

Chakraverty, B. K.

1991-01-01

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

Energy and charge transfer in nanoscale hybrid materials.

PubMed

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

2015-06-01

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

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

PubMed Central

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

2014-01-01

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

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

Hu, Dehua; Liu, Qing; Tisdale, Jeremy

This paper reports Seebeck effects driven by both surface polarization difference and entropy difference by using intramolecular charge-transfer states in n-type and p-type conjugated polymers, namely IIDT and IIDDT, based on vertical conductor/polymer/conductor thin-film devices. Large Seebeck coefficients of -898 V/K and 1300 V/K from are observed from n-type IIDT p-type IIDDT, respectively, when the charge-transfer states are generated by a white light illumination of 100 mW/cm2. Simultaneously, electrical conductivities are increased from almost insulating states in dark condition to conducting states under photoexcitation in both n-type IIDT and p-type IIDDT devices. We find that the intramolecular charge-transfer states canmore » largely enhance Seebeck effects in the n-type IIDT and p-type IIDDT devices driven by both surface polarization difference and entropy difference. Furthermore, the Seebeck effects can be shifted between polarization and entropy regimes when electrical conductivities are changed. This reveals a new concept to develop Seebeck effects by controlling polarization and entropy regimes based on charge-transfer states in vertical conductor/polymer/conductor thin-film devices.« less

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

NASA Astrophysics Data System (ADS)

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

2005-05-01

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

Electron Transfer Ion/Ion Reactions in a Three-Dimensional Quadrupole Ion Trap: Reactions of Doubly and Triply Protonated Peptides with SO2·−

PubMed Central

Pitteri, Sharon J.; Chrisman, Paul A.; Hogan, Jason M.; McLuckey, Scott A.

2005-01-01

Ion–ion reactions between a variety of peptide cations (doubly and triply charged) and SO2 anions have been studied in a 3-D quadrupole ion trap, resulting in proton and electron transfer. Electron transfer dissociation (ETD) gives many c- and z-type fragments, resulting in extensive sequence coverage in the case of triply protonated peptides with SO2·−. For triply charged neurotensin, in which a direct comparison can be made between 3-D and linear ion trap results, abundances of ETD fragments relative to one another appear to be similar. Reactions of doubly protonated peptides with SO2·− give much less structural information from ETD than triply protonated peptides. Collision-induced dissociation (CID) of singly charged ions formed in reactions with SO2·− shows a combination of proton and electron transfer products. CID of the singly charged species gives more structural information than ETD of the doubly protonated peptide, but not as much information as ETD of the triply protonated peptide. PMID:15762593

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

NASA Astrophysics Data System (ADS)

Calvo, Florent; Bacchus-Montabonel, Marie-Christine

2018-01-01

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

Fermi Level shifting, Charge Transfer and Induced Magnetic Coupling at La0.7Ca0.3MnO3/LaNiO3 Interface

PubMed Central

Ning, Xingkun; Wang, Zhanjie; Zhang, Zhidong

2015-01-01

A large magnetic coupling has been observed at the La0.7Ca0.3MnO3/LaNiO3 (LCMO/LNO) interface. The x-ray photoelectron spectroscopy (XPS) study results show that Fermi level continuously shifted across the LCMO/LNO interface in the interface region. In addition, the charge transfer between Mn and Ni ions of the type Mn3+ − Ni3+ → Mn4+ − Ni2+ with the oxygen vacancies are observed in the interface region. The intrinsic interfacial charge transfer can give rise to itinerant electrons, which results in a “shoulder feature” observed at the low binding energy in the Mn 2p core level spectra. Meanwhile, the orbital reconstruction can be mapped according to the Fermi level position and the charge transfer mode. It can be considered that the ferromagnetic interaction between Ni2+ and Mn4+ gives rise to magnetic regions that pin the ferromagnetic LCMO and cause magnetic coupling at the LCMO/LNO interface. PMID:25676088

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

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

Effect of temperature and heating rate on apparent lethal concentrations of pyrolysis products

NASA Technical Reports Server (NTRS)

Hilado, C. J.; Solis, A. N.; Marcussen, W. H.; Furst, A.

1976-01-01

The apparent lethal concentrations for 50 percent of the test animals of the pyrolysis products from twelve polymeric materials were studied as a function of temperature and heating rate. The materials were polyethylene, nylon 6, ABS, polycarbonate, polyether sulfone, polyaryl sulfone, wool fabric, aromatic polyamide fabric, polychloroprene foam, polyvinyl fluoride film, Douglas fir, and red oak. The apparent lethal concentration values of most materials vary significantly with temperature and heating rate. The apparent lethal concentration values, based on weight of sample charged, appears to effectively integrate the thermophysical, thermochemical, and physiological responses from a known quantity of material under specified imposed conditions.

Non-perturbative Quantification of Ionic Charge Transfer through Nm-Scale Protein Pores Using Graphene Microelectrodes

NASA Astrophysics Data System (ADS)

Ping, Jinglei; Johnson, A. T. Charlie; A. T. Charlie Johnson Team

Conventional electrical methods for detecting charge transfer through protein pores perturb the electrostatic condition of the solution and chemical reactivity of the pore, and are not suitable to be used for complex biofluids. We developed a non-perturbative methodology ( fW input power) for quantifying trans-pore electrical current and detecting the pore status (i.e., open vs. closes) via graphene microelectrodes. Ferritin was used as a model protein featuring a large interior compartment, well-separated from the exterior solution with discrete pores as charge commuting channels. The charge flowing through the ferritin pores transfers into the graphene microelectrode and is recorded by an electrometer. In this example, our methodology enables the quantification of an inorganic nanoparticle-protein nanopore interaction in complex biofluids. The authors acknowledge the support from the Defense Advanced Research Projects Agency (DARPA) and the U.S. Army Research Office under Grant Number W911NF1010093.

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.

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

PubMed

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

2017-08-02

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

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

PubMed Central

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

2017-01-01

The detection of furfural in transformer oil through surface enhanced Raman spectroscopy (SERS) is one of the most promising online monitoring techniques in the process of transformer aging. In this work, the Raman of individual furfural molecules and SERS of furfural-Mx (M = Ag, Au, Cu) complexes are investigated through density functional theory (DFT). In the Raman spectrum of individual furfural molecules, the vibration mode of each Raman peak is figured out, and the deviation from experimental data is analyzed by surface charge distribution. In the SERS of furfural-Mx complexes, the influence of atom number and species on SERS chemical enhancement factors (EFs) are studied, and are further analyzed by charge transfer effect. Our studies strengthen the understanding of charge transfer effect in the SERS of furfural molecules, which is important in the online monitoring of the transformer aging process through SERS. PMID:28767053

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

NASA Astrophysics Data System (ADS)

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

2017-11-01

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

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

NASA Astrophysics Data System (ADS)

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

2017-09-01

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

Electrification of particulate entrained fluid flows-Mechanisms, applications, and numerical methodology

NASA Astrophysics Data System (ADS)

Wei, Wei; Gu, Zhaolin

2015-10-01

Particulates in natural and industrial flows have two basic forms: liquid (droplet) and solid (particle). Droplets would be charged in the presence of the applied electric field (e.g. electrospray). Similar to the droplet charging, particles can also be charged under the external electric field (e.g. electrostatic precipitator), while in the absence of external electric field, tribo-electrostatic charging is almost unavoidable in gas-solid two-phase flows due to the consecutive particle contacts (e.g. electrostatic in fluidized bed or wind-blown sand). The particle charging may be beneficial, or detrimental. Although electrostatics in particulate entrained fluid flow systems have been so widely used and concerned, the mechanisms of particulate charging are still lack of a thorough understanding. The motivation of this review is to explore a clear understanding of particulate charging and movement of charged particulate in two-phase flows, by summarizing the electrification mechanisms, physical models of particulate charging, and methods of charging/charged particulate entrained fluid flow simulations. Two effective methods can make droplets charged in industrial applications: corona charging and induction charging. The droplet charge to mass ratio by corona charging is more than induction discharge. The particle charging through collisions could be attributed to electron transfer, ion transfer, material transfer, and/or aqueous ion shift on particle surfaces. The charges on charged particulate surface can be measured, nevertheless, the charging process in nature or industry is difficult to monitor. The simulation method might build a bridge of investigating from the charging process to finally charged state on particulate surface in particulate entrained fluid flows. The methodology combining the interface tracking under the action of the applied electric with the fluid flow governing equations is applicable to the study of electrohydrodynamics problems. The charge distribution and mechanical behaviors of liquid surface can be predicted by using this method. The methodology combining particle charging model with Computational Fluid Dynamics (CFD) and Discrete element method (DEM) is applicable to study the particle charging/charged processes in gas-solid two phase flows, the influence factors of particle charging, such as gas-particle interaction, contact force, contact area, and various velocities, are described systematically. This review would explore a clear understanding of the particulate charging and provide theoretical references to control and utilize the charging/charged particulate entrained fluid system.

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

PubMed

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

2017-06-01

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

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

PubMed

Ha, Phuc Thi; Moon, Hyunsoo; Kim, Byung Hong; Ng, How Yong; Chang, In Seop

2010-03-15

An alternative method for determining the charge transfer resistance and double-layer capacitance of microbial fuel cells (MFCs), easily implemented without a potentiostat, was developed. A dynamic model with two parameters, the charge transfer resistance and double-layer capacitance of electrodes, was derived from a linear differential equation to depict the current generation with respect to activation overvoltage. This model was then used to fit the transient cell voltage response to the current step change during the continuous operation of a flat-plate type MFC fed with acetate. Variations of the charge transfer resistance and the capacitance value with respect to the MFC design conditions (biocatalyst existence and electrode area) and operating parameters (acetate concentration and buffer strength in the catholyte) were then determined to elucidate the validity of the proposed method. This model was able to describe the dynamic behavior of the MFC during current change in the activation loss region; having an R(2) value of over 0.99 in most tests. Variations of the charge transfer resistance value (thousands of Omega) according to the change of the design factors and operational factors were well-correlated with the corresponding MFC performances. However, though the capacitance values (approximately 0.02 F) reflected the expected trend according to the electrode area change and catalyst property, they did not show significant variation with changes in either the acetate concentration or buffer strength. (c) 2009 Elsevier B.V. All rights reserved.

Enhancing SERS by Means of Supramolecular Charge Transfer

NASA Technical Reports Server (NTRS)

Wong, Eric; Flood, Amar; Morales, Alfredo

2009-01-01

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

Conductive scanning probe microscopy of the semicontinuous gold film and its SERS enhancement toward two-step photo-induced charge transfer and effect of the supportive layer

NASA Astrophysics Data System (ADS)

Sinthiptharakoon, K.; Sapcharoenkun, C.; Nuntawong, N.; Duong, B.; Wutikhun, T.; Treetong, A.; Meemuk, B.; Kasamechonchung, P.; Klamchuen, A.

2018-05-01

The semicontinuous gold film, enabling various electronic applications including development of surface-enhanced Raman scattering (SERS) substrate, is investigated using conductive atomic force microscopy (CAFM) and Kelvin probe force microscopy (KPFM) to reveal and investigate local electronic characteristics potentially associated with SERS generation of the film material. Although the gold film fully covers the underlying silicon surface, CAFM results reveal that local conductivity of the film is not continuous with insulating nanoislands appearing throughout the surface due to incomplete film percolation. Our analysis also suggests the two-step photo-induced charge transfer (CT) play the dominant role in the enhancement of SERS intensity with strong contribution from free electrons of the silicon support. Silicon-to-gold charge transport is illustrated by KPFM results showing that Fermi level of the gold film is slightly inhomogeneous and far below the silicon conduction band. We propose that inhomogeneity of the film workfunction affecting chemical charge transfer between gold and Raman probe molecule is associated with the SERS intensity varying across the surface. These findings provide deeper understanding of charge transfer mechanism for SERS which can help in design and development of the semicontinuous gold film-based SERS substrate and other electronic applications.

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

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

Yao, Yi; Berkowitz, Max L., E-mail: maxb@unc.edu, E-mail: ykanai@unc.edu; Kanai, Yosuke, E-mail: maxb@unc.edu, E-mail: ykanai@unc.edu

2015-12-28

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

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

NASA Astrophysics Data System (ADS)

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

2018-06-01

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

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

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

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.

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

PubMed

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

2016-04-21

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

Structural and vibrational characteristics of a non-linear optical material 3-(4-nitrophenyl)-1-(pyridine-3-yl) prop-2-en-1-one probed by quantum chemical computation and spectroscopic techniques

NASA Astrophysics Data System (ADS)

Kumar, Ram; Karthick, T.; Tandon, Poonam; Agarwal, Parag; Menezes, Anthoni Praveen; Jayarama, A.

2018-07-01

Chalcone and its derivatives are well-known for their high non-linear optical behavior and charge transfer characteristics. The effectiveness of charge transfer via ethylenic group and increase in NLO response of the chalcone upon substitutions are of great interest. The present study focuses the structural, charge transfer and non-linear optical properties of a new chalcone derivative "3-(4-nitrophenyl)-1-(pyridine-3-yl) prop-2-en-1-one" (hereafter abbreviated as 4 NP3AP). To accomplish this task, we have incorporated the experimental FT-IR, FT-Raman and UV-vis spectroscopic studies along with quantum chemical calculations. The frequency assignments of peaks in IR and Raman have been done on the basis of potential energy distribution and the results were compared with the earlier reports on similar kind of molecules. For obtaining the electronic transition details of 4 NP3AP, UV-vis spectrum has been simulated by considering both gaseous and solvent phase using time-dependent density functional theory (TD-DFT). The HOMO-LUMO energy gap, most important factor to be considered for studying charge transfer properties of the molecule has been calculated. The electron density surface map corresponding to the net electrostatic point charges has been generated to obtain the electrophilic and nucleophilic sites. The charge transfer originating from the occupied (donor) and unoccupied (acceptor) molecular orbitals have been analyzed with the help of natural bond orbital theory. Moreover, the estimation of second-hyperpolarizability of the molecule confirms the non-linear optical behavior of the molecule.

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

NASA Astrophysics Data System (ADS)

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

2017-03-01

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

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

PubMed

Satapathy, Sitakanta; Prasad, Edamana

2016-10-05

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

CCD radiation damage in ESA Cosmic Visions missions: assessment and mitigation

NASA Astrophysics Data System (ADS)

Lumb, David H.

2009-08-01

Charge Coupled Device (CCD) imagers have been widely used in space-borne astronomical instruments. A frequent concern has been the radiation damage effects on the CCD charge transfer properties. We review some methods for assessing the Charge Transfer Inefficiency (CTI) in CCDs. Techniques to minimise degradation using background charge injection and p-channel CCD architectures are discussed. A critical review of the claims for p-channel architectures is presented. The performance advantage for p-channel CCD performance is shown to be lower than claimed previously. Finally we present some projections for the performance in the context of some future ESA missions.

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

PubMed Central

Krasnoslobodtsev, Alexey V.; Smirnov, Sergei N.

2008-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

Large Capacitance Measurement by Multiple Uses of MBL Charge Sensor

ERIC Educational Resources Information Center

Lee, Jung Sook; Chae, Min; Kim, Jung Bog

2010-01-01

A recent article by Morse described interesting electrostatics experiments using an MBL charge sensor. In this application, the charge sensor has a large capacitance compared to the charged test object, so nearly all charges can be transferred to the sensor capacitor from the capacitor to be measured. However, the typical capacitance of commercial…

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.)

Large apparent electric size of solid-state nanopores due to spatially extended surface conduction.

PubMed

Lee, Choongyeop; Joly, Laurent; Siria, Alessandro; Biance, Anne-Laure; Fulcrand, Rémy; Bocquet, Lydéric

2012-08-08

Ion transport through nanopores drilled in thin membranes is central to numerous applications, including biosensing and ion selective membranes. This paper reports experiments, numerical calculations, and theoretical predictions demonstrating an unexpectedly large ionic conduction in solid-state nanopores, taking its origin in anomalous entrance effects. In contrast to naive expectations based on analogies with electric circuits, the surface conductance inside the nanopore is shown to perturb the three-dimensional electric current streamlines far outside the nanopore in order to meet charge conservation at the pore entrance. This unexpected contribution to the ionic conductance can be interpreted in terms of an apparent electric size of the solid-state nanopore, which is much larger than its geometric counterpart whenever the number of charges carried by the nanopore surface exceeds its bulk counterpart. This apparent electric size, which can reach hundreds of nanometers, can have a major impact on the electrical detection of translocation events through nanopores, as well as for ionic transport in biological nanopores.

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

PubMed

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

2009-01-01

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

Efficient Auger Charge-Transfer Processes in ZnO

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

Rapid electron transfer by the carbon matrix in natural pyrogenic carbon

PubMed Central

Sun, Tianran; Levin, Barnaby D. A.; Guzman, Juan J. L.; Enders, Akio; Muller, David A.; Angenent, Largus T.; Lehmann, Johannes

2017-01-01

Surface functional groups constitute major electroactive components in pyrogenic carbon. However, the electrochemical properties of pyrogenic carbon matrices and the kinetic preference of functional groups or carbon matrices for electron transfer remain unknown. Here we show that environmentally relevant pyrogenic carbon with average H/C and O/C ratios of less than 0.35 and 0.09 can directly transfer electrons more than three times faster than the charging and discharging cycles of surface functional groups and have a 1.5 V potential range for biogeochemical reactions that invoke electron transfer processes. Surface functional groups contribute to the overall electron flux of pyrogenic carbon to a lesser extent with greater pyrolysis temperature due to lower charging and discharging capacities, although the charging and discharging kinetics remain unchanged. This study could spur the development of a new generation of biogeochemical electron flux models that focus on the bacteria–carbon–mineral conductive network. PMID:28361882

Regulation control and energy management scheme for wireless power transfer

DOEpatents

Miller, John M.

2015-12-29

Power transfer rate at a charging facility can be maximized by employing a feedback scheme. The state of charge (SOC) and temperature of the regenerative energy storage system (RESS) pack of a vehicle is monitored to determine the load due to the RESS pack. An optimal frequency that cancels the imaginary component of the input impedance for the output signal from a grid converter is calculated from the load of the RESS pack, and a frequency offset f* is made to the nominal frequency f.sub.0 of the grid converter output based on the resonance frequency of a magnetically coupled circuit. The optimal frequency can maximize the efficiency of the power transfer. Further, an optimal grid converter duty ratio d* can be derived from the charge rate of the RESS pack. The grid converter duty ratio d* regulates wireless power transfer (WPT) power level.

Phonon-electron coupling and tunneling effect on charge transport in organic semi-conductor crystals of Cn-BTBT.

PubMed

Zhou, Yecheng; Deng, Wei-Qiao; Zhang, Hao-Li

2016-09-14

Cn-[1]benzothieno[3,2-b][1]-benzothiophene (BTBT) crystals show very high hole mobilities in experiments. These high mobilities are beyond existing theory prediction. Here, we employed different quantum chemistry methods to investigate charge transfer in Cn-BTBT crystals and tried to find out the reasons for the underestimation in the theory. It was found that the hopping rate estimated by the Fermi Golden Rule is higher than that of the Marcus theory due to the high temperature approximation and failure at the classic limit. More importantly, molecular dynamics simulations revealed that the phonon induced fluctuation of electronic transfer integral is much larger than the average of the electronic transfer integral itself. Mobilities become higher if simulations implement the phonon-electron coupling. This conclusion indicates that the phonon-electron coupling promotes charge transfer in organic semi-conductors at room temperature.

Phonon-electron coupling and tunneling effect on charge transport in organic semi-conductor crystals of Cn-BTBT

NASA Astrophysics Data System (ADS)

Zhou, Yecheng; Deng, Wei-Qiao; Zhang, Hao-Li

2016-09-01

Cn-[1]benzothieno[3,2-b][1]-benzothiophene (BTBT) crystals show very high hole mobilities in experiments. These high mobilities are beyond existing theory prediction. Here, we employed different quantum chemistry methods to investigate charge transfer in Cn-BTBT crystals and tried to find out the reasons for the underestimation in the theory. It was found that the hopping rate estimated by the Fermi Golden Rule is higher than that of the Marcus theory due to the high temperature approximation and failure at the classic limit. More importantly, molecular dynamics simulations revealed that the phonon induced fluctuation of electronic transfer integral is much larger than the average of the electronic transfer integral itself. Mobilities become higher if simulations implement the phonon-electron coupling. This conclusion indicates that the phonon-electron coupling promotes charge transfer in organic semi-conductors at room temperature.

The transfer behavior of different ions across anion and cation exchange membranes under vanadium flow battery medium

NASA Astrophysics Data System (ADS)

Sun, Jiawei; Li, Xianfeng; Xi, Xiaoli; Lai, Qinzhi; Liu, Tao; Zhang, Huamin

2014-12-01

The transfer behavior of different ions (V2+, V3+, VO2+, VO2+, H+, SO42-) across ion exchange membranes is investigated under vanadium flow battery (VFB) operating condition. VX-20 anion exchange membrane (AEM) and Nafion 115 cation exchange membrane (CEM) are selected to investigate the influence of fixed charged groups on the transfer behavior of different ions. The interaction between different ions and water is discussed in detail aiming to ascertain the variation of different ions in the charge-discharge process. Under the VFB medium, the transfer behavior and function of different ions are very different for the AEM and CEM. V2+ ions at the negative side accumulate when VFB is assembled with Nafion 115, while the VO2+ ions at the positive side accumulate for VX-20. The SO42- ions will transfer across Nafion 115 to balance the charges and the protons can balance the charges of VX-20. Finally the capacity fade mechanism of different membranes is investigated, showing that the capacity decay of VFB assembled with Nafion 115 mainly results from the cross mix of vanadium ions across the membrane, however, for VX-20, the side reactions can be the major reason. This paper provides important information about electrolyte for the application of VFB.

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

PubMed

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

1996-11-20

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

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

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

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

Coupled electron-nuclear dynamics, implemented using the Ehrenfest method, has been used to study charge migration with fixed nuclei, together with charge transfer when nuclei are allowed to move. Simulations were initiated at reference geometries of neutral benzene and 2-phenylethylamine (PEA), and at geometries close to potential energy surface crossings in the cations. Cationic eigenstates, and the so-called sudden approximation, involving removal of an electron from a correlated ground-state wavefunction for the neutral species, were used as initial conditions. Charge migration without coupled nuclear motion could be observed if the Ehrenfest simulation, using the sudden approximation, was started near a conicalmore » intersection where the states were both strongly coupled and quasi-degenerate. Further, the main features associated with charge migration were still recognizable when the nuclear motion was allowed to couple. In the benzene radical cation, starting from the reference neutral geometry with the sudden approximation, one could observe sub-femtosecond charge migration with a small amplitude, which results from weak interaction with higher electronic states. However, we were able to engineer large amplitude charge migration, with a period between 10 and 100 fs, corresponding to oscillation of the electronic structure between the quinoid and anti-quinoid cationic electronic configurations, by distorting the geometry along the derivative coupling vector from the D{sub 6h} Jahn-Teller crossing to lower symmetry where the states are not degenerate. When the nuclear motion becomes coupled, the period changes only slightly. In PEA, in an Ehrenfest trajectory starting from the D{sub 2} eigenstate and reference geometry, a partial charge transfer occurs after about 12 fs near the first crossing between D{sub 1}, D{sub 2} (N{sup +}-Phenyl, N-Phenyl{sup +}). If the Ehrenfest propagation is started near this point, using the sudden approximation without coupled nuclear motion, one observes an oscillation of the spin density – charge migration – between the N atom and the phenyl ring with a period of 4 fs. When the nuclear motion becomes coupled, this oscillation persists in a damped form, followed by an effective charge transfer after 30 fs.« less

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

NASA Astrophysics Data System (ADS)

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

2013-07-01

Coupled electron-nuclear dynamics, implemented using the Ehrenfest method, has been used to study charge migration with fixed nuclei, together with charge transfer when nuclei are allowed to move. Simulations were initiated at reference geometries of neutral benzene and 2-phenylethylamine (PEA), and at geometries close to potential energy surface crossings in the cations. Cationic eigenstates, and the so-called sudden approximation, involving removal of an electron from a correlated ground-state wavefunction for the neutral species, were used as initial conditions. Charge migration without coupled nuclear motion could be observed if the Ehrenfest simulation, using the sudden approximation, was started near a conical intersection where the states were both strongly coupled and quasi-degenerate. Further, the main features associated with charge migration were still recognizable when the nuclear motion was allowed to couple. In the benzene radical cation, starting from the reference neutral geometry with the sudden approximation, one could observe sub-femtosecond charge migration with a small amplitude, which results from weak interaction with higher electronic states. However, we were able to engineer large amplitude charge migration, with a period between 10 and 100 fs, corresponding to oscillation of the electronic structure between the quinoid and anti-quinoid cationic electronic configurations, by distorting the geometry along the derivative coupling vector from the D6h Jahn-Teller crossing to lower symmetry where the states are not degenerate. When the nuclear motion becomes coupled, the period changes only slightly. In PEA, in an Ehrenfest trajectory starting from the D2 eigenstate and reference geometry, a partial charge transfer occurs after about 12 fs near the first crossing between D1, D2 (N+-Phenyl, N-Phenyl+). If the Ehrenfest propagation is started near this point, using the sudden approximation without coupled nuclear motion, one observes an oscillation of the spin density - charge migration - between the N atom and the phenyl ring with a period of 4 fs. When the nuclear motion becomes coupled, this oscillation persists in a damped form, followed by an effective charge transfer after 30 fs.

Unit-dose assay of tropine alkaloids and their synthetic analogs.

PubMed

Gomaa, C; Taha, A

1975-08-01

A charge-transfer spectrophotometric method was developed for unit-dose assay of the tropine alkaloids and some of their synthetic analogs. The high molar absorptivities of the charge-transfer bands of the alkaloids with iodine in ethylene dichloride resulted in improved recoveries and good precision, particularly at the low dose levels of pediatric and hypodermic tablets.

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

Pezeshki, Alan M.; Sacci, Robert L.; Delnick, Frank M.

Here, an improved method for quantitative measurement of the charge transfer, finite diffusion, and ohmic overpotentials in redox flow batteries using electrochemical impedance spectroscopy is presented. The use of a pulse dampener in the hydraulic circuit enables the collection of impedance spectra at low frequencies with a peristaltic pump, allowing the measurement of finite diffusion resistances at operationally relevant flow rates. This method is used to resolve the rate-limiting processes for the V 2+/V 3+ redox couple on carbon felt and carbon paper electrodes in the vanadium redox flow battery. Carbon felt was limited by both charge transfer and ohmicmore » resistance, while carbon paper was limited by charge transfer, finite diffusion, and ohmic resistances. The influences of vanadium concentration and flow field design also are quantified.« less

Modelling charge transfer reactions with the frozen density embedding formalism

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

Pavanello, Michele; Neugebauer, Johannes

2011-12-21

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

Low-temperature fabrication of alkali metal-organic charge transfer complexes on cotton textile for optoelectronics and gas sensing.

PubMed

Ramanathan, Rajesh; Walia, Sumeet; Kandjani, Ahmad Esmaielzadeh; Balendran, Sivacarendran; Mohammadtaheri, Mahsa; Bhargava, Suresh Kumar; Kalantar-zadeh, Kourosh; Bansal, Vipul

2015-02-03

A generalized low-temperature approach for fabricating high aspect ratio nanorod arrays of alkali metal-TCNQ (7,7,8,8-tetracyanoquinodimethane) charge transfer complexes at 140 °C is demonstrated. This facile approach overcomes the current limitation associated with fabrication of alkali metal-TCNQ complexes that are based on physical vapor deposition processes and typically require an excess of 800 °C. The compatibility of soft substrates with the proposed low-temperature route allows direct fabrication of NaTCNQ and LiTCNQ nanoarrays on individual cotton threads interwoven within the 3D matrix of textiles. The applicability of these textile-supported TCNQ-based organic charge transfer complexes toward optoelectronics and gas sensing applications is established.

A new type of localized fast moving electronic excitations in molecular chains

NASA Astrophysics Data System (ADS)

Korshunova, A. N.; Lakhno, V. D.

2014-06-01

It is shown that in a Holstein molecular chain placed in a strong longitudinal electric field some new types of excitations can arise. These excitations can transfer a charge over large distance (more than 1000 nucleotide pairs) along the chain retaining approximately their shapes. Excitations are formed only when a strong electric field either exists or quickly arises under especially preassigned conditions. These excitations transfer a charge even in the case when Holstein polarons are practically immobile. The results obtained are applied to synthetic homogeneous PolyG/PolyC DNA duplexes. They can also be provide the basis for explanation of famous H.W. Fink and C. Schönenberger experiment on long-range charge transfer in DNA.

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

N, Rekha T.; Rajkumar, Beulah J. M., E-mail: beulah-rajkumar@yahoo.co.in

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

A comparison of various surface charge transfer hole doping of graphene grown by chemical vapour deposition

NASA Astrophysics Data System (ADS)

Chandramohan, S.; Seo, Tae Hoon; Janardhanam, V.; Hong, Chang-Hee; Suh, Eun-Kyung

2017-10-01

Charge transfer doping is a renowned route to modify the electrical and electronic properties of graphene. Understanding the stability of potentially important charge-transfer materials for graphene doping is a crucial first step. Here we present a systematic comparison on the doping efficiency and stability of single layer graphene using molybdenum trioxide (MoO3), gold chloride (AuCl3), and bis(trifluoromethanesulfonyl)amide (TFSA). Chemical dopants proved to be very effective, but MoO3 offers better thermal stability and device fabrication compatibility. Single layer graphene films with sheet resistance values between 100 and 200 ohm/square were consistently produced by implementing a two-step growth followed by doping without compromising the optical transmittance.

On the dependence of charge density on surface curvature of an isolated conductor

NASA Astrophysics Data System (ADS)

Bhattacharya, Kolahal

2016-03-01

A study of the relation between the electrostatic charge density at a point on a conducting surface and the curvature of the surface (at that point) is presented. Two major papers in the scientific literature on this topic are reviewed and the apparent discrepancy between them is resolved. Hence, a step is taken towards obtaining a general analytic formula for relating the charge density with surface curvature of conductors. The merit of this formula and its limitations are discussed.

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

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

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

2013-02-07

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

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

PubMed

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

2013-02-07

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

Organic doping of rotated double layer graphene

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

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

2016-05-06

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

Electronic and magnetic properties of transition metal doped graphyne

NASA Astrophysics Data System (ADS)

Gangan, Abhijeet Sadashiv; Yadav, Asha S.; Chakraborty, Brahmananda; Ramaniah, Lavanya M.

2017-05-01

We have theoretically investigated the interaction of few 3d (V,Mn) and 4d (Y,Zr) transition metals with the γ-graphyne structure using the spin-polarized density functional theory for its potentials application in Hydrogen storage, spintronics and nano-electronics. By doping different TMs we have observed that the system can be either metallic(Y), semi-conducting or half metallic. The system for Y and Zr doped graphyne becomes non-magnetic while V and Mn doped graphyne have a magnetic moments of l μB and 3 μB respectively From bader charge analysis it is seen that there is a charge transfer from the TM atom to the graphyne. Zr and Y have a net charge transfer of 2.15e and 1.73e respectively. Charge density analysis also shows the polarization on the carbon skeleton which becomes larger as the charge transfer for the TM atom increases. Thus we see Y and Zr are better candidates for hydrogen storage devices since they are non-magnetic and have less d electrons which is ideal for kubas-type interactions between hydrogen molecule and TM.

A novel rapid synthesis of Fe{sub 2}O{sub 3}/graphene nanocomposite using ferrate(VI) and its application as a new kind of nanocomposite modified electrode as electrochemical sensor

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

Karimi, Mohammad Ali, E-mail: ma_karimi43@yahoo.com; Department of Chemistry & Nanoscience and Nanotechnology Research Laboratory; Banifatemeh, Fatemeh

2015-10-15

Highlights: • A novel rapid synthesis of rGO–Fe{sub 2}O{sub 3} nanocomposite was developed using Fe(VI). • Fe(VI) as an environmentally friendly oxidant was introduced for GO synthesis. • Synthesized rGO–Fe{sub 2}O{sub 3} nanocomposite was applied as electrochemical sensor. • A non-enzymatic sensor was developed for H{sub 2}O{sub 2}. - Abstract: In this study, a novel, simple and sensitive non-enzymatic hydrogen peroxide electrochemical sensor was developed using reduced graphene oxide/Fe{sub 2}O{sub 3} nanocomposite modified glassy carbon electrode. This nanocomposite was synthesized by reaction of sodium ferrate with graphene in alkaline media. This reaction completed in 5 min and the products weremore » stable and its deposition on the surface of electrode is investigated. It has been found the apparent charge transfer rate constant (ks) is 0.52 and transfer coefficient (α) is 0.61 for electron transfer between the modifier and glassy carbon electrode. Electrochemical behavior of this electrode and its ability to catalyze the electro-reduction of H{sub 2}O{sub 2} has been studied by cyclic voltammetry and chronoamperometry at different experimental conditions. The analytical parameters showed the good ability of electrode as a sensor for H{sub 2}O{sub 2} amperometric reduction.« less

Surface Redox Chemistry of Immobilized Nanodiamond: Effects of Particle Size and Electrochemical Environment

NASA Astrophysics Data System (ADS)

Gupta, S.; McDonald, B.; Carrizosa, S. B.

2017-07-01

The size of the diamond particle is tailored to nanoscale (nanodiamond, ND), and the ND surface is engineered targeting specific (electrochemical and biological) applications. In this work, we investigated the complex surface redox chemistry of immobilized ND layer on conductive boron-doped diamond electrode with a broad experimental parameter space such as particle size (nano versus micron), scan rate, pH (cationic/acidic versus anionic/basic), electrolyte KCl concentration (four orders of magnitude), and redox agents (neutral and ionic). We reported on the significant enhancement of ionic currents while recording reversible oxidation of neutral ferrocene methanol (FcMeOH) by almost one order of magnitude than traditional potassium ferricyanide (K3Fe(CN)6) redox agent. The current enhancement is inversely related to ND particle diameter in the following order: 1 μm << 1000 nm < 100 nm < 10 nm ≤ 5 nm < 2 nm. We attribute the current enhancement to concurrent electrocatalytic processes, i.e. the electron transfer between redox probes and electroactive surface functional (e.g. hydroxyl, carboxyl, epoxy) moieties and the electron transfer mediated by adsorbed FcMeOH+ (or Fe(CN) 6 3+ ) ions onto ND surface. The first process is pH dependent since it depends upon ND surface functionalities for which the electron transfer is coupled to proton transfer. The adsorption mediated process is observed most apparently at slower scan rates owing to self-exchange between adsorbed FcMeOH+ ions and FcMeOH redox agent molecules in diffusion-limited bulk electrolyte solution. Alternatively, it is hypothesized that the surface functionality and defect sites ( sp 2-bonded C shell and unsaturated bonds) give rise to surface electronic states with energies within the band gap (midgap states) in undoped ND. These surface states serve as electron donors (and acceptors) depending upon their bonding (and antibonding) character and, therefore, they can support electrocatalytic redox processes in the presence of specific redox-active molecules via feedback mechanism. Apparently, FcMeOH+ tended to have electrostatic affinity for negatively charged ND surface functionalities, corroborated by present experiments. We also attempted to study biocatalytic process using model metalloprotein (cytochrome c; Cyt c) immobilized on ND particles for investigating interfacial electron transfer kinetics and compared with those of functionalized graphene (graphene oxide; GO and reduced GO). The findings are discussed in terms of interplay of sp 3-bonded C (ND core) and sp 2-bonded C (ND shell and graphene-based systems).

Diffuse charge and Faradaic reactions in porous electrodes

NASA Astrophysics Data System (ADS)

Biesheuvel, P. M.; Fu, Yeqing; Bazant, Martin Z.

2011-06-01

Porous electrodes instead of flat electrodes are widely used in electrochemical systems to boost storage capacities for ions and electrons, to improve the transport of mass and charge, and to enhance reaction rates. Existing porous electrode theories make a number of simplifying assumptions: (i) The charge-transfer rate is assumed to depend only on the local electrostatic potential difference between the electrode matrix and the pore solution, without considering the structure of the double layer (DL) formed in between; (ii) the charge-transfer rate is generally equated with the salt-transfer rate not only at the nanoscale of the matrix-pore interface, but also at the macroscopic scale of transport through the electrode pores. In this paper, we extend porous electrode theory by including the generalized Frumkin-Butler-Volmer model of Faradaic reaction kinetics, which postulates charge transfer across the molecular Stern layer located in between the electron-conducting matrix phase and the plane of closest approach for the ions in the diffuse part of the DL. This is an elegant and purely local description of the charge-transfer rate, which self-consistently determines the surface charge and does not require consideration of reference electrodes or comparison with a global equilibrium. For the description of the DLs, we consider the two natural limits: (i) the classical Gouy-Chapman-Stern model for thin DLs compared to the macroscopic pore dimensions, e.g., for high-porosity metallic foams (macropores >50 nm) and (ii) a modified Donnan model for strongly overlapping DLs, e.g., for porous activated carbon particles (micropores <2 nm). Our theory is valid for electrolytes where both ions are mobile, and it accounts for voltage and concentration differences not only on the macroscopic scale of the full electrode, but also on the local scale of the DL. The model is simple enough to allow us to derive analytical approximations for the steady-state and early transients. We also present numerical solutions to validate the analysis and to illustrate the evolution of ion densities, pore potential, surface charge, and reaction rates in response to an applied voltage.

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.

Coherent Electron Transfer at the Ag / Graphite Heterojunction Interface

NASA Astrophysics Data System (ADS)

Tan, Shijing; Dai, Yanan; Zhang, Shengmin; Liu, Liming; Zhao, Jin; Petek, Hrvoje

2018-03-01

Charge transfer in transduction of light to electrical or chemical energy at heterojunctions of metals with semiconductors or semimetals is believed to occur by photogenerated hot electrons in metal undergoing incoherent internal photoemission through the heterojunction interface. Charge transfer, however, can also occur coherently by dipole coupling of electronic bands at the heterojunction interface. Microscopic physical insights into how transfer occurs can be elucidated by following the coherent polarization of the donor and acceptor states on the time scale of electronic dephasing. By time-resolved multiphoton photoemission spectroscopy (MPP), we investigate the coherent electron transfer from an interface state that forms upon chemisorption of Ag nanoclusters onto graphite to a σ symmetry interlayer band of graphite. Multidimensional MPP spectroscopy reveals a resonant two-photon transition, which dephases within 10 fs completing the coherent transfer.

Ultrafast Interlayer Electron Transfer in Incommensurate Transition Metal Dichalcogenide Homobilayers.

PubMed

Li, Yuanyuan; Cui, Qiannan; Ceballos, Frank; Lane, Samuel D; Qi, Zeming; Zhao, Hui

2017-11-08

Two-dimensional materials, such as graphene, transition metal dichalcogenides, and phosphorene, can be used to construct van der Waals multilayer structures. This approach has shown potentials to produce new materials that combine novel properties of the participating individual layers. One key requirement for effectively harnessing emergent properties of these materials is electronic connection of the involved atomic layers through efficient interlayer charge or energy transfer. Recently, ultrafast charge transfer on a time scale shorter than 100 fs has been observed in several van der Waals bilayer heterostructures formed by two different materials. However, information on the transfer between two atomic layers of the same type is rare. Because these homobilayers are essential elements in constructing multilayer structures with desired optoelectronic properties, efficient interlayer transfer is highly desired. Here we show that electron transfer between two monolayers of MoSe 2 occurs on a picosecond time scale. Even faster transfer was observed in homobilayers of WS 2 and WSe 2 . The samples were fabricated by manually stacking two exfoliated monolayer flakes. By adding a graphene layer as a fast carrier recombination channel for one of the two monolayers, the transfer of the photoexcited carriers from the populated to the drained monolayers was time-resolved by femtosecond transient absorption measurements. The observed efficient interlayer carrier transfer indicates that such homobilayers can be used in van der Waals multilayers to enhance their optical absorption without significantly compromising the interlayer transport performance. Our results also provide valuable information for understanding interlayer charge transfer in heterostructures.

Lightning Channel Corona Formation Treated as a Large System of Streamers

NASA Astrophysics Data System (ADS)

Carlson, B.; Lehtinen, N. G.; Kochkin, P.

2017-12-01

Transfer of charge along a lightning channel leads to strong electric fields that drive such charge outward. This charge flow is nonuniform, breaking up into millimeter-scale discharge structures called streamers. The motion of such streamers can carry charge many meters outward from the channel, but each individual streamer only carries a small amount of charge. Transfer of macroscopic charge outward thus requires a large population of streamers that are expected to interact and exhibit interesting collective behaviors. We attempt to simulate such collective behaviors by approximating the behavior of each streamer but retaining streamer interactions and overall electrodynamic effects and apply this simulation to a few key scenarios. For the case of flow of charge off a lightning channel, we simulate a continually growing population of streamers injected near a charged conducting channel. Further, motivated by lightning initiation, we simulate the growth of a population of streamers from a single seed streamer as might initiate from a hydrometeor. For all cases considered, we characterize the charges and currents involved, compare to observations where possible, and characterize the collective effects including spatial and temporal non-uniformity.

Charge Separation and Recombination at Polymer-Fullerene Heterojunctions: Delocalization and Hybridization Effects.

PubMed

D'Avino, Gabriele; Muccioli, Luca; Olivier, Yoann; Beljonne, David

2016-02-04

We address charge separation and recombination in polymer/fullerene solar cells with a multiscale modeling built from accurate atomistic inputs and accounting for disorder, interface electrostatics and genuine quantum effects on equal footings. Our results show that bound localized charge transfer states at the interface coexist with a large majority of thermally accessible delocalized space-separated states that can be also reached by direct photoexcitation, thanks to their strong hybridization with singlet polymer excitons. These findings reconcile the recent experimental reports of ultrafast exciton separation ("hot" process) with the evidence that high quantum yields do not require excess electronic or vibrational energy ("cold" process), and show that delocalization, by shifting the density of charge transfer states toward larger effective electron-hole radii, may reduce energy losses through charge recombination.

Dendronized fullerene-porphyrin conjugates in ortho, meta, and para positions: a charge-transfer assay.

PubMed

Krokos, Evangelos; Schubert, Christina; Spänig, Fabian; Ruppert, Michaela; Hirsch, Andreas; Guldi, Dirk M

2012-06-01

The physicochemical characterization, that is, ground and excited state, of a new series of dendronized porphyrin/fullerene electron donor-acceptor conjugates in nonaqueous and aqueous environments is reported. In contrast to previous work, we detail the charge-separation and charge-recombination dynamics in zinc and copper metalloporphyrins as a function of first- and second-generation dendrons as well as a function of ortho, meta, and para substitution. Both have an appreciable impact on the microenvironments of the redox-active constituents, namely the porphyrins and the fullerenes. As a matter of fact, the resulting charge-transfer dynamics were considerably impacted by the interplay between the associated forces that reach from dendron-induced shielding to dipole-charge interactions. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed Central

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

2016-01-01

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

Photochemical charge separation in zeolites: Electron transfer dynamics, nanocrystals and zeolitic membranes. Final technical report

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

Dutta, Prabir K.

2001-09-30

Aluminosilicate zeolites provide an excellent host for photochemical charge separation. Because of the constraints provided by the zeolite, the back electron transfer from the reduced acceptor to the oxidized sensitizer is slowed down. This provides the opportunity to separate the charge and use it in a subsequent reaction for water oxidation and reduction. Zeolite-based ruthenium oxide catalysts have been found to be efficient for the water splitting process. This project has demonstrated the usefulness of zeolite hosts for photolytic splitting of water.

Experimental evidence of charge transfer in a functionalized hexavanadate: a high resolution X-ray diffraction study.

PubMed

Xu, Xiao; Spasojević-de Biré, Anne; Ghermani, Nour Eddine; Wei, Yongge; Novaković, Sladjana; Bošnjaković-Pavlović, Nada; Wu, Pingfan

2017-07-19

A high resolution X-ray diffraction study has been carried out on [(C 4 H 9 ) 4 N] 2 [V 6 O 13 {(OCH 2 ) 3 CCH 2 OCCH 2 CH 3 } 2 ] (V6-C3) at 100 K. The V6 core possesses a negative charge, leading to a strong polarization of the anion. A nucleophilic region localized near the organic moiety and an electrophilic region in the vicinity of the V6 core provide an overall description of charge-transfer behavior.

Dynamics of Oxidation of Aluminum Nanoclusters using Variable Charge Molecular-Dynamics Simulations on Parallel Computers

NASA Astrophysics Data System (ADS)

Campbell, Timothy; Kalia, Rajiv K.; Nakano, Aiichiro; Vashishta, Priya; Ogata, Shuji; Rodgers, Stephen

1999-06-01

Oxidation of aluminum nanoclusters is investigated with a parallel molecular-dynamics approach based on dynamic charge transfer among atoms. Structural and dynamic correlations reveal that significant charge transfer gives rise to large negative pressure in the oxide which dominates the positive pressure due to steric forces. As a result, aluminum moves outward and oxygen moves towards the interior of the cluster with the aluminum diffusivity 60% higher than that of oxygen. A stable 40 Å thick amorphous oxide is formed; this is in excellent agreement with experiments.

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.

Molecular dynamics and charge transport in organic semiconductors: a classical approach to modeling electron transfer† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c6sc04547b Click here for additional data file.

PubMed Central

Vázquez-Mayagoitia, Álvaro; Ratcliff, Laura E.; Tretiak, Sergei; Bair, Raymond A.; Gray, Stephen K.; Van Voorhis, Troy; Larsen, Ross E.; Darling, Seth B.

2017-01-01

Organic photovoltaics (OPVs) are a promising carbon-neutral energy conversion technology, with recent improvements pushing power conversion efficiencies over 10%. A major factor limiting OPV performance is inefficiency of charge transport in organic semiconducting materials (OSCs). Due to strong coupling with lattice degrees of freedom, the charges form polarons, localized quasi-particles comprised of charges dressed with phonons. These polarons can be conceptualized as pseudo-atoms with a greater effective mass than a bare charge. We propose that due to this increased mass, polarons can be modeled with Langevin molecular dynamics (LMD), a classical approach with a computational cost much lower than most quantum mechanical methods. Here we present LMD simulations of charge transfer between a pair of fullerene molecules, which commonly serve as electron acceptors in OSCs. We find transfer rates consistent with experimental measurements of charge mobility, suggesting that this method may provide quantitative predictions of efficiency when used to simulate materials on the device scale. Our approach also offers information that is not captured in the overall transfer rate or mobility: in the simulation data, we observe exactly when and why intermolecular transfer events occur. In addition, we demonstrate that these simulations can shed light on the properties of polarons in OSCs. Much remains to be learned about these quasi-particles, and there are no widely accepted methods for calculating properties such as effective mass and friction. Our model offers a promising approach to exploring mass and friction as well as providing insight into the details of polaron transport in OSCs. PMID:28553494

High-Crystallinity Urchin-like VS4 Anode for High-Performance Lithium-Ion Storage.

PubMed

Yang, Guang; Zhang, Bowei; Feng, Jianyong; Wang, Huanhuan; Ma, Mingbo; Huang, Kang; Liu, Jilei; Madhavi, Srinivasan; Shen, Zexiang; Huang, Yizhong

2018-05-02

VS 4 anode materials with controllable morphologies from hierarchical microflower, octopus-like structure, seagrass-like structure to urchin-like structure have been successfully synthesized by a facile solvothermal synthesis approach using different alcohols as solvents. Their structures and electrochemical properties with various morphologies are systematically investigated, and the structure-property relationship is established. Experimental results reveal that Li + ion storage behavior in VS 4 significantly depends on physical features such as the morphology, crystallite size, and specific surface area. According to this study, electrochemical performance degrades on the order of urchin-like VS 4 > octopus-like VS 4 > seagrass-like VS 4 > flower-like VS 4 . Among them, urchin-like VS 4 demonstrates the best electrochemical performance benefiting from its peculiar structure which possesses large surface area that accommodates the volume change to a certain extent, and single-crystal thorns that provide fast electron transportation. Kinetic parameters derived from EIS spectra and sweep-rate-dependent CV curves, such as charge-transfer resistances, Li + ion apparent diffusion coefficients and stored charge ratio of capacitive and intercalation contributions, both support this claim well. In addition, the EIS measurement was conducted during the first discharge/charge process to study the solid electrolyte interface (SEI) formation on urchin-like VS 4 and kinetics behavior of Li + ion diffusion. A better fundamental understanding on Li + storage behavior in VS 4 is promoted, which is applicable to other vanadium-based materials as well. This study also provides invaluable guidance for morphology-controlled synthesis tailored for optimal electrochemical performance.

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

NASA Astrophysics Data System (ADS)

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

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

Possible charge analogues of spin transfer torques in bulk superconductors

NASA Astrophysics Data System (ADS)

Garate, Ion

2014-03-01

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

Apparent electric charge of protein molecules. Human thyroxine - binding proteins.

PubMed

Hocman, G; Sadlon, J

1977-01-01

1. By comparison of electrophoretic mobilities of two different charged particles under the same conditions the net elementary electrostatic charge of one particle could be calculated when the charge of the other is known. 2. The electrophoretic mobility of human thyroxine - binding globulin does not depend upon the concentration of Tris - HCl buffer in the range 0.05 to 0.20 molar. The value of this mobility is 0.078 and 0.083 cm2 vol(-1) hour(-1) at pH 7.0 and 8.6, respectively. 3. The net elementary electrostatic charge of the human thyroxine - binding globulin appears to be approximately 22 negative elementary electrostatic units in mild alkaline solutions.

Theoretical insights of proton transfer and hydrogen bonded charge transfer complex of 1,2-dimethylimidazolium-3,5-dinitrobenzoate crystal

NASA Astrophysics Data System (ADS)

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

2018-04-01

Proton transfer (PT) and hydrogen bonded charge transfer (HBCT) 1:1 complex of 1,2-dimethylimidazole (DMI) and 3,5-dinitrobenzoic acid (DNBA) have been theoretically analyzed and compared with reported experimental results. Both the structures in the isolated gaseous state have been optimized at DFT/B3LYP/6-311G(d,p) level of theory and further, the PT energy barrier has been calculated from potential energy surface scan. Along with structural investigations, theoretical vibrational spectra have been inspected and compared with the FTIR spectrum. Moreover, frontier molecular analysis has also been carried out.

Energetics and kinetics of primary charge separation in bacterial photosynthesis.

PubMed

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

2008-08-21

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

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

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

Dust motions in quasi-statically charged binary asteroid systems

NASA Astrophysics Data System (ADS)

Maruskin, Jared M.; Bellerose, Julie; Wong, Macken; Mitchell, Lara; Richardson, David; Mathews, Douglas; Nguyen, Tri; Ganeshalingam, Usha; Ma, Gina

2013-03-01

In this paper, we discuss dust motion and investigate possible mass transfer of charged particles in a binary asteroid system, in which the asteroids are electrically charged due to solar radiation. The surface potential of the asteroids is assumed to be a piecewise function, with positive potential on the sunlit half and negative potential on the shadow half. We derive the nonautonomous equations of motion for charged particles and an analytic representation for their lofting conditions. Particle trajectories and temporary relative equilibria are examined in relation to their moving forbidden regions, a concept we define and discuss. Finally, we use a Monte Carlo simulation for a case study on mass transfer and loss rates between the asteroids.

Interfacial Charge Transfer States in Condensed Phase Systems

NASA Astrophysics Data System (ADS)

Vandewal, Koen

2016-05-01

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

Quantum Effects in Cation Interactions with First and Second Coordination Shell Ligands in Metalloproteins

PubMed Central

2015-01-01

Despite decades of investigations, the principal mechanisms responsible for the high affinity and specificity of proteins for key physiological cations K+, Na+, and Ca2+ remain a hotly debated topic. At the core of the debate is an apparent need (or lack thereof) for an accurate description of the electrostatic response of the charge distribution in a protein to the binding of an ion. These effects range from partial electronic polarization of the directly ligating atoms to long-range effects related to partial charge transfer and electronic delocalization effects. While accurate modeling of cation recognition by metalloproteins warrants the use of quantum-mechanics (QM) calculations, the most popular approximations used in major biomolecular simulation packages rely on the implicit modeling of electronic polarization effects. That is, high-level QM computations for ion binding to proteins are desirable, but they are often unfeasible, because of the large size of the reactive-site models and the need to sample conformational space exhaustively at finite temperature. Several solutions to this challenge have been proposed in the field, ranging from the recently developed Drude polarizable force-field for simulations of metalloproteins to approximate tight-binding density functional theory (DFTB). To delineate the usefulness of different approximations, we examined the accuracy of three recent and commonly used theoretical models and numerical algorithms, namely, CHARMM C36, the latest developed Drude polarizable force fields, and DFTB3 with the latest 3OB parameters. We performed MD simulations for 30 cation-selective proteins with high-resolution X-ray structures to create ensembles of structures for analysis with different levels of theory, e.g., additive and polarizable force fields, DFTB3, and DFT. The results from DFT computations were used to benchmark CHARMM C36, Drude, and DFTB3 performance. The explicit modeling of quantum effects unveils the key electrostatic properties of the protein sites and the importance of specific ion-protein interactions. One of the most interesting findings is that secondary coordination shells of proteins are noticeably perturbed in a cation-dependent manner, showing significant delocalization and long-range effects of charge transfer and polarization upon binding Ca2+. PMID:26574284

Novel Polymers for High Efficiency Renewable and Portable Power Applications

DTIC Science & Technology

2015-07-30

photoelectric, thermoelectric , energy conversions, charge transfer, energy transfer, photoluminescence (PL). REPORT DOCUMENTATION PAGE 11. SPONSOR...of polymer/dye interface of photo generated excitons in the covalent system resulting in more efficient exciton dissociations. 4) For thermoelectric ...studies, it appears the thermoelectric charge carrier generations of the four conjugated polymers doped with iodine at room temperature are in the

SERS of semiconducting nanoparticles (TiO{sub 2} hybrid composites).

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

Musumeci, A.; Gosztola, D.; Schiller, T.

Raman scattering of molecules adsorbed on the surface of TiO{sub 2} nanoparticles was investigated. We find strong enhancement of Raman scattering in hybrid composites that exhibit charge transfer absorption with TiO{sub 2} nanoparticles. An enhancement factor up to {approx}10{sup 3} was observed in the solutions containing TiO{sub 2} nanoparticles and biomolecules, including the important class of neurotransmitters such as dopamine and dopac (3,4-dihydroxy-phenylacetic acid). Only selected vibrations are enhanced, indicating molecular specificity due to distinct binding and orientation of the biomolecules coupled to the TiO{sub 2} surface. All enhanced modes are associated with the asymmetric vibrations of attached molecules thatmore » lower the symmetry of the charge transfer complex. The intensity and the energy of selected vibrations are dependent on the size and shape of nanoparticle support. Moreover, we show that localization of the charge in quantized nanoparticles (2 nm), demonstrated as the blue shift of particle absorption, diminishes SERS enhancement. Importantly, the smallest concentration of adsorbed molecules shows the largest Raman enhancements suggesting the possibility for high sensitivity of this system in the detection of biomolecules that form a charge transfer complex with metal oxide nanoparticles. The wavelength-dependent properties of a hybrid composite suggest a Raman resonant state. Adsorbed molecules that do not show a charge transfer complex show weak enhancements probably due to the dielectric cavity effect.« less

SERS of semiconducting nanoparticles (TIO{sub 2} hybrid composites).

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

Rajh, T.; Musumeci, A.; Gosztola, D.

Raman scattering of molecules adsorbed on the surface of TiO{sub 2} nanoparticles was investigated. We find strong enhancement of Raman scattering in hybrid composites that exhibit charge transfer absorption with TiO{sub 2} nanoparticles. An enhancement factor up to {approx}10{sup 3} was observed in the solutions containing TiO{sub 2} nanoparticles and biomolecules, including the important class of neurotransmitters such as dopamine and dopac (3,4-dihydroxy-phenylacetic acid). Only selected vibrations are enhanced, indicating molecular specificity due to distinct binding and orientation of the biomolecules coupled to the TiO{sub 2} surface. All enhanced modes are associated with the asymmetric vibrations of attached molecules thatmore » lower the symmetry of the charge transfer complex. The intensity and the energy of selected vibrations are dependent on the size and shape of nanoparticle support. Moreover, we show that localization of the charge in quantized nanoparticles (2 nm), demonstrated as the blue shift of particle absorption, diminishes SERS enhancement. Importantly, the smallest concentration of adsorbed molecules shows the largest Raman enhancements suggesting the possibility for high sensitivity of this system in the detection of biomolecules that form a charge transfer complex with metal oxide nanoparticles. The wavelength-dependent properties of a hybrid composite suggest a Raman resonant state. Adsorbed molecules that do not show a charge transfer complex show weak enhancements probably due to the dielectric cavity effect.« less

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.

The simplest equivalent circuit of a pulsed dielectric barrier discharge and the determination of the gas gap charge transfer

NASA Astrophysics Data System (ADS)

Pipa, A. V.; Koskulics, J.; Brandenburg, R.; Hoder, T.

2012-11-01

The concept of the simplest equivalent circuit for a dielectric barrier discharge (DBD) is critically reviewed. It is shown that the approach is consistent with experimental data measured either in large-scale sinusoidal-voltage driven or miniature pulse-voltage driven DBDs. An expression for the charge transferred through the gas gap q(t) is obtained with an accurate account for the displacement current and the values of DBD reactor capacitance. This enables (i) the significant reduction of experimental error in the determination of q(t) in pulsed DBDs, (ii) the verification of the classical electrical theory of ozonizers about maximal transferred charge qmax, and (iii) the development of a graphical method for the determination of qmax from charge-voltage characteristics (Q-V plots, often referred as Lissajous figures) measured under pulsed excitation. The method of graphical presentation of qmax is demonstrated with an example of a Q-V plot measured under pulsed excitation. The relations between the discharge current jR(t), the transferred charge q(t), and the measurable parameters are presented in new forms, which enable the qualitative interpretation of the measured current and voltage waveforms without the knowledge about the value of the dielectric barrier capacitance Cd. Whereas for quantitative evaluation of electrical measurements, the accurate estimation of the Cd is important.

Energy and charge transfer in ionized argon coated water clusters.

PubMed

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

2013-12-07

We investigate the electron ionization of clusters generated in mixed Ar-water expansions. The electron energy dependent ion yields reveal the neutral cluster composition and structure: water clusters fully covered with the Ar solvation shell are formed under certain expansion conditions. The argon atoms shield the embedded (H2O)n clusters resulting in the ionization threshold above ≈15 eV for all fragments. The argon atoms also mediate more complex reactions in the clusters: e.g., the charge transfer between Ar(+) and water occurs above the threshold; at higher electron energies above ~28 eV, an excitonic transfer process between Ar(+)* and water opens leading to new products Ar(n)H(+) and (H2O)(n)H(+). On the other hand, the excitonic transfer from the neutral Ar* state at lower energies is not observed although this resonant process was demonstrated previously in a photoionization experiment. Doubly charged fragments (H2O)(n)H2(2+) and (H2O)(n)(2+) ions are observed and Intermolecular Coulomb decay (ICD) processes are invoked to explain their thresholds. The Coulomb explosion of the doubly charged cluster formed within the ICD process is prevented by the stabilization effect of the argon solvent.

Seebeck Effects in N-Type and P-Type Polymers Driven Simultaneously by Surface Polarization and Entropy Differences Based on Conductor/Polymer/Conductor Thin-Film Devices

DOE PAGES

Hu, Dehua; Liu, Qing; Tisdale, Jeremy; ...

2015-04-15

This paper reports Seebeck effects driven by both surface polarization difference and entropy difference by using intramolecular charge-transfer states in n-type and p-type conjugated polymers, namely IIDT and IIDDT, based on vertical conductor/polymer/conductor thin-film devices. Large Seebeck coefficients of -898 V/K and 1300 V/K from are observed from n-type IIDT p-type IIDDT, respectively, when the charge-transfer states are generated by a white light illumination of 100 mW/cm2. Simultaneously, electrical conductivities are increased from almost insulating states in dark condition to conducting states under photoexcitation in both n-type IIDT and p-type IIDDT devices. We find that the intramolecular charge-transfer states canmore » largely enhance Seebeck effects in the n-type IIDT and p-type IIDDT devices driven by both surface polarization difference and entropy difference. Furthermore, the Seebeck effects can be shifted between polarization and entropy regimes when electrical conductivities are changed. This reveals a new concept to develop Seebeck effects by controlling polarization and entropy regimes based on charge-transfer states in vertical conductor/polymer/conductor thin-film devices.« less

Electronic structures of 1-ML C84/Ag(111): Energy level alignment and work function variation

NASA Astrophysics Data System (ADS)

Wang, Peng; Zhao, Li-Li; Zhang, Jin-Juan; Li, Wen-Jie; Liu, Wei-Hui; Chen, Da; Sheng, Chun-Qi; Wang, Jia-Ou; Qian, Hai-Jie; Ibrahim, Kurash; Li, Hong-Nian

2017-12-01

The electronic structures of fullerene/metal interface are critical to the performance of devices based on fullerene in molecular electronics and organic electronics. Herein, we investigate the electronic structures at the interface between C84 and Ag(111) by photoelectron spectroscopy and soft X-ray absorption spectroscopy techniques. It is observed that C84 monolayer on Ag(111) surface (1-ML C84/Ag(111)) has metallic nature. A charge transfer from substrate to the unoccupied states of C84 is determined to be 1.3 electrons per molecule. However, the work function of 1-ML C84 (4.72 eV) is observed slightly larger than that of the clean Ag(111) substrate (4.50 eV). A bidirectional charge transfer model is introduced to understand the work function variation of the fullerene/metal system. In addition to the charge transfer from substrate to the adsorbate's unoccupied states, there exists non-negligible back charge transfer from fullerene occupied molecular orbital to the metal substrate through interfacial hybridization. The Fermi level will be pinned at ∼4.72 eV for C84 monolayer on coinage metal substrate.

Preparation, spectroscopic and antibacterial studies on charge-transfer complexes of 2-hydroxypyridine with picric acid and 7,7‧,8,8‧-tetracyano-p-quinodimethane

NASA Astrophysics Data System (ADS)

Gaballa, Akmal S.; Amin, Alaa S.

2015-06-01

The reactions of electron acceptors such as picric acid (HPA) and 7,7‧,8,8‧-tetracyano-p-quinodimethane (TCNQ) with 2-hydroxypyridine (HPyO) have been investigated in EtOH at room temperature. Based on elemental analysis and IR spectra of the solid CT-complexes along with the photometric titration curves for the reactions, the data obtained indicate the formation of 1:1 charge transfer complexes [(H2PyO)(PA)] and [(PyO)(HTCNQ)], respectively. The infrared and 1H NMR spectroscopic data indicate a charge transfer interaction associated with a proton migration from the acceptor to the donor followed by intramolecular hydrogen bonding in [(H2PyO)(PA)] complex. Another charge transfer interaction was observed in [(PyO)(HTCNQ)] complex. The formation constants (KCT) for the CT-complexes are shown to be strongly dependent on the type and structure of the electron acceptors. Factors affecting the CT-processes and the kinetics of thermal decomposition of the complexes have been studied. The CT complexes were screened for their antibacterial activities against selected bacterial strains.

Preparation, spectroscopic and antibacterial studies on charge-transfer complexes of 2-hydroxypyridine with picric acid and 7,7',8,8'-tetracyano-p-quinodimethane.

PubMed

Gaballa, Akmal S; Amin, Alaa S

2015-06-15

The reactions of electron acceptors such as picric acid (HPA) and 7,7',8,8'-tetracyano-p-quinodimethane (TCNQ) with 2-hydroxypyridine (HPyO) have been investigated in EtOH at room temperature. Based on elemental analysis and IR spectra of the solid CT-complexes along with the photometric titration curves for the reactions, the data obtained indicate the formation of 1:1 charge transfer complexes [(H2PyO)(PA)] and [(PyO)(HTCNQ)], respectively. The infrared and (1)H NMR spectroscopic data indicate a charge transfer interaction associated with a proton migration from the acceptor to the donor followed by intramolecular hydrogen bonding in [(H2PyO)(PA)] complex. Another charge transfer interaction was observed in [(PyO)(HTCNQ)] complex. The formation constants (KCT) for the CT-complexes are shown to be strongly dependent on the type and structure of the electron acceptors. Factors affecting the CT-processes and the kinetics of thermal decomposition of the complexes have been studied. The CT complexes were screened for their antibacterial activities against selected bacterial strains. Copyright © 2015 Elsevier B.V. All rights reserved.

Synthesis, spectroscopic, thermal and electrical conductivity studies of three charge transfer complexes formed between 1,3-di[( E)-1-(2-hydroxyphenyl)methylideneamino]-2-propanol Schiff base and different acceptors

NASA Astrophysics Data System (ADS)

Refat, Moamen S.; Ibrahim, Mohamed M.; Moussa, Mohamed A. A.

2012-01-01

Charge-transfer complexes (CTC) resulting from interactions of 1,3-di[( E)-1-(2-hydroxyphenyl) methylideneamino]-2-propanol Schiff base with some acceptors such as iodine (I2), bromine (Br2), and picric acid (PiA) have been isolated in the solid state in a chloroform solvent at room temperature. Based on elemental analysis, UV-Vis, infrared, and 1H NMR spectra, and thermogravimetric analysis (TG/DTG) of the solid CTC, [(Schiff)(I2)] (1), [(Schiff)(Br2)] complexes with a ratio of 1:1 and [(Schiff)(PiA)3] complexes with 1:3 have been prepared. In the picric acid complex, infrared and 1H NMR spectroscopic data indicate that the charge-transfer interaction is associated with a hydrogen bonding, whereas the iodine and bromine complexes were interpreted in terms of the formation of dative ion pairs [Schiff+, I{2/•-}] and [Schiff+, Br{2/•-}], respectively. Kinetic parameters were obtained for each stage of thermal degradation of the CT complexes using Coats-Redfern and Horowitz-Metzger methods. DC electrical properties as a function of temperature of these charge transfer complexes have been studied.

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

NASA Astrophysics Data System (ADS)

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

2018-06-01

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

Influence of external mass transfer limitation on apparent kinetic parameters of penicillin G acylase immobilized on nonporous ultrafine silica particles.

PubMed

Kheirolomoom, Azadeh; Khorasheh, Farhad; Fazelinia, Hossein

2002-01-01

Immobilization of enzymes on nonporous supports provides a suitable model for investigating the effect of external mass transfer limitation on the reaction rate in the absence of internal diffusional resistance. In this study, deacylation of penicillin G was investigated using penicillin acylase immobilized on ultrafine silica particles. Kinetic studies were performed within the low-substrate-concentration region, where the external mass transfer limitation becomes significant. To predict the apparent kinetic parameters and the overall effectiveness factor, knowledge of the external mass transfer coefficient, k(L)a, is necessary. Although various correlations exist for estimation of k(L)a, in this study, an optimization scheme was utilized to obtain this coefficient. Using the optimum values of k(L)a, the initial reaction rates were predicted and found to be in good agreement with the experimental data.

33 CFR 127.319 - LNG transfer.

Code of Federal Regulations, 2010 CFR

2010-07-01

... that— (1) The marine transfer area for LNG is under the supervision of a person in charge, who has no other assigned duties during the transfer operation; (2) Personnel transferring fuel or oily waste are... discontinued— (i) Before electrical storms or uncontrolled fires are adjacent to the marine transfer area for...

33 CFR 127.319 - LNG transfer.

Code of Federal Regulations, 2011 CFR

2011-07-01

... that— (1) The marine transfer area for LNG is under the supervision of a person in charge, who has no other assigned duties during the transfer operation; (2) Personnel transferring fuel or oily waste are... discontinued— (i) Before electrical storms or uncontrolled fires are adjacent to the marine transfer area for...

Collaborative Research: Polymeric Multiferroics

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

Ren, Shenqiang

2017-04-20

The goal of this project is to investigate room temperature magnetism and magnetoelectric coupling of polymeric multiferroics. A new family of molecular charge-transfer crystals has been emerged as a fascinating opportunity for the development of all-organic electrics and spintronics due to its weak hyperfine interaction and low spin-orbit coupling; nevertheless, direct observations of room temperature magnetic spin ordering have yet to be accomplished in organic charge-transfer solids. Furthermore, room temperature magnetoelectric coupling effect hitherto known multiferroics, is anticipated in organic donor-acceptor complexes because of magnetic field effects on charge-transfer dipoles, yet this is also unexplored. The PI seeks to fundamentalmore » understanding of the control of organic crystals to demonstrate and explore room temperature multiferroicity. The experimental results have been verified through the theoretical modeling.« less

Bands dispersion and charge transfer in β-BeH2

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

Ab Initio Analysis of Auger-Assisted Electron Transfer.

PubMed

Hyeon-Deuk, Kim; Kim, Joonghan; Prezhdo, Oleg V

2015-01-15

Quantum confinement in nanoscale materials allows Auger-type electron-hole energy exchange. We show by direct time-domain atomistic simulation and analytic theory that Auger processes give rise to a new mechanism of charge transfer (CT) on the nanoscale. Auger-assisted CT eliminates the renown Marcus inverted regime, rationalizing recent experiments on CT from quantum dots to molecular adsorbates. The ab initio simulation reveals a complex interplay of the electron-hole and charge-phonon channels of energy exchange, demonstrating a variety of CT scenarios. The developed Marcus rate theory for Auger-assisted CT describes, without adjustable parameters, the experimental plateau of the CT rate in the region of large donor-acceptor energy gap. The analytic theory and atomistic insights apply broadly to charge and energy transfer in nanoscale systems.

Theoretical study of the rhenium–alkane interaction in transition metal–alkane σ-complexes

PubMed Central

Cobar, Erika A.; Khaliullin, Rustam Z.; Bergman, Robert G.; Head-Gordon, Martin

2007-01-01

Metal–alkane binding energies have been calculated for [CpRe(CO)2](alkane) and [(CO)2M(C5H4)CC(C5H4)M(CO)2](alkane), where M = Re or Mn. Calculated binding energies were found to increase with the number of metal–alkane interaction sites. In all cases examined, the manganese–alkane binding energies were predicted to be significantly lower than those for the analogous rhenium–alkane complexes. The metal (Mn or Re)–alkane interaction was predicted to be primarily one of charge transfer, both from the alkane to the metal complex (70–80% of total charge transfer) and from the metal complex to the alkane (20–30% of the total charge transfer). PMID:17442751

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.

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.

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

PubMed

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

2017-10-11

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

Transition rate diagrams and excitation of titanium in a glow discharge in argon and neon

NASA Astrophysics Data System (ADS)

Weiss, Zdeněk; Steers, Edward B. M.; Pickering, Juliet C.

2018-06-01

Emission spectra of titanium in a Grimm-type glow discharge in argon and neon were studied using the formalism of transition rate diagrams. Ti I spectra in argon and neon discharges are similar, without signs of selective excitation, and populations of Ti I levels exhibit a decreasing trend as function of energy, except for some scatter. A major excitation process of Ti II in argon discharge is charge transfer from argon ions to neutral titanium. In neon discharge, a strong selective excitation was observed of Ti II levels at ≈13.3-13.4 eV relative to the Ti I ground state. It was attributed to charge transfer from doubly charged titanium ions to neutral titanium, while the Ti++ ions are produced by charge transfer and ionization of neutral titanium by neon ions. Cascade excitation is important for Ti II levels up to an energy of ≈13 eV relative to the Ti I ground state, both in argon and neon discharges.

Energy and charge transfer dynamics between Alq3 and CdSeS nanocrystals.

PubMed

Zhang, Shuping; Liu, Yuqiang; Yang, Yanqiang

2010-03-01

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

Kinetic and Spectral Properties of Isovaleryl-CoA Dehydrogenase and Interaction with Ligands

PubMed Central

Mohsen, Al-Walid A.; Vockley, Jerry

2014-01-01

Isovaleryl-CoA dehydrogenase (IVD) catalyzes the conversion of isovaleryl-CoA to 3-methylcrotonyl-CoA and the transfer of electrons to the electron transfer flavoprotein (ETF). Recombinant human IVD purifies with bound CoA-persulfide. A modified purification protocol was developed to isolate IVD without bound CoA-persulfide and to protect the protein thiols from oxidation. The CoA-persulfide-free IVD specific activity was 112.5 µmol porcine ETF•min−1•mg−1, which was ~20-fold higher than that of its CoA-persulfide bound form. The Km and catalytic efficiency (kcat/Km) for isovaleryl-CoA were 1.0 µM and 4.3 × 106•M−1•sec−1 per monomer, respectively, and its Km for ETF was 2.0 µM. Anaerobic titration of isovaleryl-CoA into an IVD solution resulted in a stable blue complex with increased absorbance at 310 nm, decreased absorbance at 373 and 447 nm, and the appearance of the charge transfer complex band at 584 nm. The apparent dissociation constant (KD app) determined spectrally for isovaleryl-CoA was 0.54 µM. Isovaleryl-CoA, acetoacetyl-CoA, methylenecyclopropylacetyl-CoA, and ETF induced CD spectral changes at the 250–500 nm region while isobutyryl-CoA did not, suggesting conformational changes occur at the flavin ring that are ligand specific. Replacement of the IVD Trp166 with a Phe did not block IVD interaction with ETF, indicating that its indole ring is not essential for electron transfer to ETF. A twelve amino acid synthetic peptide that matches the sequence of the ETF docking peptide competitively inhibited the enzyme reaction when ETF was used as the electron acceptor with a Ki of 1.5 mM. PMID:25450250

Counterion adsorption theory of dilute polyelectrolyte solutions: Apparent molecular weight, second virial coefficient, and intermolecular structure factor

PubMed Central

Muthukumar, M.

2012-01-01

Polyelectrolyte chains are well known to be strongly correlated even in extremely dilute solutions in the absence of additional strong electrolytes. Such correlations result in severe difficulties in interpreting light scattering measurements in the determination of the molecular weight, radius of gyration, and the second virial coefficient of charged macromolecules at lower ionic strengths from added strong electrolytes. By accounting for charge-regularization of the polyelectrolyte by the counterions, we present a theory of the apparent molecular weight, second virial coefficient, and the intermolecular structure factor in dilute polyelectrolyte solutions in terms of concentrations of the polymer and the added strong electrolyte. The counterion adsorption of the polyelectrolyte chains to differing levels at different concentrations of the strong electrolyte can lead to even an order of magnitude discrepancy in the molecular weight inferred from light scattering measurements. Based on counterion-mediated charge regularization, the second virial coefficient of the polyelectrolyte and the interchain structure factor are derived self-consistently. The effect of the interchain correlations, dominating at lower salt concentrations, on the inference of the radius of gyration and on molecular weight is derived. Conditions for the onset of nonmonotonic scattering wave vector dependence of scattered intensity upon lowering the electrolyte concentration and interpretation of the apparent radius of gyration are derived in terms of the counterion adsorption mechanism. PMID:22830728

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

NASA Astrophysics Data System (ADS)

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

2010-12-01

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

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

NASA Astrophysics Data System (ADS)

Bibes, Manuel

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

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

Kar, Durga P.; Nayak, Praveen P.; Bhuyan, Satyanarayan

In order to power or charge electronic devices wirelessly, a bi-directional wireless power transfer method has been proposed and experimentally investigated. In the proposed design, two receiving coils are used on both sides of a transmitting coil along its central axis to receive the power wirelessly from the generated magnetic fields through strongly coupled magnetic resonance. It has been observed experimentally that the maximum power transfer occurs at the operating resonant frequency for optimum electric load connected across the receiving coils on both side. The optimum wireless power transfer efficiency is 88% for the bi-directional power transfer technique compared 84%more » in the one side receiver system. By adopting the developed bi-directional power transfer method, two electronic devices can be powered up or charged simultaneously instead of a single device through usual one side receiver system without affecting the optimum power transfer efficiency.« less

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

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

Cohen, S.G.

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

Study of interactions between metal ions and protein model compounds by energy decomposition analyses and the AMOEBA force field

NASA Astrophysics Data System (ADS)

Jing, Zhifeng; Qi, Rui; Liu, Chengwen; Ren, Pengyu

2017-10-01

The interactions between metal ions and proteins are ubiquitous in biology. The selective binding of metal ions has a variety of regulatory functions. Therefore, there is a need to understand the mechanism of protein-ion binding. The interactions involving metal ions are complicated in nature, where short-range charge-penetration, charge transfer, polarization, and many-body effects all contribute significantly, and a quantitative description of all these interactions is lacking. In addition, it is unclear how well current polarizable force fields can capture these energy terms and whether these polarization models are good enough to describe the many-body effects. In this work, two energy decomposition methods, absolutely localized molecular orbitals and symmetry-adapted perturbation theory, were utilized to study the interactions between Mg2+/Ca2+ and model compounds for amino acids. Comparison of individual interaction components revealed that while there are significant charge-penetration and charge-transfer effects in Ca complexes, these effects can be captured by the van der Waals (vdW) term in the AMOEBA force field. The electrostatic interaction in Mg complexes is well described by AMOEBA since the charge penetration is small, but the distance-dependent polarization energy is problematic. Many-body effects were shown to be important for protein-ion binding. In the absence of many-body effects, highly charged binding pockets will be over-stabilized, and the pockets will always favor Mg and thus lose selectivity. Therefore, many-body effects must be incorporated in the force field in order to predict the structure and energetics of metalloproteins. Also, the many-body effects of charge transfer in Ca complexes were found to be non-negligible. The absorption of charge-transfer energy into the additive vdW term was a main source of error for the AMOEBA many-body interaction energies.

12 CFR 1228.1 - Definitions.

Code of Federal Regulations, 2013 CFR

2013-01-01

... continuing basis each time a property is transferred (except for transfers specifically excepted) for a period of time or indefinitely. A private transfer fee does not include fees, charges, payments, or other... SECURITY INTERESTS IN, MORTGAGES ON PROPERTIES ENCUMBERED BY CERTAIN PRIVATE TRANSFER FEE COVENANTS AND...

Direct Measurement of Charge Regulation in Metalloprotein Electron Transfer.

PubMed

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

2018-05-04

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

Electron Transfer Dissociation with Supplemental Activation to Differentiate Aspartic and Isoaspartic Residues in Doubly Charged Peptide Cations

PubMed Central

Chan, Wai Yi Kelly; Chan, T. W. Dominic; O’Connor, Peter B.

2011-01-01

Electron-transfer dissociation (ETD) with supplemental activation of the doubly charged deamidated tryptic digested peptide ions allows differentiation of isoaspartic acid and aspartic acid residues using c + 57 or z• − 57 peaks. The diagnostic peak clearly localizes and characterizes the isoaspartic acid residue. Supplemental activation in ETD of the doubly charged peptide ions involves resonant excitation of the charge reduced precursor radical cations and leads to further dissociation, including extra backbone cleavages and secondary fragmentation. Supplemental activation is essential to obtain a high quality ETD spectrum (especially for doubly charged peptide ions) with sequence information. Unfortunately, the low-resolution of the ion trap mass spectrometer makes detection of the diagnostic peak for the aspartic acid residue difficult due to interference with side-chain loss from arginine and glutamic acid residues. PMID:20304674