WorldWideScience

Sample records for hopfield charge-transfer band

  1. Band Alignment and Charge Transfer in Complex Oxide Interfaces

    Directory of Open Access Journals (Sweden)

    Zhicheng Zhong

    2017-03-01

    Full Text Available The synthesis of transition metal heterostructures is currently one of the most vivid fields in the design of novel functional materials. In this paper, we propose a simple scheme to predict band alignment and charge transfer in complex oxide interfaces. For semiconductor heterostructures, band-alignment rules like the well-known Anderson or Schottky-Mott rule are based on comparison of the work function or electron affinity of the bulk components. This scheme breaks down for oxides because of the invalidity of a single work-function approximation as recently shown in [Phys. Rev. B 93, 235116 (2016PRBMDO2469-995010.1103/PhysRevB.93.235116; Adv. Funct. Mater. 26, 5471 (2016AFMDC61616-301X10.1002/adfm.201600243]. Here, we propose a new scheme that is built on a continuity condition of valence states originating in the compounds’ shared network of oxygen. It allows for the prediction of sign and relative amplitude of the intrinsic charge transfer, taking as input only information about the bulk properties of the components. We support our claims by numerical density functional theory simulations as well as (where available experimental evidence. Specific applications include (i controlled doping of SrTiO_{3} layers with the use of 4d and 5d transition metal oxides and (ii the control of magnetic ordering in manganites through tuned charge transfer.

  2. Electron transfer mechanism and photochemistry of ferrioxalate induced by excitation in the charge transfer band.

    Science.gov (United States)

    Chen, Jie; Zhang, Hua; Tomov, Ivan V; Rentzepis, Peter M

    2008-03-17

    The photoredox reaction of ferrioxalate after 266/267 nm excitation in the charge transfer band has been studied by means of ultrafast extended X-ray absorption fine structure (EXAFS) analysis, optical transient spectroscopy, and quantum chemistry calculations. The Fe-O bond length changes combined with the transient spectra and kinetics have been measured and in combination with ultrahigh frequency density functional theory (UHF/DFT) calculations are used to determine the photochemical mechanism for the Fe(III) to Fe(II) redox reaction. The present data and the results obtained with 266/267 nm excitations strongly suggest that the primary reaction is the dissociation of the Fe-O bond before intramolecular electron transfer occurs. Low quantum yield electron photodetachment from ferrioxalate has also been observed.

  3. Photochemistry and electron-transfer mechanism of transition metal oxalato complexes excited in the charge transfer band.

    Science.gov (United States)

    Chen, Jie; Zhang, Hua; Tomov, Ivan V; Ding, Xunliang; Rentzepis, Peter M

    2008-10-07

    The photoredox reaction of trisoxalato cobaltate (III) has been studied by means of ultrafast extended x-ray absorption fine structure and optical transient spectroscopy after excitation in the charge-transfer band with 267-nm femtosecond pulses. The Co-O transient bond length changes and the optical spectra and kinetics have been measured and compared with those of ferrioxalate. Data presented here strongly suggest that both of these metal oxalato complexes operate under similar photoredox reaction mechanisms where the primary reaction involves the dissociation of a metal-oxygen bond. These results also indicate that excitation in the charge-transfer band is not a sufficient condition for the intramolecular electron transfer to be the dominant photochemistry reaction mechanism.

  4. Synthesis and energy band characterization of hybrid molecular materials based on organic–polyoxometalate charge-transfer salts

    Energy Technology Data Exchange (ETDEWEB)

    Tan, Chunxia [Key Laboratory of Nonferrous Metals Chemistry and Resources Utilization of Gansu Province and College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou City, Gansu Province (China); Traditional Chinese Medicine College of Gansu, Gansu (China); Bu, Weifeng, E-mail: buwf@lzu.edu.cn [Key Laboratory of Nonferrous Metals Chemistry and Resources Utilization of Gansu Province and College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou City, Gansu Province (China)

    2014-11-15

    A cationic amphiphilic molecule was synthesized and employed to encapsulate Lindqvist ([M{sub 6}O{sub 19}]{sup 2−}) and Keggin polyoxometalates ([SiM{sub 12}O{sub 40}]{sup 4−}, M=Mo, W) to form hybrid molecules through electrostatic interaction. The X-ray diffraction results illustrate that the former hybrids possess lamellar nanostructures in their solid states, while the latter hybrids show a cubic Im3m packing model with low intensities and poor long-range order. These hybrids have clear charge-transfer characters as shown in their deeper colors and UV–vis diffuse reflectance spectra. According to the reported reduction potentials of the POM acceptors and the band gaps deduced from their diffuse reflectance spectra, we have calculated the theoretical values of the lowest unoccupied molecular orbital (LUMO) position similar to the electron affinity (E{sub A}) of solid materials. Such energy level parameters are comparable to those of electroluminescence and electron-transport materials commonly used in organic electroluminescence devices. These organic–polyoxometalate charge-transfer salts have more advantages, such as higher decomposition temperatures, easier film fabrication and better electron affinities, which presumably would be used for electron-transport materials in the area of the electroluminescence. - Graphical abstract: Hybrid molecular materials with charge-transfer characters formed by a positively charged donor L and acceptors of the Lindqvist-type and Keggin-type POMs have lamellar and cubic structures in their solid state. - Highlights: • Charge-transfer salts are obtained by self-assembling POMs with an anthracene cation. • Their energy parameters are comparable to those of optoelectronic materials in OLEDs. • These POM-based hybrids could be applied in the area of optoelectronic devices.

  5. Fano-Hopfield model and photonic band gaps for an arbitrary atomic lattice

    OpenAIRE

    Antezza, Mauro; Castin, Yvan

    2009-01-01

    15 pages; 6 figures; International audience; We study the light dispersion relation in a periodic ensemble of atoms at fixed positions in the Fano-Hopfield model (the atomic dipole being modeled with harmonic oscillators). Compared to earlier works, we do not restrict to cubic lattices, and we do not regularize the theory by hand but we renormalize it in a systematic way using a Gaussian cut-off in momentum space. Whereas no omnidirectional spectral gap is known for light in a Bravais atomic ...

  6. Investigation of electronic band structure and charge transfer mechanism of oxidized three-dimensional graphene as metal-free anodes material for dye sensitized solar cell application

    Science.gov (United States)

    Loeblein, Manuela; Bruno, Annalisa; Loh, G. C.; Bolker, Asaf; Saguy, Cecile; Antila, Liisa; Tsang, Siu Hon; Teo, Edwin Hang Tong

    2017-10-01

    Dye-sensitized solar cells (DSSCs) offer an optimal trade-off between conversion-efficiency and low-cost fabrication. However, since all its electrodes need to fulfill stringent work-function requirements, its materials have remained unchanged since DSSC's first report early-90s. Here we describe a new material, oxidized-three-dimensional-graphene (o-3D-C), with a band gap of 0.2 eV and suitable electronic band-structure as alternative metal-free material for DSSCs-anodes. o-3D-C/dye-complex has a strong chemical bonding via carboxylic-group chemisorption with full saturation after 12 sec at capacity of ∼450 mg/g (600x faster and 7x higher than optimized metal surfaces). Furthermore, fluorescence quenching of life-time by 28-35% was measured demonstrating charge-transfer from dye to o-3D-C.

  7. Coupling of narrow and wide band-gap semiconductors on uniform films active in bacterial disinfection under low intensity visible light: Implications of the interfacial charge transfer (IFCT)

    Energy Technology Data Exchange (ETDEWEB)

    Rtimi, S., E-mail: sami.rtimi@epfl.ch [Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-GPAO, Station 6, CH-1015 Lausanne (Switzerland); UR Catalyse/Matériaux pour l‘Environnement et les Procédés (URCMEP), Faculté des Sciences de Gabès, Université de Gabès, 6072 Gabès (Tunisia); Sanjines, R. [Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-IPMC-LNNME, Bat PH, Station 3, CH1015 Lausanne (Switzerland); Pulgarin, C., E-mail: cesar.pulgarin@epfl.ch [Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-GPAO, Station 6, CH-1015 Lausanne (Switzerland); Houas, A. [UR Catalyse/Matériaux pour l‘Environnement et les Procédés (URCMEP), Faculté des Sciences de Gabès, Université de Gabès, 6072 Gabès (Tunisia); Lavanchy, J.-C. [Université de Lausanne, IMG, Centre d’Analyse Minérale, Bat Anthropole, CH-1015 Lausanne (Switzerland); Kiwi, J. [Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LPI, Bat Chimie, Station 6, CH1015 Lausanne (Switzerland)

    2013-09-15

    Highlights: • Design, preparation, testing and characterization of uniform sputtered films. • Interfacial charge transfer from the Ag{sub 2}O (cb) to the lower laying Ta{sub 2}O{sub 5} (cb). • The optical absorption of TaON and TaON/Ag was proportional to E. coli inactivation. • Self-cleaning of the TaON/Ag polyester enables repetitive E. coli inactivation. -- Abstract: This study reports the design, preparation, testing and surface characterization of uniform films deposited by sputtering Ag and Ta on non-heat resistant polyester to evaluate the Escherichia coli inactivation by TaON, TaN/Ag, Ag and TaON/Ag polyester. Co-sputtering for 120 s Ta and Ag in the presence of N{sub 2} and O{sub 2} led to the faster E. coli inactivation by a TaON/Ag sample within ∼40 min under visible light irradiation. The deconvolution of TaON/Ag peaks obtained by X-ray photoelectron spectroscopy (XPS) allowed the assignment of the Ta{sub 2}O{sub 5} and Ag-species. The shifts observed for the XPS peaks have been assigned to AgO to Ag{sub 2}O and Ag{sup 0}, and are a function of the applied sputtering times. The mechanism of interfacial charge transfer (IFCT) from the Ag{sub 2}O conduction band (cb) to the lower laying Ta{sub 2}O{sub 5} (cb) is discussed suggesting a reaction mechanism. The optical absorption of the TaON and TaON/Ag samples found by diffuse reflectance spectroscopy (DRS) correlated well with the kinetics of E. coli inactivation. The TaON/Ag sample microstructure was characterized by contact angle (CA) and by atomic force microscopy (AFM). Self-cleaning of the TaON/Ag polyester after each disinfection cycle enabled repetitive E. coli inactivation.

  8. Open-Circuit Voltage in Organic Solar Cells: The Impacts of Donor Semicrystallinity and Coexistence of Multiple Interfacial Charge-Transfer Bands

    KAUST Repository

    Ngongang Ndjawa, Guy Olivier

    2017-01-16

    In organic solar cells (OSCs), the energy of the charge-transfer (CT) complexes at the donor-acceptor interface, E , determines the maximum open-circuit voltage (V ). The coexistence of phases with different degrees of order in the donor or the acceptor, as in blends of semi-crystalline donors and fullerenes in bulk heterojunction layers, influences the distribution of CT states and the V enormously. Yet, the question of how structural heterogeneities alter CT states and the V is seldom addressed systematically. In this work, we combine experimental measurements of vacuum-deposited rubrene/C bilayer OSCs, with varying microstructure and texture, with density functional theory calculations to determine how relative molecular orientations and extents of structural order influence E and V . We find that varying the microstructure of rubrene gives rise to CT bands with varying energies. The CT band that originates from crystalline rubrene lies up to ≈0.4 eV lower in energy compared to the one that arises from amorphous rubrene. These low-lying CT states contribute strongly to V losses and result mainly from hole delocalization in aggregated rubrene. This work points to the importance of realizing interfacial structural control that prevents the formation of low E configurations and maximizes V .

  9. UV-Vis spectroscopy and density functional study of solvent effect on the charge transfer band of the n → σ* complexes of 2-Methylpyridine and 2-Chloropyridine with molecular iodine

    Science.gov (United States)

    Gogoi, Pallavi; Mohan, Uttam; Borpuzari, Manash Protim; Boruah, Abhijit; Baruah, Surjya Kumar

    2017-03-01

    UV-Vis spectroscopy has established that Pyridine substitutes form n→σ* charge transfer (CT) complexes with molecular Iodine. This study is a combined approach of purely experimental UV-Vis spectroscopy, Multiple linear regression theory and Computational chemistry to analyze the effect of solvent upon the charge transfer band of 2-Methylpyridine-I2 and 2-Chloropyridine-I2 complexes. Regression analysis verifies the dependence of the CT band upon different solvent parameters. Dielectric constant and refractive index are considered among the bulk solvent parameters and Hansen, Kamlet and Catalan parameters are taken into consideration at the molecular level. Density Functional Theory results explain well the blue shift of the CT bands in polar medium as an outcome of stronger donor acceptor interaction. A logarithmic relation between the bond length of the bridging atoms of the donor and the acceptor with the dielectric constant of the medium is established. Tauc plot and TDDFT study indicates a non-vertical electronic transition in the complexes. Buckingham and Lippert Mataga equations are applied to check the Polarizability effect on the CT band.

  10. Probing charge transfer between molecular semiconductors and graphene.

    Science.gov (United States)

    Matković, Aleksandar; Kratzer, Markus; Kaufmann, Benjamin; Vujin, Jasna; Gajić, Radoš; Teichert, Christian

    2017-08-25

    The unique density of states and exceptionally low electrical noise allow graphene-based field effect devices to be utilized as extremely sensitive potentiometers for probing charge transfer with adsorbed species. On the other hand, molecular level alignment at the interface with electrodes can strongly influence the performance of organic-based devices. For this reason, interfacial band engineering is crucial for potential applications of graphene/organic semiconductor heterostructures. Here, we demonstrate charge transfer between graphene and two molecular semiconductors, parahexaphenyl and buckminsterfullerene C 60 . Through in-situ measurements, we directly probe the charge transfer as the interfacial dipoles are formed. It is found that the adsorbed molecules do not affect electron scattering rates in graphene, indicating that charge transfer is the main mechanism governing the level alignment. From the amount of transferred charge and the molecular coverage of the grown films, the amount of charge transferred per adsorbed molecule is estimated, indicating very weak interaction.

  11. Noncovalent Functionalization and Charge Transfer in Antimonene.

    Science.gov (United States)

    Abellán, Gonzalo; Ares, Pablo; Wild, Stefan; Nuin, Edurne; Neiss, Christian; Miguel, David Rodriguez-San; Segovia, Pilar; Gibaja, Carlos; Michel, Enrique G; Görling, Andreas; Hauke, Frank; Gómez-Herrero, Julio; Hirsch, Andreas; Zamora, Félix

    2017-11-13

    Antimonene, a novel group 15 two-dimensional material, is functionalized with a tailormade perylene bisimide through strong van der Waals interactions. The functionalization process leads to a significant quenching of the perylene fluorescence, and surpasses that observed for either graphene or black phosphorus, thus allowing straightforward characterization of the flakes by scanning Raman microscopy. Furthermore, scanning photoelectron microscopy studies and theoretical calculations reveal a remarkable charge-transfer behavior, being twice that of black phosphorus. Moreover, the excellent stability under environmental conditions of pristine antimonene has been tackled, thus pointing towards the spontaneous formation of a sub-nanometric oxide passivation layer. DFT calculations revealed that the noncovalent functionalization of antimonene results in a charge-transfer band gap of 1.1 eV. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  12. Chemical bond properties and charge transfer bands of O(2-)-Eu(3+), O(2-)-Mo(6+) and O(2-)-W(6+) in Eu(3+)-doped garnet hosts Ln3M5O12 and ABO4 molybdate and tungstate phosphors.

    Science.gov (United States)

    Liu, Xiaoguang; Li, Ling; Noh, Hyeon Mi; Moon, Byung Kee; Choi, Byung Chun; Jeong, Jung Hyun

    2014-06-21

    Charge transfer (CT) energy from the ligand to the central ions is an important factor in luminescence properties for rare earth doped inorganic phosphors. The dielectric theory of complex crystals was used to calculate chemical bond properties. Combining the photoluminescence and the dielectric theory of complex crystals, the CT bands of O(2-)-Eu(3+), O(2-)-Mo(6+) and O(2-)-W(6+) for Eu(3+)-doped inorganic phosphors have been investigated experimentally and theoretically. Taking Eu(3+)-doped Ln3M5O12 (Ln = Y, Lu and M = Al, Ga), Gd3Ga5O12, MMoO4 (M = Ca, Sr, Ba) and MWO4 (M = Ca, Sr, Ba) as typical phosphors, we investigated the effects of the cation size on the CT bands and chemical bond properties including the bond length (d), the covalency (fc), the bond polarizability (αb) and the environmental factor (he) of O(2-)-Eu(3+), O(2-)-Mo(6+) and O(2-)-W(6+), respectively. For systematic isostructural Ln3M5O12 (Ln = Y, Lu and M = Al, Ga) phosphors, with the increasing M ion radius, the bond length of Ln-O decreases, but fc and αb increase, which is the main reason that the environmental factor increased. For the isostructural MMoO4:Eu, with the increasing M ion radius, the Mo-O bond length increases, but fc and αb decrease, and thus he decreases. However, in the compound system MWO4:Eu (M = Ca, Ba) with the increasing M ion radius, the O-W bond length increases, but fc and αb increase, and thus he increases and the O-W CT energy decreases. Their O(2-)-Eu(3+), O(2-)-Mo(6+) and O(2-)-W(6+) CT bands as well as their full width at half maximum (FWHM) were directly influenced by he. And with the increasing he, CT bands of O-Eu or O-Mo or O-W decrease and their FWHM increases. These results indicate a promising approach for changing the material properties, searching for new Eu(3+) doped molybdate, tungstate or other oxide phosphors and analyzing the experimental result.

  13. Boosting the Visible-Light Photoactivity of BiOCl/BiVO4/N-GQD Ternary Heterojunctions Based on Internal Z-Scheme Charge Transfer of N-GQDs: Simultaneous Band Gap Narrowing and Carrier Lifetime Prolonging.

    Science.gov (United States)

    Zhu, Mingyue; Liu, Qian; Chen, Wei; Yin, Yuanyuan; Ge, Lan; Li, Henan; Wang, Kun

    2017-11-08

    The efficient separation of photogenerated electron-hole pairs in photoactive materials is highly desired, allowing their transfer to specific sites for undergoing redox reaction in various applications. The construction of ternary heterojunctions is a practical strategy to enhance the migration of photogenerated electron that realizes the synergistic effect of multicomponents rather than the simple overlay of single component. Here, we demonstrate an available way to fabricate new BiOCl/BiVO 4 /nitrogen-doped graphene quantum dot (N-GQD) ternary heterojunctions that exhibit higher efficiency in charge separation than any binary heterojunction or pure material under visible-light irradiation. UV-vis diffuse reflectance spectroscopy demonstrated that the proposed BiOCl/BiVO 4 /N-GQD ternary heterojunctions possess the narrower band gap energy. More importantly, the ternary heterojunctions reveal the prolonged lifetime of photogenerated charges and enhanced the separation efficiency of photogenerated electron-hole pairs, which may be ascribed to sensitization based on an internal Z-scheme charge transfer at the interface of N-GQDs with oxygen functional groups. Furthermore, we examine the photoactive performance of proposed ternary heterojunctions in aqueous solution by using the photodegradation of bisphenol A as a model system and BiOCl/BiVO 4 /N-GQD ternary heterojunctions also display a dramatically enhanced photodegradation rate. The proposed charge separation and transfer process of BiOCl/BiVO 4 /N-GQD ternary heterojunctions for the enhanced photoactivity were deduced by electrochemical measurements, photoluminescence, and electron spin resonance. The results demonstrate that a Z-scheme charge process was formed between BiOCl/BiVO 4 binary heterojunctions and N-GQDs, leading to an efficient charge carrier separation and strong photocatalytic ability. Notably, this work may assist in a better understanding of the role of N-GQDs in kinds of heterojunctions

  14. Hyperbolic Hopfield neural networks.

    Science.gov (United States)

    Kobayashi, M

    2013-02-01

    In recent years, several neural networks using Clifford algebra have been studied. Clifford algebra is also called geometric algebra. Complex-valued Hopfield neural networks (CHNNs) are the most popular neural networks using Clifford algebra. The aim of this brief is to construct hyperbolic HNNs (HHNNs) as an analog of CHNNs. Hyperbolic algebra is a Clifford algebra based on Lorentzian geometry. In this brief, a hyperbolic neuron is defined in a manner analogous to a phasor neuron, which is a typical complex-valued neuron model. HHNNs share common concepts with CHNNs, such as the angle and energy. However, HHNNs and CHNNs are different in several aspects. The states of hyperbolic neurons do not form a circle, and, therefore, the start and end states are not identical. In the quantized version, unlike complex-valued neurons, hyperbolic neurons have an infinite number of states.

  15. Spectrophotometric methods based on charge transfer complexation ...

    African Journals Online (AJOL)

    The proposed methods were applied successfully for simultaneous determination of the cited drugs in their pharmaceutical formulations with good accuracy and precision and without interferences from common additives. KEY WORDS: Fluconazole, Sertaconazole nitrate, Miconazole nitrate, Charge transfer complexes, ...

  16. Electron impact study of the 100 eV emission cross section and lifetime of the Lyman-Birge-Hopfield band system of N2: Direct excitation and cascade

    Science.gov (United States)

    Ajello, J. M.; Malone, C. P.; Holsclaw, G. M.; Hoskins, A. C.; Eastes, R. W.; McClintock, W. E.; Johnson, P. V.

    2017-06-01

    We have measured the 100 eV emission cross section of the optically forbidden Lyman-Birge-Hopfield (LBH) band system (a1Πg → X1Σ+g) of N2 by electron-impact-induced fluorescence. Using a large (1.5 m diameter) vacuum chamber housing an electron gun system and the Mars Atmosphere and Volatile EvolutioN mission Imaging Ultraviolet Spectrograph optical engineering model, we have obtained calibrated spectral measurements of the LBH band system from 115 to 175 nm over a range of lines of sight to capture all of the optical emissions. These measurements represent the first experiment to directly isolate in the laboratory single-scattering electron-impact-induced fluorescence from both direct excitation of the a1Πg state and cascading contributions to the a1Πg state (a'1Σ-u and w1Δu → a1Πg → X1Σ+g). The determination of the total LBH emission cross section is accomplished by measuring the entire cylindrical glow pattern of the metastable emission from electron impact by imaging lines of sight that measure the glow intensity from zero to 400 mm radial distance and calculating the ratio of the integrated intensity from the LBH glow pattern to that of a simultaneously observed optically allowed transition with a well-established cross section: NI 120.0 nm. The "direct" emission cross section of the a1Πg state at 100 eV was determined to be σemdir = (6.41 ± 1.3) × 10-18 cm2. An important observation from the glow pattern behavior is that the total (direct + cascading) emission cross section is pressure dependent due to collision-induced cascade transitions between close-lying electronic states.

  17. Charge transfer in conjugated oligomers encapsulated into carbon nanotubes

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-11-15

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

  18. Graphene Charge Transfer, Spectroscopy, and Photochemical Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Brus, Louis [Columbia Univ., New York, NY (United States)

    2017-01-31

    This project focused on the special electronic and optical properties of graphene and adsorbed molecular species. Graphene makes an excellent substrate for current collection in nanostructured photovoltaic designs. Graphene is almost transparent, and can be used as a solar cell window. It also has no surface states, and thus current is efficiently transported over long distances. Progress in graphene synthesis indicates that there will soon be practical methods for making large pieces of graphene for devices. We now need to understand exactly what happens to both ground state and electronically excited molecules and Qdots near graphene, if we are going to use them to absorb light in a nano-structured photovoltaic device using graphene to collect photocurrent. We also need to understand how to shift the graphene Fermi level, to optimize the kinetics of electron transfer to graphene. And we need to learn how to convert local graphene areas to semiconductor structure, to make useful spatially patterned graphenes. In this final report, we describe how we addressed these goals. We explored the question of possible Surface Enhanced Raman spectroscopy from molecular Charge Transfer onto Graphene substrates. We observed strong hole doping of graphene by adsorbed halogens as indicated by the shift of the graphene G Raman band. In the case of iodine adsorption, we also observed the anionic species made by hole doping. At low frequency in the Raman spectrum, we saw quite intense lines from I3- and I5- , suggesting possible SERS. We reported on Fresnel calculations on this thin film system, which did not show any net electromagnetic field enhancement.

  19. Quantum-trajectory analysis for charge transfer in solid materials induced by strong laser fields

    Science.gov (United States)

    Jiang, Shicheng; Yu, Chao; Yuan, Guanglu; Wu, Tong; Wang, Ziwen; Lu, Ruifeng

    2017-07-01

    We investigate the dependence of charge transfer on the intensity of driving laser field when SiO2 crystal is irradiated by an 800 nm laser. It is surprising that the direction of charge transfer undergoes a sudden reversal when the driving laser intensity exceeds critical values with different carrier-envelope phases. By applying quantum-trajectory analysis, we find that the Bloch oscillation plays an important role in charge transfer in solids. Also, we study the interaction of a strong laser with gallium nitride (GaN), which is widely used in optoelectronics. A pump-probe scheme is applied to control the quantum trajectories of the electrons in the conduction band. The signal of charge transfer is controlled successfully by means of a theoretically proposed approach.

  20. Optics of Chromites and Charge-Transfer Transitions

    Directory of Open Access Journals (Sweden)

    Andrei V. Zenkov

    2008-01-01

    Full Text Available Specific features of the charge-transfer (CT states and O2p→Cr3d transitions in the octahedral (CrO69− complex are considered in the cluster approach. The reduced matrix elements of the electric-dipole transition operator are calculated on many-electron wave functions of the complex corresponding to the initial and final states of a CT transition. Modeling the optic spectrum of chromites has yielded a complicated CT band. The model spectrum is in satisfactory agreement with experimental data which demonstrates the limited validity of the generally accepted concept of a simple structure of CT spectra.

  1. THERMODYNAMIC STUDY OF CHARGE-TRANSFER COMPLEX ...

    African Journals Online (AJOL)

    a

    ... thiacrown ethers in solution [19-21]. In connection with our previous studies made on the charge-transfer complexes of iodine with crown ethers and their aza derivatives in various solvents [22-28], in this work, we report the results of spectrophotometric study concerning the interaction of iodine with HT18C6 in chloroform.

  2. spectrophotometric methods based on charge transfer complexation

    African Journals Online (AJOL)

    methanol or ethanol, however, the color intensity was lower than in acetonitrile. Figure 5. Effect of solvent on the absorbance of charge transfer complex of FLU with DDQ, I2, p-CLA, and TCNQ acceptors. Effect of reaction time and temperature. Complete color development, was attained instantaneously using iodine for all ...

  3. spectrophotometric study of the charge transfer complexation

    African Journals Online (AJOL)

    Preferred Customer

    complex, Spectrophotometry. INTRODUCTION. Charge-transfer (CT) complexes are formed by interaction between electron donors and electron acceptors. CT complexation is important phenomenon in biochemical and bioelectrochemical energy transfer process [1]. The CT reaction has been widely studied in recent years ...

  4. Parallel Dynamics of Continuous Hopfield Model Revisited

    Science.gov (United States)

    Mimura, Kazushi

    2009-03-01

    We have applied the generating functional analysis (GFA) to the continuous Hopfield model. We have also confirmed that the GFA predictions in some typical cases exhibit good consistency with computer simulation results. When a retarded self-interaction term is omitted, the GFA result becomes identical to that obtained using the statistical neurodynamics as well as the case of the sequential binary Hopfield model.

  5. Partial charge transfer process in adsorption phenomena

    Energy Technology Data Exchange (ETDEWEB)

    Roque, R.; Pascual, R.; Diaz, C. (Centro Nacional de Investigacion Cientifica, Habana (Cuba))

    1981-01-01

    The adsorption of Fe/sup 3 +/ ions on the surface of activated charcoal was studied by Moessbauer spectroscopy. As a result of the numerical interpretation of the spectra, the existence of a chemically adsorbed state with an oxidation number larger than +3 was found. This indicates that an electron is shared between the ion and the surface and therefore, it is related with a partial charge transfer process.

  6. Intramolecular Energy Transfer, Charge Transfer & Hydrogen Bond

    Indian Academy of Sciences (India)

    Ultrafast Dynamics of Chemical Reactions in Condensed Phase: Intramolecular Energy Transfer, Charge Transfer & Hydrogen Bond · PowerPoint Presentation · Slide 3 · Slide 4 · Slide 5 · Slide 6 · Slide 7 · Slide 8 · Slide 9 · Slide 10 · Slide 11 · Slide 12 · Slide 13 · Slide 14 · Slide 15 · Slide 16 · Slide 17 · Slide 18 · Slide 19.

  7. Charge transfer in green fluorescent protein.

    Science.gov (United States)

    van Thor, Jasper J; Sage, J Timothy

    2006-06-01

    Charge transfer reactions that contribute to the photoreactions of the wild type green fluorescent protein (GFP) do not occur in the isolated p-hydroxybenzylidene-imidazolidinone chromophore, demonstrating the role of the protein environment. The high quantum efficiency of the fluorescence photocycle that includes excited state proton transfer and the suppression of non-radiative pathways by the protein environment have been correlated with structural dynamics in the chromophore environment. A low quantum efficiency competing phototransformation reaction of GFP is accompanied by both proton and electron transfer, and closely mimics the charge redistribution that is occurring in the fluorescence photocycle. The protein response to this destabilising event has been demonstrated by cryo-trapping of early products in the reaction pathway and is found to be strong even at 100 K, including displacements of chromophore, protein, solvent and a photogenerated CO2 molecule derived from the decarboxylated Glu 222 side chain. We discuss the ramifications of the observation of strong conformational perturbations below the protein dynamical transition at approximately 200 K, in view of low temperature work on other light sensitive proteins such as myoglobin and bacteriorhodopsin. The proton and electron transfer in the phototransformation pathway mimics the proton and charge transfer which occurs during the fluorescence cycle, which leads to common structural responses in both photoreactions as shown by ultrafast spectroscopy. We review and discuss literature on light-induced and thermal charge transfer events, focusing on recent findings addressing conformational dynamics and implications for thermodynamic properties.

  8. Charge transfer and polarization screening at organic-metal interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Peisert, Heiko; Kolacyak, Daniel; Chasse, Thomas [University of Tuebingen (Germany). Institute of Physical and Theoretical Chemistry

    2009-07-01

    Core hole screening effects at organic/metal interfaces were studied using core level X-ray photoemission spectroscopy (XPS), x-ray excited Auger electron spectroscopy (XAES) and valence band ultraviolet photoemission spectroscopy (UPS). The comparison of energetic shifts in XPS and XAES enables the estimation of electronic relaxation energy (screening ability). Magnesium phthalocyanine (MgPc), zinc phthalocyanine (ZnPc) and perfluorinated zinc phthalocyanine (ZnPcF16) evaporated on single crystalline Au(100) were used as model molecules. Two different features in the metal Auger spectra can be clearly separated for (sub-)monolayer coverages while only minor changes of the shape of corresponding photoemission features are observed. In contrast, Auger spectra of fluorine in ZnPcF16 do not show different components for ultrathin films. Applying a dielectric continuum model, the major screening mechanism cannot be described sufficiently by polarization screening due to mirror charges, significant contributions by charge transfer screening have to be considered.

  9. Metastable charge-transfer state of californium(iii) compounds.

    Science.gov (United States)

    Liu, Guokui; Cary, Samantha K; Albrecht-Schmitt, Thomas E

    2015-06-28

    Among a series of anomalous physical and chemical properties of Cf(iii) compounds revealed by recent investigations, the present work addresses the characteristics of the optical spectra of An(HDPA)3·H2O (An = Am, Cm, and Cf), especially the broadband photoluminescence from Cf(HDPA)3·H2O induced by ligand-to-metal charge transfer (CT). As a result of strong ion-ligand interactions and the relative ease of reducing Cf(iii) to Cf(ii), a CT transition occurs at low energy (transfer state undergoes radiative and non-radiative relaxations. Broadening of the CT transition arises from strong vibronic coupling and hole-charge interactions in the valence band. The non-radiative relaxation of the metastable CT state results from a competition between phonon-relaxation and thermal tunneling that populates the excited states of Cf(iii).

  10. Computational Approach to Electron Charge Transfer Reactions

    DEFF Research Database (Denmark)

    Jónsson, Elvar Örn

    -molecular mechanics scheme, and tools to analyse statistical data and generate relative free energies and free energy surfaces. The methodology is applied to several charge transfer species and reactions in chemical environments - chemical in the sense that solvent, counter ions and substrate surfaces are taken...... statistics and a simple post-sampling scheme used to generate free energy surfaces - which compare to full ab initio calculations. In the last part both the molecular dynamics and hybrid classical and quantum mechanics method are used to generate a vast data set for the accurate analysis of dynamical...... in to account - which directly influence the reactants and resulting reaction through both physical and chemical interactions. All methods are though general and can be applied to different types of chemistry. First, the basis of the various theoretical tools is presented and applied to several test systems...

  11. Nonradiative charge transfer in collisions of protons with rubidium atoms

    Science.gov (United States)

    Yan, Ling-Ling; Qu, Yi-Zhi; Liu, Chun-Hua; Zhang, Yu; Wang, Jian-Guo; Buenker, Robert J.

    2012-06-01

    The nonradiative charge-transfer cross sections for protons colliding with Rb(5s) atoms are calculated by using the quantum-mechanical molecularorbital close-coupling method in an energy range of 10-3 keV-10 keV. The total and state-selective charge-transfer cross sections are in good agreement with the experimental data in the relatively low energy region. The importance of rotational coupling for chargetransfer process is stressed. Compared with the radiative charge-transfer process, nonradiative charge transfer is a dominant mechanism at energies above 15 eV. The resonance structures of state-selective charge-transfer cross sections arising from the competition among channels are analysed in detail. The radiative and nonradiative charge-transfer rate coefficients from low to high temperature are presented.

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

    Science.gov (United States)

    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.

  13. Intervalence charge transfer transition in mixed valence complexes ...

    Indian Academy of Sciences (India)

    Permanent link: http://www.ias.ac.in/article/fulltext/jcsc/114/04/0431-0442. Keywords. Mixed valence complexes; intervalence charge transfer; rotaxane; inclusion complex; optical electron transfer; cyclodextrin. Abstract. Intervalence charge transfer properties were studied for a set of mixed valence complexes incorporating ...

  14. Excited state intramolecular charge transfer reaction of 4 ...

    Indian Academy of Sciences (India)

    Administrator

    We will use the twisted intramolecular charge transfer (TICT) model to explain the photo-induced charge transfer ..... full width at half maxima (Γ) are expressed in 103 cm–1. –ΔGr are in kJ mol–1 units. PFH: per- ..... incorrect values of thermodynamic and kinetic parameters calculated using these reaction times, leading to ...

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

    Science.gov (United States)

    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.

  16. Improved Charge-Transfer Fluorescent Dyes

    Science.gov (United States)

    Meador, Michael

    2005-01-01

    Improved charge-transfer fluorescent dyes have been developed for use as molecular probes. These dyes are based on benzofuran nuclei with attached phenyl groups substituted with, variously, electron donors, electron acceptors, or combinations of donors and acceptors. Optionally, these dyes could be incorporated as parts of polymer backbones or as pendant groups or attached to certain surfaces via self-assembly-based methods. These dyes exhibit high fluorescence quantum yields -- ranging from 0.2 to 0.98, depending upon solvents and chemical structures. The wavelengths, quantum yields, intensities, and lifetimes of the fluorescence emitted by these dyes vary with (and, hence, can be used as indicators of) the polarities of solvents in which they are dissolved: In solvents of increasing polarity, fluorescence spectra shift to longer wavelengths, fluorescence quantum yields decrease, and fluorescence lifetimes increase. The wavelengths, quantum yields, intensities, and lifetimes are also expected to be sensitive to viscosities and/or glass-transition temperatures. Some chemical species -- especially amines, amino acids, and metal ions -- quench the fluorescence of these dyes, with consequent reductions in intensities, quantum yields, and lifetimes. As a result, the dyes can be used to detect these species. Another useful characteristic of these dyes is a capability for both two-photon and one-photon absorption. Typically, these dyes absorb single photons in the ultraviolet region of the spectrum (wavelengths fluorescence spectra identical to those obtained in response to excitation by single photons at half the corresponding wavelengths (300 to 400 nm). While many prior fluorescent dyes exhibit high quantum yields, solvent-polarity- dependent fluorescence behavior, susceptibility to quenching by certain chemical species, and/or two-photon fluorescence, none of them has the combination of all of these attributes. Because the present dyes do have all of these attributes

  17. Thermodynamic study of charge-transfer complex of iodine with ...

    African Journals Online (AJOL)

    Thermodynamic study of charge-transfer complex of iodine with HT18C6 in chloroform solution. Mahmoud Javadian Jazi, Ali Reza Firooz, Abolfazl Semnani, Hamid Reza Pouretedal, Mohammad Hossein Keshavarz ...

  18. Correlation between stick-slip frictional sliding and charge transfer

    OpenAIRE

    Ananthakrishna, G.; Kumar, Jagadish

    2010-01-01

    A decade ago, Budakian and Putterman (Phys. Rev. Lett., {\\bf 85}, 1000 (2000)) ascribed friction to the formation of bonds arising from contact charging when a gold tip of a surface force apparatus was dragged on polymethylmethacrylate surface. We propose a stick-slip model that captures the observed correlation between stick-slip events and charge transfer, and the lack of dependence of the scale factor connecting the force jumps and charge transfer on normal load. Here, stick-slip dynamics ...

  19. Charge transfer in time-dependent density functional theory

    Science.gov (United States)

    Maitra, Neepa T.

    2017-10-01

    Charge transfer plays a crucial role in many processes of interest in physics, chemistry, and bio-chemistry. In many applications the size of the systems involved calls for time-dependent density functional theory (TDDFT) to be used in their computational modeling, due to its unprecedented balance between accuracy and efficiency. However, although exact in principle, in practise approximations must be made for the exchange-correlation functional in this theory, and the standard functional approximations perform poorly for excitations which have a long-range charge-transfer component. Intense progress has been made in developing more sophisticated functionals for this problem, which we review. We point out an essential difference between the properties of the exchange-correlation kernel needed for an accurate description of charge-transfer between open-shell fragments and between closed-shell fragments. We then turn to charge-transfer dynamics, which, in contrast to the excitation problem, is a highly non-equilibrium, non-perturbative, process involving a transfer of one full electron in space. This turns out to be a much more challenging problem for TDDFT functionals. We describe dynamical step and peak features in the exact functional evolving over time, that are missing in the functionals currently used. The latter underestimate the amount of charge transferred and manifest a spurious shift in the charge transfer resonance position. We discuss some explicit examples.

  20. Charge transfer for slow H atoms interacting with Al: Atomic levels and linewidths

    Science.gov (United States)

    Merino, J.; Lorente, N.; Pou, P.; Flores, F.

    1996-10-01

    The charge transfer of slow H atoms colliding with an Al(100) surface is studied by means of a linear combination of atomic orbitals method with local-density many-body contributions. The method is developed in order to calculate atomic levels and associated linewidths. Unlike previous theories, the present method is able to study the effect of the corrugation of the surface, together with the self-consistent potentials involved. This leads to a shift of atomic levels nonlinear on the external charge, contrary to the traditionally assumed image shift. The method works best at very short distances, where the strong coupling between atom and surface promotes molecular orbitals. Thus, the theory expounded in this work can describe the charge-transfer processes of systems in which the atomic levels are near the band edges, as protons scattered off aluminum.

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

    Science.gov (United States)

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

    2017-10-01

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

  2. Charge migration and charge transfer in molecular systems

    Directory of Open Access Journals (Sweden)

    Hans Jakob Wörner

    2017-11-01

    Full Text Available 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.

  3. Molecular Arrangement and Charge Transfer in C60/Graphene Heterostructures.

    Science.gov (United States)

    Ojeda-Aristizabal, Claudia; Santos, Elton J G; Onishi, Seita; Yan, Aiming; Rasool, Haider I; Kahn, Salman; Lv, Yinchuan; Latzke, Drew W; Velasco, Jairo; Crommie, Michael F; Sorensen, Matthew; Gotlieb, Kenneth; Lin, Chiu-Yun; Watanabe, Kenji; Taniguchi, Takashi; Lanzara, Alessandra; Zettl, Alex

    2017-05-23

    Charge transfer at the interface between dissimilar materials is at the heart of electronics and photovoltaics. Here we study the molecular orientation, electronic structure, and local charge transfer at the interface region of C60 deposited on graphene, with and without supporting substrates such as hexagonal boron nitride. We employ ab initio density functional theory with van der Waals interactions and experimentally characterize interface devices using high-resolution transmission electron microscopy and electronic transport. Charge transfer between C60 and the graphene is found to be sensitive to the nature of the underlying supporting substrate and to the crystallinity and local orientation of the C60. Even at room temperature, C60 molecules interfaced to graphene are orientationally locked into position. High electron and hole mobilities are preserved in graphene with crystalline C60 overlayers, which has ramifications for organic high-mobility field-effect devices.

  4. Charge Transfer and Catalysis at the Metal Support Interface

    Energy Technology Data Exchange (ETDEWEB)

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

    2012-07-31

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

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

    Science.gov (United States)

    Haverkate, Lucas A.; Zbiri, Mohamed; Johnson, Mark R.; Carter, Elizabeth; Kotlewski, Arek; Picken, S.; Mulder, Fokko M.; Kearley, Gordon J.

    2014-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-01-07

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

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

    Science.gov (United States)

    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.

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

    DEFF Research Database (Denmark)

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

    2003-01-01

    We have thoroughly characterized the surfaces of the organic charge-transfer salts TTF-TCNQ and (TMTSF)(2)PF6 which are generally acknowledged as prototypical examples of one-dimensional conductors. In particular x-ray-induced photoemission spectroscopy turns out to be a valuable nondestructive...... diagnostic tool. We show that the observation of generic one-dimensional signatures in photoemission spectra of the valence band close to the Fermi level can be strongly affected by surface effects. Especially, great care must be exercised taking evidence for an unusual one-dimensional many-body state...

  9. Excited state intramolecular charge transfer reaction in non-aqueous ...

    Indian Academy of Sciences (India)

    concentration dependent reaction rate constant of a. TICT reaction already measured in bulk electrolyte solutions.44–46 Here, we report such a study where photo-induced intramolecular charge transfer reaction has been investigated in AOT/heptane non-aqueous reverse micelles at different Ws values, and also in.

  10. Photoinduced intramolecular charge-transfer reactions in 4-amino-3 ...

    Indian Academy of Sciences (India)

    Photoinduced intramolecular charge-transfer reactions in 4-amino-3-methyl benzoic acid methyl ester (AMBME) have been investigated spectroscopically. AMBME, with its weak charge donor primary amino group, shows dual emission in polar solvents. Absorption and emission measurements in the condensed phase ...

  11. Development of Two Charge-Transfer Complex Spectrophotometric ...

    African Journals Online (AJOL)

    Development of Two Charge-Transfer Complex. Spectrophotometric Methods for Determination of ... Purpose: To develop an easy, fast and sensible spectrophotometric method for determination of tofisopam in tablet dosage form. Methods: ..... profiles of tofisopam and diazepam. Eur J Clin. Pharmacol 1982; 22: 137-142. 2.

  12. b-Cyclodextrin-assisted intervalence charge transfer in mixed- valent

    Indian Academy of Sciences (India)

    Administrator

    b-Cyclodextrin-assisted intervalence charge transfer in mixed- valent [2]rotaxane complexes having metal centres linked by interrupted p-electron systems. ATINDRA D SHUKLA, H C BAJAJ and AMITAVA DAS. Silicates and Catalysis Discipline, Central Salt and Marine Chemicals. Research Institute, Bhavnagar 364 002, ...

  13. CNDO/SCF molecular orbital structural studies and charge transfer ...

    African Journals Online (AJOL)

    CNDO/SCF molecular orbital structural studies and charge transfer complex formation between 4,4'-dimethoxydiquinone and uracil. ... potentials and the electron affinities of the studied molecules have been calculated in addition to their charge densities giving the columbic potential energy of the donor and acceptor.

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

    Indian Academy of Sciences (India)

    Evaluation of intramolecular charge transfer state of. 4-N, N-dimethylamino cinnamaldehyde using time-dependent density functional theory. SURAJIT GHOSHa, K V S GIRISHb and SUBHADIP GHOSHb,∗. aDepartment of Physics and Technophysics, Vidyasagar University, Midnapore 721 102, India. bSchool of Chemical ...

  15. Kinetic and Thermodynamic Studies of Charge-Transfer Complex ...

    African Journals Online (AJOL)

    NICOLAAS

    the donor in the two solvents was estimated and compared with the theoretical values. KEYWORDS. Charge-transfer complex ... drug-receptor binding mechanisms,7 in solar energy storage 8,9 and in surface chemistry10 as well as in many ..... dyes-sensitized solar cells, Renew. Energ., 2010, 35, 1724–1728. 10 S.M. ...

  16. Effects of acid concentration on intramolecular charge transfer ...

    Indian Academy of Sciences (India)

    Effects of acid concentration on excited state intramolecular charge transfer reaction of 4-(azetidinyl) benzonitrile (P4C) in aprotic (acetonitrile and ethyl acetate) and protic (ethanol) solvents have been studied by means of steady state absorption and fluorescence, and time resolved fluorescence spectroscopic techniques.

  17. Correlating electronic and vibrational motions in charge transfer systems

    Energy Technology Data Exchange (ETDEWEB)

    Khalil, Munira [Univ. of Washington, Seattle, WA (United States)

    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.

  18. Valence Topological Charge-Transfer Indices for Dipole Moments

    Directory of Open Access Journals (Sweden)

    Francisco Torrens

    2003-01-01

    Full Text Available New valence topological charge-transfer indices are applied to the calculation of dipole moments. The algebraic and vector semisum charge-transfer indices are defined. The combination of the charge-transfer indices allows the estimation of the dipole moments. The model is generalized for molecules with heteroatoms. The ability of the indices for the description of the molecular charge distribution is established by comparing them with the dipole moments of a homologous series of phenyl alcohols. Linear and non-linear correlation models are obtained. The new charge-transfer indices improve the multivariable non-linear regression equations for the dipole moment. When comparing with previous results, the variance decreases 92%. No superposition of the corresponding Gk–Jk and GkV – JkV pairs is observed. This diminishes the risk of co-linearity. Inclusion of the oxygen atom in the p-electron system is beneficial for the description of the dipole moment, owing to either the role of the additional p orbitals provided by the heteroatom or the role of steric factors in the p-electron conjugation. Linear and non-linear correlations between the fractal dimension and various descriptors point not only to a homogeneous molecular structure but also to the ability to predict and tailor drug properties.

  19. Excited state intramolecular charge transfer reaction in 4-(1 ...

    Indian Academy of Sciences (India)

    Administrator

    Abstract. Excited state intramolecular charge transfer reaction of 4-(1-azetidinyl) benzonitrile (P4C) in deuterated and normal methanol, ethanol and acetonitrile has been studied in order to investigate the solvent isotope effects on reaction rates and yields. These quantities (reaction rates and yields) along with several.

  20. Excited state intramolecular charge transfer reaction in 4-(1 ...

    Indian Academy of Sciences (India)

    Excited state intramolecular charge transfer reaction of 4-(1-azetidinyl) benzonitrile (P4C) in deuterated and normal methanol, ethanol and acetonitrile has been studied in order to investigate the solvent isotope effects on reaction rates and yields. These quantities (reaction rates and yields) along with several other ...

  1. Charge-Transfer Interactions in Organic Functional Materials

    Directory of Open Access Journals (Sweden)

    Bih-Yaw Jin

    2010-08-01

    Full Text Available Our goal in this review is three-fold. First, we provide an overview of a number of quantum-chemical methods that can abstract charge-transfer (CT information on the excited-state species of organic conjugated materials, which can then be exploited for the understanding and design of organic photodiodes and solar cells at the molecular level. We stress that the Composite-Molecule (CM model is useful for evaluating the electronic excited states and excitonic couplings of the organic molecules in the solid state. We start from a simple polyene dimer as an example to illustrate how interchain separation and chain size affect the intercahin interaction and the role of the charge transfer interaction in the excited state of the polyene dimers. With the basic knowledge from analysis of the polyene system, we then study more practical organic materials such as oligophenylenevinylenes (OPVn, oligothiophenes (OTn, and oligophenylenes (OPn. Finally, we apply this method to address the delocalization pathway (through-bond and/or through-space in the lowest excited state for cyclophanes by combining the charge-transfer contributions calculated on the cyclophanes and the corresponding hypothetical molecules with tethers removed. This review represents a step forward in the understanding of the nature of the charge-transfer interactions in the excited state of organic functional materials.

  2. Charge-Transfer Complexes Studied by Dynamic Force Spectroscopy

    Directory of Open Access Journals (Sweden)

    Jurriaan Huskens

    2013-03-01

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

  3. BOUNDARY DEPTH INFORMATION USING HOPFIELD NEURAL NETWORK

    Directory of Open Access Journals (Sweden)

    S. Xu

    2016-06-01

    Full Text Available Depth information is widely used for representation, reconstruction and modeling of 3D scene. Generally two kinds of methods can obtain the depth information. One is to use the distance cues from the depth camera, but the results heavily depend on the device, and the accuracy is degraded greatly when the distance from the object is increased. The other one uses the binocular cues from the matching to obtain the depth information. It is more and more mature and convenient to collect the depth information of different scenes by stereo matching methods. In the objective function, the data term is to ensure that the difference between the matched pixels is small, and the smoothness term is to smooth the neighbors with different disparities. Nonetheless, the smoothness term blurs the boundary depth information of the object which becomes the bottleneck of the stereo matching. This paper proposes a novel energy function for the boundary to keep the discontinuities and uses the Hopfield neural network to solve the optimization. We first extract the region of interest areas which are the boundary pixels in original images. Then, we develop the boundary energy function to calculate the matching cost. At last, we solve the optimization globally by the Hopfield neural network. The Middlebury stereo benchmark is used to test the proposed method, and results show that our boundary depth information is more accurate than other state-of-the-art methods and can be used to optimize the results of other stereo matching methods.

  4. Charge Transfer and Support Effects in Heterogeneous Catalysis

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-12-21

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

  5. Why do Physicists Love Charge-Transfer Salts?

    Science.gov (United States)

    Singleton, John

    2002-11-01

    I describe some of the phenomena encountered in charge-transfer salts that make them very attractive for condensed-matter physicists. These materials exhibit many interesting electronic properties, including reduced dimensionality, strong electron-electron and electron-phonon interactions and the proximity of antiferromagnetism, insulator states and superconductivity. A wide variety of low-temperature groundstates have been observed in the salts; frequently, one is able to move between these states by applying magnetic field, temperature, pressure or "chemical pressure". In spite of this complex behavior, the charge-transfer salts possess very simple electronic bandstructure which it is often possible to measure in great detail. Hence, one can use the salts as "model systems" in which tractable theoretical calculations for phenomena such as superconductivity are compared directly with experiment.

  6. Radiative charge transfer in collisions of C with He+

    CERN Document Server

    Babb, James F

    2016-01-01

    Radiative charge exchange collisions between a carbon atom C(${}^3$P) and a helium ion He+, both in their ground state, are investigated theoretically. Detailed quantum chemistry calculations are carried out to obtain potential energy curves and transition dipole matrix elements for doublet and quartet molecular states of the HeC+ cation. Radiative charge transfer cross sections and rate coefficients are calculated and are found at thermal and lower energies to be large compared to those for direct charge transfer. The present results might be applicable to modelling the complex interplay of [C II] (or C+), C, and CO at the boundaries of photon dominated regions (PDRs) and in xray dominated regions (XDRs), where the abundance of He+ affects the abundance of CO.

  7. Imaging charge transfer in iodomethane upon x-ray photoabsorption.

    Science.gov (United States)

    Erk, Benjamin; Boll, Rebecca; Trippel, Sebastian; Anielski, Denis; Foucar, Lutz; Rudek, Benedikt; Epp, Sascha W; Coffee, Ryan; Carron, Sebastian; Schorb, Sebastian; Ferguson, Ken R; Swiggers, Michele; Bozek, John D; Simon, Marc; Marchenko, Tatiana; Küpper, Jochen; Schlichting, Ilme; Ullrich, Joachim; Bostedt, Christoph; Rolles, Daniel; Rudenko, Artem

    2014-07-18

    Studies of charge transfer are often hampered by difficulties in determining the charge localization at a given time. Here, we used ultrashort x-ray free-electron laser pulses to image charge rearrangement dynamics within gas-phase iodomethane molecules during dissociation induced by a synchronized near-infrared (NIR) laser pulse. Inner-shell photoionization creates positive charge, which is initially localized on the iodine atom. We map the electron transfer between the methyl and iodine fragments as a function of their interatomic separation set by the NIR-x-ray delay. We observe signatures of electron transfer for distances up to 20 angstroms and show that a realistic estimate of its effective spatial range can be obtained from a classical over-the-barrier model. The presented technique is applicable for spatiotemporal imaging of charge transfer dynamics in a wide range of molecular systems. Copyright © 2014, American Association for the Advancement of Science.

  8. Exact quantisation of the relativistic Hopfield model

    Energy Technology Data Exchange (ETDEWEB)

    Belgiorno, F., E-mail: francesco.belgiorno@polimi.it [Dipartimento di Matematica, Politecnico di Milano, Piazza Leonardo 32, IT-20133 Milano (Italy); INdAM-GNFM (Italy); Cacciatori, S.L., E-mail: sergio.cacciatori@uninsubria.it [Department of Science and High Technology, Università dell’Insubria, Via Valleggio 11, IT-22100 Como (Italy); INFN sezione di Milano, via Celoria 16, IT-20133 Milano (Italy); Dalla Piazza, F., E-mail: f.dallapiazza@gmail.com [Università “La Sapienza”, Dipartimento di Matematica, Piazzale A. Moro 2, I-00185, Roma (Italy); Doronzo, M., E-mail: m.doronzo@uninsubria.it [Department of Science and High Technology, Università dell’Insubria, Via Valleggio 11, IT-22100 Como (Italy)

    2016-11-15

    We investigate the quantisation in the Heisenberg representation of a relativistically covariant version of the Hopfield model for dielectric media, which entails the interaction of the quantum electromagnetic field with the matter dipole fields, represented by a mesoscopic polarisation field. A full quantisation of the model is provided in a covariant gauge, with the aim of maintaining explicit relativistic covariance. Breaking of the Lorentz invariance due to the intrinsic presence in the model of a preferred reference frame is also taken into account. Relativistic covariance forces us to deal with the unphysical (scalar and longitudinal) components of the fields, furthermore it introduces, in a more tricky form, the well-known dipole ghost of standard QED in a covariant gauge. In order to correctly dispose of this contribution, we implement a generalised Lautrup trick. Furthermore, causality and the relation of the model with the Wightman axioms are also discussed.

  9. Understanding Charge Transfer in Carbon Nanotube–Fullerene Bulk Heterojunctions

    Energy Technology Data Exchange (ETDEWEB)

    Gong, Maogang; Shastry, Tejas A.; Cui, Qiannan; Kohlmeyer, Ryan R. [National Research Council, Washington, D.C. 20001, United States; Soft; Luck, Kyle A.; Rowberg, Andrew; Marks, Tobin J.; Durstock, Michael F. [Soft; Zhao, Hui; Hersam, Mark C.; Ren, Shenqiang

    2015-03-27

    Semiconducting single-walled carbon nanotube/fullerene bulk heterojunctions exhibit unique optoelectronic properties highly suitable for flexible, efficient, and robust photovoltaics and photodetectors. We investigate charge-transfer dynamics in inverted devices featuring a polyethylenimine-coated ZnO nanowire array infiltrated with these blends and find that trap-assisted recombination dominates transport within the blend and at the active layer/nanowire interface. We find that electrode modifiers suppress this recombination, leading to high performance.

  10. Excited state charge transfer reaction in (mixed solvent + electrolyte ...

    Indian Academy of Sciences (India)

    charge transfer reaction of 4-(1-azetidinyl)benzonitrile (P4C) in two sets of mixed solvents, (1-propanol + ethyl acetate) and (propylene ...... Harun Al Rasid Gazi and Ranjit Biswas. PrOH+EA. Normalized F.I.. 0. 1. Normalized F.I.. 0. 1. -3. 0. 3. 3000. 4000. 5000. 6000. Residual. -3. 0. 3. Residual. -3. 0. 3. Time(ps). 3000. 4000.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    Benson, Michelle C.

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

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

    KAUST Repository

    Fonari, Alexandr

    2014-10-21

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

  14. Charge Transfer at Hybrid Interfaces: Plasmonics of Aromatic Thiol-Capped Gold Nanoparticles.

    Science.gov (United States)

    Goldmann, Claire; Lazzari, Rémi; Paquez, Xavier; Boissière, Cédric; Ribot, François; Sanchez, Clément; Chanéac, Corinne; Portehault, David

    2015-07-28

    Although gold nanoparticles stabilized by organic thiols are the building blocks in a wide range of applications, the role of the ligands on the plasmon resonance of the metal core has been mostly ignored until now. Herein, a methodology based on the combination of spectroscopic ellipsometry and UV-vis spectroscopy is applied to extract dielectric functions of the different components. It is shown that aromatic thiols allow a significant charge transfer at the hybrid interface with the s and d bands of the gold core that yields "giant" red shifts of the plasmon band, up to 40 nm for spherical particles in the size range of 3-5 nm. These results suggest that hybrid nanoplasmonic devices may be designed through the suitable choice of metal core and organic components for optimized charge exchange.

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

    Science.gov (United States)

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

    2017-07-01

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

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

    Science.gov (United States)

    Friedrich, Johannes; Kreutzer, Sebastian; Schmidt, Christoph

    2017-04-01

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

  17. Positron Annihilation in Solid Charge-Transfer Complexes

    DEFF Research Database (Denmark)

    Lévay, B.; Jansen, P.

    1979-01-01

    Positron lifetime and angular correlation measurements have been carried out on 1:1 charge-transfer complexes, on their pure donor and acceptor components and on the 1:1 M mechanical mixtures of these components. Complex formation reduced the intensity of the long-lifetime component of the donor ...... compounds nearly to the low level of the acceptors. The angular correlation curves obtained for the pure acceptor and the complex were practically identical and were substantially broadened as compared to that of the donor....

  18. Charge transfer effects on the Fermi surface of Ba0.5K 0.5Fe2As2

    KAUST Repository

    Nazir, Safdar

    2011-01-31

    Ab-initio calculations within density functional theory are performed to obtain a more systematic understanding of the electronic structure of iron pnictides. As a prototypical compound we study Ba0.5K 0.5Fe2As2 and analyze the changes of its electronic structure when the interaction between the Fe2As 2 layers and their surrounding is modified. We find strong effects on the density of states near the Fermi energy as well as the Fermi surface. The role of the electron donor atoms in iron pnictides thus cannot be understood in a rigid band picture. Instead, the bonding within the Fe2As 2 layers reacts to a modified charge transfer from the donor atoms by adapting the intra-layer Fe-As hybridization and charge transfer in order to maintain an As3- valence state. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. IR, 1H NMR, mass, XRD and TGA/DTA investigations on the ciprofloxacin/iodine charge-transfer complex

    Science.gov (United States)

    Refat, Moamen S.; El-Hawary, W. F.; Moussa, Mohamed A. A.

    2011-05-01

    The charge-transfer complex (CTC) of ciprofloxacin drug (CIP) as a donor with iodine (I 2) as a sigma acceptor has been studied spectrophotometrically in CHCl 3. At maximum absorption bands, the stoichiometry of CIP:iodine system was found to be 1:1 ratio according to molar ratio method. The essential spectroscopic data like formation constant ( KCT), molar extinction coefficient ( ɛCT), standard free energy (Δ G°), oscillator strength ( f), transition dipole moment ( μ), resonance energy ( RN) and ionization potential ( ID) were estimated. The spectroscopic techniques such as IR, 1H NMR, mass and UV-vis spectra and elemental analyses (CHN) as well as TG-DTG and DTA investigations were used to characterize the chelating behavior of CIP/iodine charge-transfer complex. The iodine CT interaction was associated with a presence of intermolecular hydrogen bond. The X-ray investigation was carried out to investigate the iodine doping in the synthetic CT complex.

  20. Super-iron Nanoparticles with Facile Cathodic Charge Transfer

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-12-31

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

  1. Analytical Study for the Charge-Transfer Complexes of Pregabalin

    Directory of Open Access Journals (Sweden)

    Hesham Salem

    2009-01-01

    Full Text Available Studies were carried out, for the first time, to investigate the charge-transfer reactions of Pregabalin (PRE as n-electron donor with various π-acceptors: 7,7,8,8-tetracyanoquinodimethane (TCNQ, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ, 2,5-dichloro-3,6-dihydroxy-1,4-benzoquinone (chloranilic acid, pCA, tetracyanoethylene (TCNE and 2,3,5,6-tetrachloro-1,4-benzoquinone (chloranil. Different colored charge-transfer complexes and radical anions were obtained. Different variables affecting the reactions were studied and optimized. The formations of the colored complexes were utilized in the development of simple, rapid and accurate spectrophotometric methods for the analysis of PRE in pure form as well as in its pharmaceutical preparation. Under the optimum reaction conditions, linear relationships with good correlation coefficients (0.9995-0.9999 were found between the absorbance and the concentrations of PRE in the range of 8-400 µg mL-1. The limits of assays detection ranged from 0.60 to 8.11 µg mL-1. No interference could be observed from the additives commonly present in the capsules. The methods were successfully applied to the analysis of capsules that contain PRE, with good accuracy and precision; the recovery percentages ranged from 100.19±0.83 to 100.50±0.53. The results were compared favorably with the reported method.

  2. Manipulation of charge transfer and transport in plasmonic-ferroelectric hybrids for photoelectrochemical applications

    Science.gov (United States)

    Wang, Zhijie; Cao, Dawei; Wen, Liaoyong; Xu, Rui; Obergfell, Manuel; Mi, Yan; Zhan, Zhibing; Nasori, Nasori; Demsar, Jure; Lei, Yong

    2016-01-01

    Utilizing plasmonic nanostructures for efficient and flexible conversion of solar energy into electricity or fuel presents a new paradigm in photovoltaics and photoelectrochemistry research. In a conventional photoelectrochemical cell, consisting of a plasmonic structure in contact with a semiconductor, the type of photoelectrochemical reaction is determined by the band bending at the semiconductor/electrolyte interface. The nature of the reaction is thus hard to tune. Here instead of using a semiconductor, we employed a ferroelectric material, Pb(Zr,Ti)O3 (PZT). By depositing gold nanoparticle arrays and PZT films on ITO substrates, and studying the photocurrent as well as the femtosecond transient absorbance in different configurations, we demonstrate an effective charge transfer between the nanoparticle array and PZT. Most importantly, we show that the photocurrent can be tuned by nearly an order of magnitude when changing the ferroelectric polarization in PZT, demonstrating a versatile and tunable system for energy harvesting.

  3. Charge transfer from and to manganese phthalocyanine: bulk materials and interfaces

    Directory of Open Access Journals (Sweden)

    Florian Rückerl

    2017-08-01

    Full Text Available Manganese phthalocyanine (MnPc is a member of the family of transition-metal phthalocyanines, which combines interesting electronic behavior in the fields of organic and molecular electronics with local magnetic moments. MnPc is characterized by hybrid states between the Mn 3d orbitals and the π orbitals of the ligand very close to the Fermi level. This causes particular physical properties, different from those of the other phthalocyanines, such as a rather small ionization potential, a small band gap and a large electron affinity. These can be exploited to prepare particular compounds and interfaces with appropriate partners, which are characterized by a charge transfer from or to MnPc. We summarize recent spectroscopic and theoretical results that have been achieved in this regard.

  4. Spectroscopic and thermodynamic study of charge transfer complexes of cloxacillin sodium in aqueous ethanol medium

    Science.gov (United States)

    Roy, Dalim Kumar; Saha, Avijit; Mukherjee, Asok K.

    2005-07-01

    Cloxacillin sodium has been shown to form charge transfer (CT) complexes of 1:1 stoichiometry with a number of electron acceptors in 50% (v/v) aqueous ethanol medium. From the trends in the CT absorption bands, the vertical ionization potential of the drug molecule (cloxacillin sodium) has been estimated to be 7.89 eV. The enthalpies and entropies of formation of two such complexes have been determined by estimating the formation constants spectrophotometrically at five different temperatures. The oscillator strengths and transition dipole moments of these complexes have been determined. It has further been noted that the reduction of o-chloranil by aqueous ethanol is completely inhibited by cloxacillin sodium, a phenomenon that makes the present study of formation equilibrium possible.

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

    Science.gov (United States)

    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.

  6. Chaotic Hopfield Neural Network Swarm Optimization and Its Application

    Directory of Open Access Journals (Sweden)

    Yanxia Sun

    2013-01-01

    Full Text Available A new neural network based optimization algorithm is proposed. The presented model is a discrete-time, continuous-state Hopfield neural network and the states of the model are updated synchronously. The proposed algorithm combines the advantages of traditional PSO, chaos and Hopfield neural networks: particles learn from their own experience and the experiences of surrounding particles, their search behavior is ergodic, and convergence of the swarm is guaranteed. The effectiveness of the proposed approach is demonstrated using simulations and typical optimization problems.

  7. Charge Transfer Plasmons: Optical Frequency Conductances and Tunable Infrared Resonances.

    Science.gov (United States)

    Wen, Fangfang; Zhang, Yue; Gottheim, Samuel; King, Nicholas S; Zhang, Yu; Nordlander, Peter; Halas, Naomi J

    2015-06-23

    A charge transfer plasmon (CTP) appears when an optical-frequency conductive pathway between two metallic nanoparticles is established, enabling the transfer of charge between nanoparticles when the plasmon is excited. Here we investigate the properties of the CTP in a nanowire-bridged dimer geometry. Varying the junction geometry controls its conductance, which modifies the resonance energies and scattering intensities of the CTP while also altering the other plasmon modes of the nanostructure. Reducing the junction conductance shifts this resonance to substantially lower energies in the near- and mid-infrared regions of the spectrum. The CTP offers both a high-information probe of optical frequency conductances in nanoscale junctions and a new, unique approach to controllably engineering tunable plasmon modes at infrared wavelengths.

  8. Study of charge transfer reactions in a microbial fuel cell

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-07-01

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

  9. Positron annihilation studies of some charge transfer molecular complexes

    CERN Document Server

    El-Sayed, A; Boraei, A A A

    2000-01-01

    Positron annihilation lifetimes were measured for some solid charge transfer (CT) molecular complexes of quinoline compounds (2,6-dimethylquinoline, 6-methoxyquinoline, quinoline, 6-methylquinoline, 3-bromoquinoline and 2-chloro-4-methylquinoline) as electron donor and picric acid as an electron acceptor. The infrared spectra (IR) of the solid complexes clearly indicated the formation of the hydrogen-bonding CT-complexes. The annihilation spectra were analyzed into two lifetime components using PATFIT program. The values of the average and bulk lifetimes divide the complexes into two groups according to the non-bonding ionization potential of the donor (electron donating power) and the molecular weight of the complexes. Also, it is found that the ionization potential of the donors and molecular weight of the complexes have a conspicuous effect on the average and bulk lifetime values. The bulk lifetime values of the complexes are consistent with the formation of stable hydrogen-bonding CT-complexes as inferred...

  10. Self-interaction effects on charge-transfer collisions

    CERN Document Server

    Quashie, Edwin E; Andrade, Xavier; Correa, Alfredo A

    2016-01-01

    In this article, we investigate the role of the self-interaction error in the simulation of collisions using time-dependent density functional theory (TDDFT) and Ehrenfest dynamics. We compare many different approximations of the exchange and correlation potential, using as a test system the collision of $\\mathrm{H^+ + CH_4}$ at $30~\\mathrm{eV}$. We find that semi-local approximations, like PBE, and even hybrid functionals, like B3LYP, produce qualitatively incorrect predictions for the scattering of the proton. This discrepancy appears because the self-interaction error allows the electrons to jump too easily to the proton, leading to radically different forces with respect to the non-self-interacting case. From our results, we conclude that using a functional that is self-interaction free is essential to properly describe charge-transfer collisions between ions and molecules in TDDFT.

  11. Octahedral engineering of orbital polarizations in charge transfer oxides

    Science.gov (United States)

    Cammarata, Antonio; Rondinelli, James M.

    2013-04-01

    Negative charge transfer ABO3 oxides may undergo electronic metal-insulator transitions (MIT) concomitant with a dilation and contraction of nearly rigid octahedra. On both sides of the MIT are in-phase or out-of-phase (or both) rotations of adjacent octahedra that buckle the B-O-B bond angle away from 180∘. Using density functional theory with the PBEsol +U approach, we describe an octahedral engineering avenue to control the B 3d and O 2p orbital polarization through enhancement of the BO6 rotation “sense” rather than solely through conventional changes to the B-O bond lengths, i.e., crystal field distortions. Using CaFeO3 as a prototypical material, we show the flavor of the octahedral rotation pattern when combined with strain-rotation coupling and thin film engineering strategies offers a promising avenue to fine tune orbital polarizations near electronic phase boundaries.

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

    Science.gov (United States)

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

    2016-04-28

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

  13. Charge transfer and transport in polymer-fullerene solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Parisi, J.; Dyakonov, V.; Pientka, M.; Riedel, I.; Deibel, C. [Faculty of Physics, Dept. of Energy and Semiconductor Research, Univ. of Oldenburg, Oldenburg (Germany); Brabec, C.J. [Faculty of Physics, Dept. of Energy and Semiconductor Research, Univ. of Oldenburg, Oldenburg (Germany); Siemens AG, CT MM1 Innovative Polymers, Erlangen (Germany); Sariciftci, N.S. [Faculty of Physics, Dept. of Energy and Semiconductor Research, Univ. of Oldenburg, Oldenburg (Germany); Inst. of Physical Chemistry and Linz Inst. of Organic Solar Cells, Univ. of Linz, Linz (Austria); Hummelen, J.C. [Faculty of Physics, Dept. of Energy and Semiconductor Research, Univ. of Oldenburg, Oldenburg (Germany); Stratingh Inst. and Materials Research Center, Univ. of Groningen, Groningen (Netherlands)

    2002-12-01

    The development of polymer-fullerene plastic solar cells has made significant progress in recent years. These devices excel by an efficient charge generation process as a consequence of a photo-induced charge transfer between the photo-excited conjugated polymer donor and acceptor-type fullerene molecules. Due to the paramagnetic nature of the radical species, the photo-induced charge transfer can be analyzed by the help of light-induced electron spin resonance spectroscopy. Upon looking at an interpenetrating donor-acceptor composite consisting of the polymer MDMO-PPV and the fullerene derivative PCBM, we disclose two well separated line groups having a strongly anisotropic structure. The line shape can be attributed to an environmental axial symmetry of the polymer cation and a lower rhombohedric symmetry of the fullerene anion. Since the signals were found to be independent of one another with different spin-lattice relaxation times, the radical species can be discriminated via separate characterization procedures. In order to study the bulk charge transport properties, we carried out admittance spectroscopy on the polymer-fullerene solar cell device including a transparent semiconductor oxide front contact (ITO/PEDOT:PSS) and a metal back contact (Al). The temperature- and frequency-dependent device capacitance clearly uncovers two different defect states, the first, having an activation energy of 9 meV, indicates a shallow trap due to a bulk impurity, the latter, having an activation energy of 177 meV, can be assigned to an interfacial defect state located between the polymer-fullerene composite and the metal back contact. (orig.)

  14. Multiple-charge transfer and trapping in DNA dimers

    Science.gov (United States)

    Tornow, Sabine; Bulla, Ralf; Anders, Frithjof B.; Zwicknagl, Gertrud

    2010-11-01

    We investigate the charge transfer characteristics of one and two excess charges in a DNA base-pair dimer using a model Hamiltonian approach. The electron part comprises diagonal and off-diagonal Coulomb matrix elements such a correlated hopping and the bond-bond interaction, which were recently calculated by Starikov [E. B. Starikov, Philos. Mag. Lett. 83, 699 (2003)10.1080/0950083031000151374] for different DNA dimers. The electronic degrees of freedom are coupled to an ohmic or a superohmic bath serving as dissipative environment. We employ the numerical renormalization group method in the nuclear tunneling regime and compare the results to Marcus theory for the thermal activation regime. For realistic parameters, the rate that at least one charge is transferred from the donor to the acceptor in the subspace of two excess electrons significantly exceeds the rate in the single charge sector. Moreover, the dynamics is strongly influenced by the Coulomb matrix elements. We find sequential and pair transfer as well as a regime where both charges remain self-trapped. The transfer rate reaches its maximum when the difference of the on-site and intersite Coulomb matrix element is equal to the reorganization energy which is the case in a guanine/cytosine (GC)-dimer. Charge transfer is completely suppressed for two excess electrons in adenine/thymine (AT)-dimer in an ohmic bath and replaced by damped coherent electron-pair oscillations in a superohmic bath. A finite bond-bond interaction W alters the transfer rate: it increases as function of W when the effective Coulomb repulsion exceeds the reorganization energy (inverted regime) and decreases for smaller Coulomb repulsion.

  15. Charge Transfer and Triplet States in High Efficiency OPV Materials and Devices

    Science.gov (United States)

    Dyakonov, Vladimir

    2013-03-01

    The advantage of using polymers and molecules in electronic devices, such as light-emitting diodes (LED), field-effect transistors (FET) and, more recently, solar cells (SC) is justified by the unique combination of high device performance and processing of the semiconductors used. Power conversion efficiency of nanostructured polymer SC is in the range of 10% on lab scale, making them ready for up-scaling. Efficient charge carrier generation and recombination in SC are strongly related to dissociation of the primary singlet excitons. The dissociation (or charge transfer) process should be very efficient in photovoltaics. The mechanisms governing charge carrier generation, recombination and transport in SC based on the so-called bulk-heterojunctions, i.e. blends of two or more semiconductors with different electron affinities, appear to be very complex, as they imply the presence of the intermediate excited states, neutral and charged ones. Charge transfer states, or polaron pairs, are the intermediate states between free electrons/holes and strongly bound excitons. Interestingly, the mostly efficient OLEDs to date are based on the so-called triplet emitters, which utilize the triplet-triplet annihilation process. In SC, recent investigations indicated that on illumination of the device active layer, not only mobile charges but also triplet states were formed. With respect to triplets, it is unclear how these excited states are generated, via inter-system crossing or via back transfer of the electron from acceptor to donor. Triplet formation may be considered as charge carrier loss channel; however, the fusion of two triplets may lead to a formation of singlet excitons instead. In such case, a generation of charges by utilizing of the so far unused photons will be possible. The fundamental understanding of the processes involving the charge transfer and triplet states and their relation to nanoscale morphology and/or energetics of blends is essential for the

  16. CHARGE TRANSFER. Efficient hot-electron transfer by a plasmon-induced interfacial charge-transfer transition.

    Science.gov (United States)

    Wu, K; Chen, J; McBride, J R; Lian, T

    2015-08-07

    Plasmon-induced hot-electron transfer from metal nanostructures is a potential new paradigm for solar energy conversion; however, the reported efficiencies of devices based on this concept are often low because of the loss of hot electrons via ultrafast electron-electron scattering. We propose a pathway, called the plasmon-induced interfacial charge-transfer transition (PICTT), that enables the decay of a plasmon by directly exciting an electron from the metal to a strongly coupled acceptor. We demonstrated this concept in cadmium selenide nanorods with gold tips, in which the gold plasmon was strongly damped by cadmium selenide through interfacial electron transfer. The quantum efficiency of the PICTT process was high (>24%), independent of excitation photon energy over a ~1-electron volt range, and dependent on the excitation polarization. Copyright © 2015, American Association for the Advancement of Science.

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

    National Research Council Canada - National Science Library

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

    2008-01-01

    .... In addition, understanding the insertion of metals into molybdenite and evaluation of charge-transfer mechanism and dynamics is important to utilize these minerals in technological applications...

  18. Continuous-time symmetric Hopfield nets are computationally universal.

    Science.gov (United States)

    Síma, Jirí; Orponen, Pekka

    2003-03-01

    We establish a fundamental result in the theory of computation by continuous-time dynamical systems by showing that systems corresponding to so-called continuous-time symmetric Hopfield nets are capable of general computation. As is well known, such networks have very constrained Lyapunov-function controlled dynamics. Nevertheless, we show that they are universal and efficient computational devices, in the sense that any convergent synchronous fully parallel computation by a recurrent network of n discrete-time binary neurons, with in general asymmetric coupling weights, can be simulated by a symmetric continuous-time Hopfield net containing only 18n + 7 units employing the saturated-linear activation function. Moreover, if the asymmetric network has maximum integer weight size w(max) and converges in discrete time t*, then the corresponding Hopfield net can be designed to operate in continuous time Theta(t*/epsilon) for any epsilon > 0 such that w(max)2(12n) computation models, our result implies that any polynomially space-bounded Turing machine can be simulated by a family of polynomial-size continuous-time symmetric Hopfield nets.

  19. Charge transfer at F{sub 16}CoPc and CoPc interfaces to Au

    Energy Technology Data Exchange (ETDEWEB)

    Lindner, Susi; Treske, Uwe; Grobosch, Mandy; Knupfer, Martin [IFW Dresden (Germany)

    2011-12-15

    We analyze the electronic properties of the interfaces between cobalt phthalocyanine (CoPc), as well as fluorinated cobalt phthalocyanine (F{sub 16}CoPc), and an Au(100) single-crystal using X-ray photoemission spectroscopy and valence band ultraviolet photoemission spectroscopy. Our data demonstrate that for the monolayers of both materials a charge transfer occurs from the substrate to the center of the organic molecules resulting in a central Co(I) ion. This leads to the conclusion that this effect essentially is fluorination- and ligand-independent. (orig.)

  20. Charge orders in organic charge-transfer salts

    Science.gov (United States)

    Kaneko, Ryui; Tocchio, Luca F.; Valentí, Roser; Becca, Federico

    2017-10-01

    Motivated by recent experimental suggestions of charge-order-driven ferroelectricity in organic charge-transfer salts, such as κ-(BEDT-TTF)2Cu[N(CN)2]Cl, we investigate magnetic and charge-ordered phases that emerge in an extended two-orbital Hubbard model on the anisotropic triangular lattice at 3/4 filling. This model takes into account the presence of two organic BEDT-TTF molecules, which form a dimer on each site of the lattice, and includes short-range intramolecular and intermolecular interactions and hoppings. By using variational wave functions and quantum Monte Carlo techniques, we find two polar states with charge disproportionation inside the dimer, hinting to ferroelectricity. These charge-ordered insulating phases are stabilized in the strongly correlated limit and their actual charge pattern is determined by the relative strength of intradimer to interdimer couplings. Our results suggest that ferroelectricity is not driven by magnetism, since these polar phases can be stabilized also without antiferromagnetic order and provide a possible microscopic explanation of the experimental observations. In addition, a conventional dimer-Mott state (with uniform density and antiferromagnetic order) and a nonpolar charge-ordered state (with charge-rich and charge-poor dimers forming a checkerboard pattern) can be stabilized in the strong-coupling regime. Finally, when electron–electron interactions are weak, metallic states appear, with either uniform charge distribution or a peculiar 12-site periodicity that generates honeycomb-like charge order.

  1. Excitation of Terahertz Charge Transfer Plasmons in Metallic Fractal Structures

    Science.gov (United States)

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

    2017-08-01

    There have been extensive researches on terahertz (THz) plasmonic structures supporting resonant modes to demonstrate nano and microscale devices with high efficiency and responsivity as well as frequency selectivity. Here, using antisymmetric plasmonic fractal Y-shaped (FYS) structures as building blocks, we introduce a highly tunable four-member fractal assembly to support charge transfer plasmons (CTPs) and classical dipolar resonant modes with significant absorption cross section in the THz domain. We first present that the unique geometrical nature of the FYS system and corresponding spectral response allow for supporting intensified dipolar plasmonic modes under polarised light exposure in a standalone structure. In addition to classical dipolar mode, for the very first time, we demonstrated CTPs in the THz domain due to the direct shuttling of the charges across the metallic fractal microantenna which led to sharp resonant absorption peaks. Using both numerical and experimental studies, we have investigated and confirmed the excitation of the CTP modes and highly tunable spectral response of the proposed plasmonic fractal structure. This understanding opens new and promising horizons for tightly integrated THz devices with high efficiency and functionality.

  2. Versatile charge transfer through anthraquinone films for electrochemical sensing applications

    Energy Technology Data Exchange (ETDEWEB)

    Venarusso, Luna B. [Department of Chemistry, Universidade Federal de Mato Grosso do Sul, Caixa Postal 549, Campo Grande, MS 79070-900 (Brazil); Tammeveski, Kaido [Institute of Chemistry, University of Tartu, Ravila 14a, 50411 Tartu (Estonia); Maia, Gilberto, E-mail: gilberto.maia@ufms.br [Department of Chemistry, Universidade Federal de Mato Grosso do Sul, Caixa Postal 549, Campo Grande, MS 79070-900 (Brazil)

    2011-10-01

    Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were employed to study the effect of anthraquinone (AQ) films on the charge transfer rate of {beta}-nicotinamide adenine dinucleotide (NAD{sup +}), dopamine (DA), and ferricyanide on glassy carbon (GC) electrodes in solutions of different pH. Maximum blocking action on the Fe(CN){sub 6}{sup 3-} redox probe was observed at pH 7 and open-circuit potential (OCP). However, maximum electron hopping effect was observed at pH 9 at both -0.58 V and -0.85 V for Fe(CN){sub 6}{sup 3-}, pH 7 at -0.58 V for NAD{sup +}, and pH 9 at -0.58 V for DA, suggesting that electron hopping in AQ films on a GC surface is dependent on both pH and electrode potential. These findings lend support for the application of these films in the detection of soluble redox probes such as NAD{sup +} and DA at biological pH values (from 7 to 9).

  3. Doping graphene films via chemically mediated charge transfer

    Directory of Open Access Journals (Sweden)

    Ishikawa Ryousuke

    2011-01-01

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

  4. Intramolecular charge transfer effects on 3-aminobenzoic acid

    Energy Technology Data Exchange (ETDEWEB)

    Stalin, T. [Department of Chemistry, Annamalai University, Annamalainagar, Chidambaram 608 002, Tamil Nadu (India); Rajendiran, N. [Department of Chemistry, Annamalai University, Annamalainagar, Chidambaram 608 002, Tamil Nadu (India)], E-mail: drrajendiran@rediffmail.com

    2006-03-20

    Effect of solvents, buffer solutions of different pH and {beta}-cyclodextrin on the absorption and fluorescence spectra of 3-aminobenzoic acid (3ABA) have been investigated. The solid inclusion complex of 3ABA with {beta}-CD is discussed by UV-Vis, fluorimetry, semiempirical quantum calculations (AM1), FT-IR, {sup 1}H NMR and Scanning Electron Microscope (SEM). The thermodynamic parameters ({delta}H, {delta}G and {delta}S) of the inclusion process are also determined. The experimental results indicated that the inclusion processes is an exothermic and spontaneous. The large Stokes shift emission in solvents with 3ABA are correlated with different solvent polarity scales suggest that, 3ABA molecule is more polar in the S{sub 1} state. Solvent, {beta}-CD studies and excited state dipole moment values confirms that the presence of intramolecular charge transfer (ICT) in 3ABA. Acidity constants for different prototropic equilibria of 3ABA in the S{sub 0} and S{sub 1} states are calculated. {beta}-Cyclodextrin studies shows that 3ABA forms a 1:1 inclusion complex with {beta}-CD. {beta}-CD studies suggest COOH group present in non-polar part and amino group present in hydrophilic part of the {beta}-CD cavity. A mechanism is proposed to explain the inclusion process.

  5. A Modified Hopfield Neural Network Algorithm (MHNNA Using ALOS Image for Water Quality Mapping

    Directory of Open Access Journals (Sweden)

    Ahmed Asal Kzar

    2015-12-01

    Full Text Available Decreasing water pollution is a big problem in coastal waters. Coastal health of ecosystems can be affected by high concentrations of suspended sediment. In this work, a Modified Hopfield Neural Network Algorithm (MHNNA was used with remote sensing imagery to classify the total suspended solids (TSS concentrations in the waters of coastal Langkawi Island, Malaysia. The adopted remote sensing image is the Advanced Land Observation Satellite (ALOS image acquired on 18 January 2010. Our modification allows the Hopfield neural network to convert and classify color satellite images. The samples were collected from the study area simultaneously with the acquiring of satellite imagery. The sample locations were determined using a handheld global positioning system (GPS. The TSS concentration measurements were conducted in a lab and used for validation (real data, classification, and accuracy assessments. Mapping was achieved by using the MHNNA to classify the concentrations according to their reflectance values in band 1, band 2, and band 3. The TSS map was color-coded for visual interpretation. The efficiency of the proposed algorithm was investigated by dividing the validation data into two groups. The first group was used as source samples for supervisor classification via the MHNNA. The second group was used to test the MHNNA efficiency. After mapping, the locations of the second group in the produced classes were detected. Next, the correlation coefficient (R and root mean square error (RMSE were calculated between the two groups, according to their corresponding locations in the classes. The MHNNA exhibited a higher R (0.977 and lower RMSE (2.887. In addition, we test the MHNNA with noise, where it proves its accuracy with noisy images over a range of noise levels. All results have been compared with a minimum distance classifier (Min-Dis. Therefore, TSS mapping of polluted water in the coastal Langkawi Island, Malaysia can be performed using the

  6. The thermochromic behavior of aromatic amine-SO2 charge transfer complexes

    Science.gov (United States)

    Monezi, Natália M.; Borin, Antonio C.; Santos, Paulo S.; Ando, Rômulo A.

    2017-02-01

    The distinct thermochromism observed in solutions containing N,N-dimethylaniline (DMA) and N,N-diethylaniline (DEA) and SO2 was investigated by resonance Raman spectroscopy in a wide range of temperatures. The results indicate in addition to the charge transfer (CT) complexes DMA-SO2 and DEA-SO2, the presence of collision complexes involving the CT complexes and excess DMA and DEA molecules. The latter in fact is the chromophore responsible for the long wavelength absorption originating the color. The Raman signature of the collision complex was attributed to the distinct enhancement of a band at 1140 cm- 1 assigned to νs(SO2), in contrast to the same mode in the 1:1 complex at 1115 cm- 1. The intensity of such band, assigned to the collision complex is favored at high temperatures and depends on the steric hindrance associated to amines, as well as the SO2 molar fraction. Quantum chemical calculations based on time-dependent density functional theory (TDDFT) support the proposed interpretation.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-04-02

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-09-01

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

  9. Charge-transfer interactions of Cr species with DNA.

    Science.gov (United States)

    Nowicka, Anna M; Matysiak-Brynda, Edyta; Hepel, Maria

    2017-10-01

    Interactions of Cr species with nucleic acids in living organisms depend strongly on Cr oxidation state and the environmental conditions. As the effects of these interactions range from benign to pre-mutagenic to carcinogenic, careful assessment of the hazard they pose to human health is necessary. We have investigated methods that would enable quantifying the DNA damage caused by Cr species under varying environmental conditions, including UV, O 2 , and redox potential, using simple instrumental techniques which could be in future combined into a field-deployable instrumentation. We have employed electrochemical quartz crystal nanogravimetry (EQCN), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS) to evaluate the extent of DNA damage expressed in terms of guanine oxidation yield (η) and changes in specific characteristics provided by these techniques. The effects of the interactions of Cr species with DNA were analyzed using a model calf thymus DNA (ctDNA) film on a gold electrode (Au@ctDNA) in different media, including: (i) Cr(VI), (ii) Cr(VI) reduced at -0.2V, (iii) Cr(III)+UV radiation+O 2 , and Cr(III), obtaining the η values: 7.4±1.4, 1.5±0.4, 1.1±0.31%, and 0%, respectively, thus quantifying the hazard posed. The EIS measurements have enabled utilizing the decrease in charge-transfer resistance (R ct ) for ferri/ferrocyanide redox probe at an Au@ctDNA electrode to assess the oxidative ctDNA damage by Cr(VI) species. In this case, circular dichroism indicates an extensive damage to the ctDNA hydrogen bonding. On the other hand, Cr(III) species have not induced any damage to ctDNA, although the EQCN measurements show an electrostatic binding to DNA. Copyright © 2017 Elsevier Inc. All rights reserved.

  10. Self-interaction and charge transfer in organic semiconductors

    Energy Technology Data Exchange (ETDEWEB)

    Koerzdoerfer, Thomas

    2009-12-18

    This work concentrates on the problem of self-interaction, which is one of the most serious problems of commonly used approximative density functionals. As a major result of this work, it is demonstrated that self-interaction plays a decisive role for the performance of different approximative functionals in predicting accurate electronic properties of organic molecular semiconductors. In search for a solution to the self-interaction problem, a new concept for correcting commonly used density functionals for self-interaction is introduced and applied to a variety of systems, spanning small molecules, extended molecular chains, and organic molecular semiconductors. It is further shown that the performance of functionals that are not free from self-interaction can vary strongly for different systems and observables of interest, thus entailing the danger of misinterpretation of the results obtained from those functionals. The underlying reasons for the varying performance of commonly used density functionals are discussed thoroughly in this work. Finally, this thesis provides strategies that allow to analyze the reliability of commonly used approximations to the exchange-correlation functional for particular systems of interest. This cumulative dissertation is divided into three parts. Part I gives a short introduction into DFT and its time-dependent extension (TDDFT). Part II provides further insights into the self-interaction problem, presents a newly developed concept for the correction of self-interaction, gives an introduction into the publications, and discusses their basic results. Finally, the four publications on self-interaction and charge-transfer in extended molecular systems and organic molecular semiconductors are collected in Part III. (orig.)

  11. Flavin Charge Transfer Transitions Assist DNA Photolyase Electron Transfer

    Science.gov (United States)

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

    2007-12-01

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

  12. Architecture Analysis of an FPGA-Based Hopfield Neural Network

    Directory of Open Access Journals (Sweden)

    Miguel Angelo de Abreu de Sousa

    2014-01-01

    Full Text Available Interconnections between electronic circuits and neural computation have been a strongly researched topic in the machine learning field in order to approach several practical requirements, including decreasing training and operation times in high performance applications and reducing cost, size, and energy consumption for autonomous or embedded developments. Field programmable gate array (FPGA hardware shows some inherent features typically associated with neural networks, such as, parallel processing, modular executions, and dynamic adaptation, and works on different types of FPGA-based neural networks were presented in recent years. This paper aims to address different aspects of architectural characteristics analysis on a Hopfield Neural Network implemented in FPGA, such as maximum operating frequency and chip-area occupancy according to the network capacity. Also, the FPGA implementation methodology, which does not employ multipliers in the architecture developed for the Hopfield neural model, is presented, in detail.

  13. Real-space Hopfield diagonalization of inhomogeneous dispersive media

    Science.gov (United States)

    Gubbin, Christopher R.; Maier, Stefan A.; De Liberato, Simone

    2016-11-01

    We introduce a real-space technique able to extend the standard Hopfield approach commonly used in quantum polaritonics to the case of inhomogeneous lossless materials interacting with the electromagnetic field. We derive the creation and annihilation polaritonic operators for the system normal modes as linear, space-dependent superpositions of the microscopic light and matter fields. We prove their completeness and invert the Hopfield transformation expressing the microscopic fields as functions of the polaritonic operators. As an example, we apply our approach to the case of a planar interface between vacuum and a polar dielectric, showing how we can consistently treat both propagative and surface modes, and express their nonlinear interactions, arising from phonon anharmonicity, as polaritonic scattering terms. We also show that our theory, including the proof of completeness, can be naturally extended to the case of dissipative materials.

  14. On the equivalence of Hopfield networks and Boltzmann Machines.

    Science.gov (United States)

    Barra, Adriano; Bernacchia, Alberto; Santucci, Enrica; Contucci, Pierluigi

    2012-10-01

    A specific type of neural networks, the Restricted Boltzmann Machines (RBM), are implemented for classification and feature detection in machine learning. They are characterized by separate layers of visible and hidden units, which are able to learn efficiently a generative model of the observed data. We study a "hybrid" version of RBMs, in which hidden units are analog and visible units are binary, and we show that thermodynamics of visible units are equivalent to those of a Hopfield network, in which the N visible units are the neurons and the P hidden units are the learned patterns. We apply the method of stochastic stability to derive the thermodynamics of the model, by considering a formal extension of this technique to the case of multiple sets of stored patterns, which may act as a benchmark for the study of correlated sets. Our results imply that simulating the dynamics of a Hopfield network, requiring the update of N neurons and the storage of N(N-1)/2 synapses, can be accomplished by a hybrid Boltzmann Machine, requiring the update of N+P neurons but the storage of only NP synapses. In addition, the well known glass transition of the Hopfield network has a counterpart in the Boltzmann Machine: it corresponds to an optimum criterion for selecting the relative sizes of the hidden and visible layers, resolving the trade-off between flexibility and generality of the model. The low storage phase of the Hopfield model corresponds to few hidden units and hence a overly constrained RBM, while the spin-glass phase (too many hidden units) corresponds to unconstrained RBM prone to overfitting of the observed data. Copyright © 2012 Elsevier Ltd. All rights reserved.

  15. Hopfield's Model of Patterns Recognition and Laws of Artistic Perception

    Science.gov (United States)

    Yevin, Igor; Koblyakov, Alexander

    The model of patterns recognition or attractor network model of associative memory, offered by J.Hopfield 1982, is the most known model in theoretical neuroscience. This paper aims to show, that such well-known laws of art perception as the Wundt curve, perception of visual ambiguity in art, and also the model perception of musical tonalities are nothing else than special cases of the Hopfield’s model of patterns recognition.

  16. Reptation Quantum Monte Carlo Calculation of Charge Transfer in The Na-Cl Dimer

    Science.gov (United States)

    Yao, Yi; Kanai, Yosuke

    2015-03-01

    Reptation Quantum Monte Carlo (QMC) calculations are performed to describe the charge transfer behavior in a NaCl dimer. Influence of fixed node approximation on the charge transfer was examined by obtaining electron density via reputation QMC. We employ Slater-Jastrow wavefunction as the trial wavefunction, and the fermion nodes are obtained from single particle orbitals of Hartree-Fock and Density Functional Theory (DFT) with several exchange-correlation approximations. We will discuss our QMC results together with DFT calculations to give insights into observed dependence of the charge transfer behavior on the fixed-node approximation.

  17. Ionic manipulation of charge-transfer and photodynamics of [60]fullerene confined in pyrrolo-tetrathiafulvalene cage

    DEFF Research Database (Denmark)

    Bähring, Steffen; Larsen, Karina R; Supur, Mustafa

    2017-01-01

    A cage molecule incorporating three electron donating monopyrrolotetrathiafulvalene units was synthesised to host electron accepting [60]fullerenes. Formation of a strong 1 : 1 donor-acceptor (D-A) complex C60⊂1 was confirmed by solid state X-ray analysis as well as (1)H NMR and absorption...... spectroscopic analyses of the arising charge-transfer (CT) band (λ = 735 nm, ε ≈ 840 M(-1) cm(-1)). Inserting Li(+) inside the [60]fullerene increased the binding 28-fold (Ka = 3.7 × 10(6) M(-1)) and a large bathochromic shift of the CT band to the near infrared (NIR) region (λ = 1104 nm, ε ≈ 4800 M(-1) cm(-1...

  18. Analysis of Charge Transfer for in Situ Li Intercalated Carbon Nanotubes

    KAUST Repository

    Rana, Kuldeep

    2012-05-24

    Vertically aligned carbon nanotube (VA-CNT) arrays have been synthesized with lithium (Li) intercalation through an alcohol-catalyzed chemical vapor deposition technique by using a Li-containing catalyst. Scanning electron microscopy images display that synthesized carbon nanotubes (CNTs) are dense and vertically aligned. The effect of the Li-containing catalyst on VA-CNTs has been studied by using Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and electron energy loss spectroscopy (EELS). XPS results show the change in binding energy of Li 1s and C 1s peaks, which indicates that Li is inserted in VA-CNTs during growth. Analysis of Raman spectra reveals that the G-band profile of CNTs synthesized with the Li-containing catalyst is shifted, suggesting an electronic interaction between Li and neighboring C atoms of the CNTs. The EELS spectra of the C K edge and Li K edge from CNTs also confirmed that Li is inserted into CNTs during synthesis. We have performed ab inito calculations based on density functional theory for a further understanding of the structural and electronic properties of Li intercalated CNTs, especially addressing the controversial charge-transfer state between Li and C. © 2012 American Chemical Society.

  19. Thickness dependent charge transfer states and dark carriers density in vacuum deposited small molecule organic photocell

    Science.gov (United States)

    Shekhar, Himanshu; Tzabari, Lior; Solomeshch, Olga; Tessler, Nir

    2016-10-01

    We have investigated the influence of the active layer thickness on the balance of the internal mechanisms affecting the efficiency of copper phthalocyanine - fullerene (C60) based vacuum deposited bulk heterojunction organic photocell. We fabricated a range of devices for which we varied the thickness of the active layer from 40 to 120 nm and assessed their performance using optical and electrical characterization techniques. As reported previously for phthalocyanine:C60, the performance of the device is highly dependent on the active layer thickness and of all the thicknesses we tried, the 40 nm thin active layer device showed the best solar cell characteristic parameters. Using the transfer matrix based optical model, which includes interference effects, we calculated the optical power absorbed in the active layers for the entire absorption band, and we found that this cannot explain the trend with thickness. Measurement of the cell quantum efficiency as a function of light intensity showed that the relative weight of the device internal processes changes when going from 40 nm to 120 nm thick active layer. Electrical modeling of the device, which takes different internal processes into account, allowed to quantify the changes in the processes affecting the generation - recombination balance. Sub gap external quantum efficiency and morphological analysis of the surface of the films agree with the model's result. We found that as the thickness grows the density of charge transfer states and of dark carriers goes up and the uniformity in the vertical direction is reduced.

  20. Engineering Interfacial Charge Transfer in CsPbBr3 Perovskite Nanocrystals by Heterovalent Doping

    KAUST Repository

    Begum, Raihana

    2016-12-17

    Since compelling device efficiencies of perovskite solar cells have been achieved, investigative efforts have turned to understand other key challenges in these systems, such as engineering interfacial energy-level alignment and charge transfer (CT). However, these types of studies on perovskite thin-film devices are impeded by the morphological and compositional heterogeneity of the films and their ill-defined surfaces. Here, we use well-defined ligand-protected perovskite nanocrystals (NCs) as model systems to elucidate the role of heterovalent doping on charge-carrier dynamics and energy level alignment at the interface of perovskite NCs with molecular acceptors. More specifically, we develop an in situ doping approach for colloidal CsPbBr3 perovskite NCs with heterovalent Bi3+ ions by hot injection to precisely tune their band structure and excited-state dynamics. This synthetic method allowed us to map the impact of doping on CT from the NCs to different molecular acceptors. Using time-resolved spectroscopy with broadband capability, we clearly demonstrate that CT at the interface of NCs can be tuned and promoted by metal ion doping. We found that doping increases the energy difference between states of the molecular acceptor and the donor moieties, subsequently facilitating the interfacial CT process. This work highlights the key variable components not only for promoting interfacial CT in perovskites, but also for establishing a higher degree of precision and control over the surface and the interface of perovskite molecular acceptors.

  1. Ag@AgCl QDs decorated g-C3N4 nanoplates: The photoinduced charge transfer behavior under visible light and full arc irradiation

    Science.gov (United States)

    Li, Junqi; Hao, Hongjuan; Zhou, Jian; Li, Weijie; Lei, Nan; Guo, Liu

    2017-11-01

    The quantum dots (QDs) Ag@AgCl decorated g-C3N4 nanoplates was synthesized via a facile oil-in-water self-assembly method, which possessed high dispersion by characterization of scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The as-obtained Ag@AgCl/g-C3N4 nano-heterostructure contained a wide band gap of AgCl nanoparticles (NPs), the surface plasmon resonance (SPR) of Ag NPs and a narrow band gap of g-C3N4 nanoplates. The AgCl NPs with a wide band gap was excited under UV-light, which played a key role on the photoinduced charge transfer of Ag@AgCl/g-C3N4. Under the visible light irradiation, the electrons transfered to the CB of AgCl (electron acceptor) and the holes lefted in the VB of g-C3N4. Nevertheless, under the full arc irradiation, the electrons and holes stayed in the CB of g-C3N4 and VB of AgCl, respectively, then the AgCl was electron donor. The photoinduced charge transfer behavior of Ag@AgCl/g-C3N4 was verified by the photoelectrochemical measurements under the visible light and the full arc irradiation. The results showed that the difference of charge transfer behavior under visible light and the full arc influences on the photoinduced charge transfer ability, further leading to changing the water redox potential in the Ag@AgCl/g-C3N4 nano-heterostructure

  2. Charge-Transfer in Time-Dependent Density Functional Theory: Insights from the Asymmetric Hubbard Dimer

    CERN Document Server

    Fuks, J I

    2013-01-01

    We show that an asymmetric two-fermion two-site Hubbard model illustrates the essential features of long-range charge-transfer dynamics in a real-space molecule. We apply a resonant field that transfers one fermion from one site to the other. Via constrained search we find the exact ground-state exchange-correlation functional, and use it to propagate the Kohn-Sham system, giving the first "adiabatically-exact" calculation of time-resolved charge-transfer. This propagation fails to properly transfer charge. We analyze why by comparing the exact and adiabatically-exact potentials and discuss the role of the derivative discontinuity. The implication for real-space molecules is that even the best possible adiabatic approximation, despite capturing non-local step features relevant to dissociation and charge-transfer excitations, cannot capture fully time-resolved charge-transfer dynamics.

  3. Delocalization and dielectric screening of charge transfer states in organic photovoltaic cells

    National Research Council Canada - National Science Library

    Bernardo, B; Cheyns, D; Verreet, B; Schaller, R D; Rand, B P; Giebink, N C

    2014-01-01

    Charge transfer (CT) states at a donor-acceptor heterojunction have a key role in the charge photogeneration process of organic solar cells, however, the mechanism by which these states dissociate efficiently into free...

  4. Charge-transfer stabilization of molecular bicimers: ion pair formation in diarylmethanes

    Energy Technology Data Exchange (ETDEWEB)

    Locke, R.J.; Modiano, S.H.; Lim, E.C.

    1988-04-07

    The authors demonstrate here that the bicimer of aromatic hydrocarbons is stabilized largely by charge-transfer interactions. The bicimer is a dimeric species formed by the association of two identical, electronically excited molecules.

  5. Positronium Inhibition and Quenching by Organic Electron Acceptors and Charge Transfer Complexes

    DEFF Research Database (Denmark)

    Jansen, P.; Eldrup, Morten Mostgaard; Jensen, Bror Skytte

    1975-01-01

    Positron lifetime measurements were performed on a series of organic electron acceptors and charge-transfer complexes in solution. The acceptors cause both positronium (Ps) inhibition (with maybe one exception) and quenching, but when an acceptor takes part in a charge-transfer complex...... in terms of the spur reaction model of Ps formation. Correlation was also made to gas phase reaction between electron acceptors and free electron, as well as to pulse radiolysis data....

  6. Femtosecond Charge Transfer Dynamics of a Modified DNA Base: 2-Aminopurine in Complexes with Nucleotides

    OpenAIRE

    Fiebig, Torsten; Wan, Chaozhi; Zewail, Ahmed H.

    2002-01-01

    As a fluorescent isomer of adenine, 2-aminopurine (Ap) is a powerful probe of DNA dynamics and DNA-mediated charge transfer processes. Here, we report studies with femtosecond resolution of the excited-state dynamics of Ap in various solvents and in bimolecular complexes with nucleotides. Using time-resolved transient absorption and fluorescence up-conversion methods we identify charge transfer as the origin for the quenching of the Ap fluorescence by all four DNA nucleotides. The direction o...

  7. Charge Transfer Interaction and Hydrogen Bonding between Vitamine K1 and Dihydrovitamine K1

    Science.gov (United States)

    Nagahira, Yukio; Matsuki, Kazunori; Fukutome, Hideo

    1981-01-01

    We studied visible and infrared spectra, in particular their temperature dependence, of Vitamine K1 oil dissolving dihydrovitamine K1. Vitamine K1 and dihydrovitamine K1 were found to form charge transfer complexes and hydrogen bonds in the mixture. A co-crystal of Dihydrovitamine K1 and Vitamine K1 with charge transfer interaction and hydrogen bonding was shown to grow in a narrow temperature range near -20°C.

  8. Charge transfer in the electron donor-acceptor complexes of a meso-phenol BODIPY dye with chloranils and fullerenes.

    Science.gov (United States)

    Karmakar, Animesh; Chaudhuri, Tandrima; Mula, Soumyaditya; Chattopadhyay, Subrata

    2015-02-25

    UV-Vis spectral investigations of electron donor-acceptor complexes of laser dye 2,6-Diethyl-4,4-difluoro-1,3,5,7-tetramethyl-8-(4'-hydroxyphenyl)-4-bora-3a,4a-diaza-s-indecene (1c) with chloranils and fullerenes are reported in toluene medium. Well defined charge transfer (CT) absorption bands have been located in the visible region. Oscillator strengths, transition dipole and resonance energies of the CT complexes have been estimated. Vertical ionization potential of 1c has been determined utilizing Mulliken's equation. A possible mechanism for the interaction between electronic subsystems of chloranils, [60]- and [70]fullerenes with three different BODIPY dyes (1a, 1b and 1c shown in Fig. 1) have been discussed in comparing the parameters like degree of charge transfer and binding constant in nonpolar toluene. Comparison of 1c complexes is done with DFT/B3LYP/6-31G optimized gas phase geometries. Copyright © 2014 Elsevier B.V. All rights reserved.

  9. Two-dimensional CsPbBr3/PCBM heterojunctions for sensitive, fast and flexible photodetectors boosted by charge transfer

    Science.gov (United States)

    Shen, Yalong; Yu, Dejian; Wang, Xiong; Huo, Chengxue; Wu, Ye; Zhu, Zhengfeng; Zeng, Haibo

    2018-02-01

    Inorganic halide perovskites exhibited promising potentials for high-performance wide-band photodetectors (PDs) due to their high light absorption coefficients, long carrier diffusion length and wide light absorption ranges. Here, we report two-dimensional (2D) CsPbBr3/PCBM heterojunctions for sensitive, fast and flexible PDs, whose performances can be greatly boosted by the charge transfer through the energy-aligned interface. The 2D CsPbBr3 nanosheets with high crystallinity were fabricated via a simple solution-process at room temperature, and then assembled into flexible heterojunctions films with polymerphenyl-C61-butyric acid methyl ester (PCBM). Significantly, the efficient and fast charge transfer at the heterojunctions interface was evidenced by the obvious photoluminescence quenching and variation of recombination dynamics. Subsequently, such heterojunctions PD exhibited an enhanced responsivity of 10.85 A W‑1 and an ultrahigh detectivity of 3.06 × 1013 Jones. In addition, the PD shows a broad linear dynamic range of 73 dB, a fast response speed with rise time of 44 μs and decay time of 390 μs, respectively. Moreover, the PD lying on polyethylene terephthalate substrates exhibited an outstanding mechanical flexibility and a robust electrical stability. These results could provide a new avenue for integration of 2D perovskites and organic functional materials and for high-performance flexible PDs.

  10. High performance organic integrated device with ultraviolet photodetective and electroluminescent properties consisting of a charge-transfer-featured naphthalimide derivative

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Hanyu; Wang, Xu; Yu, Junsheng, E-mail: luzhiyun@scu.edu.cn, E-mail: jsyu@uestc.edu.cn [State Key Laboratory of Electronic Thin Films and Integrated Devices, School of Optoelectronic Information, University of Electronic Science and Technology of China, Chengdu 610054 (China); Zhou, Jie; Lu, Zhiyun, E-mail: luzhiyun@scu.edu.cn, E-mail: jsyu@uestc.edu.cn [College of Chemistry, Sichuan University, Chengdu 610064 (China)

    2014-08-11

    A high performance organic integrated device (OID) with ultraviolet photodetective and electroluminescent (EL) properties was fabricated by using a charge-transfer-featured naphthalimide derivative of 6-(3,5-bis-[9-(4-t-butylphenyl)-9H-carbazol-3-yl]-phenoxy)-2- (4-t-butylphenyl)-benzo[de]isoquinoline-1,3-dione (CzPhONI) as the active layer. The results showed that the OID had a high detectivity of 1.5 × 10{sup 11} Jones at −3 V under the UV-350 nm illumination with an intensity of 0.6 mW/cm{sup 2}, and yielded an exciplex EL light emission with a maximum brightness of 1437 cd/m{sup 2}. Based on the energy band diagram, both the charge transfer feature of CzPhONI and matched energy level alignment were responsible for the dual ultraviolet photodetective and EL functions of OID.

  11. Charge Transfer across Quantum Dot-Oxide Interfaces for High-Efficiency Photovoltaics

    Science.gov (United States)

    Bonn, Mischa

    Metal oxides constitute robust and relatively cheap semiconductor materials that are finding increasing applications in opto-electronics, but their band gaps are typically prohibitively wide for the generation of free charges through the absorption of visible light. Several approaches have been developed to circumvent this drawback. Specifically, the sensitization of mesoporous oxides by semiconductor quantum dot (QD) nanocrystals represents a promising route for the development of low-cost photovoltaics in QD sensitized solar cells. In addition to their tuneable band gap, QDs have the ability to generate multiple charge carriers from single photons by a process called carrier multiplication (CM), which potentially provides a means towards high-efficiency photovoltaics. Although CM has been widely interrogated in colloidal QDs in solution, the collection of those multiple charge carriers at oxide electrodes has not been clearly elucidated. The contribution of CM towards the overall device performance is ultimately determined by a competition between transfer to the electrode material and charge recombination within the QDs. We report interfacial electron transfer dynamics from quantum dots grown directly onto mesoporous oxide films. Such systems are well-suited for achieving efficient multiple charge transfer by CM, as electron transfer from QD-to-oxide is substantially faster than charge recombination. However, despite CM occurring in the QD, only one electron is transferred to the oxide. This seemingly counterintuitive result can be understood by noting that efficient hot electron transfer at the QD-oxide interface can compete with CM within the QDs. Hot electron transfer is observed to occur on sub-100 fs timescales, nulling the CM efficiency. Implications of these results for solar energy conversion are discussed.

  12. Stability of Delayed Hopfield Neural Networks with Variable-Time Impulses

    Directory of Open Access Journals (Sweden)

    Yangjun Pei

    2014-01-01

    Full Text Available In this paper the globally exponential stability criteria of delayed Hopfield neural networks with variable-time impulses are established. The proposed criteria can also be applied in Hopfield neural networks with fixed-time impulses. A numerical example is presented to illustrate the effectiveness of our theoretical results.

  13. Genetic Algorithm for Restricted Maximum k-Satisfiability in the Hopfield Network

    Directory of Open Access Journals (Sweden)

    Mohd Shareduwan Bin Mohd Kasihmuddin

    2016-12-01

    Full Text Available The restricted Maximum k-Satisfiability MAX- kSAT is an enhanced Boolean satisfiability counterpart that has attracted numerous amount of research. Genetic algorithm has been the prominent optimization heuristic algorithm to solve constraint optimization problem. The core motivation of this paper is to introduce Hopfield network incorporated with genetic algorithm in solving MAX-kSAT problem. Genetic algorithm will be integrated with Hopfield network as a single network. The proposed method will be compared with the conventional Hopfield network. The results demonstrate that Hopfield network with genetic algorithm outperforms conventional Hopfield networks. Furthermore, the outcome had provided a solid evidence of the robustness of our proposed algorithms to be used in other satisfiability problem.

  14. Absence of superconductivity and valence bond order in the Hubbard-Heisenberg model for organic charge-transfer solids.

    Science.gov (United States)

    Gomes, N; Clay, R T; Mazumdar, S

    2013-09-25

    A frustrated, effective ½-filled band Hubbard-Heisenberg model has been proposed for describing the strongly dimerized charge-transfer solid families κ-(ET)2X and Z[Pd(dmit)2]2. In addition to showing unconventional superconductivity, these materials also exhibit antiferromagnetism, candidate spin-liquid phases, and, in the case of Z=EtMe3P, a spin-gapped phase that has sometimes been referred to as a valence bond solid. We show that neither superconductivity nor the valence bond order phase occurs within the Hubbard-Heisenberg model. We suggest that a description based on ¼-filling, that is reached when the carrier concentration per molecule instead of per dimer is considered, thus may be appropriate.

  15. Absence of superconductivity and valence bond order in the Hubbard-Heisenberg model for organic charge-transfer solids

    Science.gov (United States)

    Gomes, N.; Clay, R. T.; Mazumdar, S.

    2013-09-01

    A frustrated, effective \\frac{1}{2}-filled band Hubbard-Heisenberg model has been proposed for describing the strongly dimerized charge-transfer solid families κ-(ET)2X and Z[Pd(dmit)2]2. In addition to showing unconventional superconductivity, these materials also exhibit antiferromagnetism, candidate spin-liquid phases, and, in the case of Z=EtMe3P, a spin-gapped phase that has sometimes been referred to as a valence bond solid. We show that neither superconductivity nor the valence bond order phase occurs within the Hubbard-Heisenberg model. We suggest that a description based on \\frac{1}{4}-filling, that is reached when the carrier concentration per molecule instead of per dimer is considered, thus may be appropriate.

  16. Dynamical correlations in one-dimensional charge-transfer insulators

    OpenAIRE

    Penc, Karlo; Stephan, Walter

    2000-01-01

    The single-particle spectral function and the density response of a two band Emery model for CuO chains is calculated for large on-site Cu repulsion U and large on-site energy difference \\Delta. For U>>U-\\Delta>>t the eigenfunctions are products of charge and spin parts, which allows analytical calculation of spectral functions in that limit. For other parameters numerical diagonalization is used. The low energy hole carriers are shown to be the one-dimensional analogs of the Zhang-Rice singl...

  17. Photophysical investigations on supramolecular fullerene/phthalocyanine charge transfer interactions in solution.

    Science.gov (United States)

    Ray, Anamika; Pal, Haridas; Bhattacharya, Sumanta

    2014-01-03

    The photophysical features of non-covalently linked fullerenes C60 and C70 with a designed free-base phthalocyanine, namely, 2,3,9,10,16,17,23,24-octakis-(octyloxy)-29H,31H-phthalocyanine (1) have been investigated employing various spectroscopic tools like UV-vis absorption spectrophotometry, steady state and time resolved fluorescence along with proton NMR measurements in toluene. The ground state interaction between fullerenes and 1 is nicely demonstrated with the appearance of well defined charge transfer absorption bands in the visible region of the electronic spectra. Steady state fluorescence experiment reveals efficient quenching of the excited singlet state of 1 in presence of both C60 and C70. The average values of binding constants for the non-covalent complexes of C60 and C70 with 1 are determined to be ~18,150 and ~32,000 dm(3) mol(-1), respectively. The magnitude of K suggests that 1 preferentially binds C70 in comparison to C60 although average value of selectivity in binding is measured to be low (~1.75). Time resolved emission measurements establish photoinduced energy transfer from the excited singlet state of 1 to fullerene in toluene. Measurements of free energy of electron transfer and free energy of radical ion-pair formation elicit that C70/1 complex is stabilized more in comparison to C60/1 complex regarding generation of charge-separated state. Proton NMR studies provide very good support in favor of effective ground state complexation between fullerenes and 1. Semi empirical theoretical calculations on fullerene/1 systems in vacuo substantiate the stronger binding between C70 and 1 in comparison to C60/1 system in terms of heat of formation value of the respective complexes, and determine the orientation of bound guest (here C70) towards the plane of 1 during complexation. Copyright © 2013 Elsevier B.V. All rights reserved.

  18. Efficient Hot Electron Transfer by Plasmon Induced Interfacial Charge Transfer Transition

    Science.gov (United States)

    Lian, Tianquan

    Surface plasmon resonance in metal nanostructures has been widely used to enhance the efficiency of semiconductors and/or molecular chromophore based solar energy conversion devices by increasing the absorption or energy transfer rate through the enhanced local field strength. In more recent years, it has been shown that excitation of plasmons in metal nanostructures can lead to the injection of hot electrons into semiconductors and enhanced photochemistry. This novel mechanism suggests that plasmonic nanostructures can potentially function as a new class of widely tunable and robust light harvesting materials for solar energy conversion. However, plasmon-induced hot electron injections from metal to semiconductor or molecules are still inefficient because of the competing ultrafast hot electron relaxation processes within the metallic domain. In this paper we discuss a recent study on the plasmon-exciton interaction mechanisms in colloidal quantum-confined semiconductor-gold nanorod heterostructures. In CdSe NRs with Au tips, the distinct plasmon band of the Au nanoparticles was completely damped due to strong interaction with the CdSe domain. Using transient absorption spectroscopy, we show that optical excitation of plasmons in the Au tip leads to efficient hot electron injection into the semiconductor nanorod. In the presence of sacrificial electron donors, this plasmon induced hot electron transfer process can be utilized to drive photoreduction reactions under continuous illumination. We propose that the strong metal/semiconductor coupling in CdSe/Au hetersostructures leads to a new pathway for this surprising efficient hot electron transfer. In this plasmon induced interfacial charge transfer transition (PICTT) the a plasmon decay by direct excitation of an electron from the metal to semiconductor, bypassing the competition with hot electron transfer in metal. Ongoing studies are examining the generality of this mechanism and exploring possible approaches

  19. Role of the charge transfer state in organic donor-acceptor solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Deibel, Carsten; Strobel, Thomas [Experimental Physics VI, Julius-Maximilians-University of Wuerzburg (Germany); Dyakonov, Vladimir [Experimental Physics VI, Julius-Maximilians-University of Wuerzburg (Germany); Bavarian Centre for Applied, Energy Research (ZAE Bayern), Wuerzburg (Germany)

    2010-10-01

    Charge transfer complexes are interfacial charge pairs residing at the donor-acceptor heterointerface in organic solar cell. Experimental evidence shows that it is crucial for the photovoltaic performance, as both photocurrent and open circuit voltage directly depend on it. For charge photogeneration, charge transfer complexes represent the intermediate but essential step between exciton dissociation and charge extraction. Recombination of free charges to the ground state is via the bound charge transfer state before being lost to the ground state. In terms of the open circuit voltage, its maximum achievable value is determined by the energy of the charge transfer state. An important question is whether or not maximum photocurrent and maximum open circuit voltage can be achieved simultaneously. The impact of increasing the CT energy - in order to raise the open circuit voltage, but lowering the kinetic excess energy of the CT complexes at the same time - on the charge photogeneration will accordingly be discussed. Clearly, the fundamental understanding of the processes involving the charge transfer state is essential for an optimisation of the performance of organic solar cells. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-10-17

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

  1. Ultrafast holography and transient absorption spectroscopy in charge-transfer polymers

    Energy Technology Data Exchange (ETDEWEB)

    McBranch, D.W.; Maniloff, E.S. [Los Alamos National Lab., NM (United States); Vacar, D.; Heeger, A.J. [Univ. of California, Santa Barbara, CA (United States). Institute for Polymers and Organic Solids

    1997-10-01

    Charge-transfer polymers are a new class of nonlinear optical materials which can be used for generating femtosecond holographic gratings. Using semiconducting polymers sensitized with varying concentrations of C{sub 60}, holographic gratings were recorded by individual ultrafast laser pulses; the diffraction efficiency and time decay of the gratings were measured using non-degenerate four-wave mixing. Using a figure of merit for dynamic data processing, the temporal diffraction efficiency, this new class of materials exhibits between two and 12 orders of magnitude higher response than previous reports. The charge transfer range at polymer/C{sub 60} interfaces was further studied using transient absorption spectroscopy. The fact that charge-transfer occurs in the picosecond-time scale in bilayer structures (thickness 200 {angstrom}) implies that diffusion of localized excitations to the interface is not the dominant mechanism; the charge transfer range is a significant fraction of the film thickness. From analysis of the excited state decay curves, we estimate the charge transfer range to be 80 {angstrom} and interpret that range as resulting from quantum delocalization of the photoexcitations.

  2. Fractional Hopfield Neural Networks: Fractional Dynamic Associative Recurrent Neural Networks.

    Science.gov (United States)

    Pu, Yi-Fei; Yi, Zhang; Zhou, Ji-Liu

    2017-10-01

    This paper mainly discusses a novel conceptual framework: fractional Hopfield neural networks (FHNN). As is commonly known, fractional calculus has been incorporated into artificial neural networks, mainly because of its long-term memory and nonlocality. Some researchers have made interesting attempts at fractional neural networks and gained competitive advantages over integer-order neural networks. Therefore, it is naturally makes one ponder how to generalize the first-order Hopfield neural networks to the fractional-order ones, and how to implement FHNN by means of fractional calculus. We propose to introduce a novel mathematical method: fractional calculus to implement FHNN. First, we implement fractor in the form of an analog circuit. Second, we implement FHNN by utilizing fractor and the fractional steepest descent approach, construct its Lyapunov function, and further analyze its attractors. Third, we perform experiments to analyze the stability and convergence of FHNN, and further discuss its applications to the defense against chip cloning attacks for anticounterfeiting. The main contribution of our work is to propose FHNN in the form of an analog circuit by utilizing a fractor and the fractional steepest descent approach, construct its Lyapunov function, prove its Lyapunov stability, analyze its attractors, and apply FHNN to the defense against chip cloning attacks for anticounterfeiting. A significant advantage of FHNN is that its attractors essentially relate to the neuron's fractional order. FHNN possesses the fractional-order-stability and fractional-order-sensitivity characteristics.

  3. Electrochromic devices based on wide band-gap nanocrystalline semiconductors functionalized with mononuclear charge transfer compounds

    DEFF Research Database (Denmark)

    Biancardo, M.; Argazzi, R.; Bignozzi, C.A.

    2006-01-01

    A series of ruthenium and iron mononuclear complexes were prepared and their spectroeletrochemical behavior characterized oil Optically Transparent Thin Layer Electrodes (OTTLE) and on Fluorine Doped SnO2 (FTO) conductive glasses coated with Sb-doped nanocrystalline SnO2. These systems display...... a reversible electrochemical response and offer potential application in electrochromic devices. On SnO2 films distinct spectral changes are observed in a narrow potential range (-0.5/0.9 V vs SCE) with switching times of the order of 0.8 s. (c) 2005 Elsevier B.V. All rights reserved....

  4. Intersystem crossing mediated by photoinduced intramolecular charge transfer: julolidine-anthracene molecules with perpendicular pi systems.

    Science.gov (United States)

    Dance, Zachary E X; Mickley, Sarah M; Wilson, Thea M; Ricks, Annie Butler; Scott, Amy M; Ratner, Mark A; Wasielewski, Michael R

    2008-05-08

    Time-resolved electron paramagnetic resonance studies show that the primary mechanism of triplet formation following photoexcitation of julolidine-anthracene molecules linked by a single bond and having perpendicular pi systems is a spin-orbit, charge-transfer intersystem crossing mechanism (SOCT-ISC). This mechanism depends on the degree of charge transfer from julolidine to anthracene, the dihedral angle (theta1) between their pi systems, and the magnitude of the electronic coupling between julolidine and anthracene. We compare 4-(9-anthracenyl)-julolidine with the more sterically encumbered 4-(9-anthracenyl)-3,5-dimethyljulolidine and find that fixing theta1 congruent with 90 degrees serves to enhance SOCT-ISC by increasing the change in orbital angular momentum accompanying charge transfer. Given that the requirements for the SOCT-ISC mechanism are quite general, we expect it to occur in a variety of electron donor-acceptor systems.

  5. Organic narrowband near-infrared photodetectors based on intermolecular charge-transfer absorption

    Science.gov (United States)

    Siegmund, Bernhard; Mischok, Andreas; Benduhn, Johannes; Zeika, Olaf; Ullbrich, Sascha; Nehm, Frederik; Böhm, Matthias; Spoltore, Donato; Fröb, Hartmut; Körner, Christian; Leo, Karl; Vandewal, Koen

    2017-06-01

    Blending organic electron donors and acceptors yields intermolecular charge-transfer states with additional optical transitions below their optical gaps. In organic photovoltaic devices, such states play a crucial role and limit the operating voltage. Due to its extremely weak nature, direct intermolecular charge-transfer absorption often remains undetected and unused for photocurrent generation. Here, we use an optical microcavity to increase the typically negligible external quantum efficiency in the spectral region of charge-transfer absorption by more than 40 times, yielding values over 20%. We demonstrate narrowband detection with spectral widths down to 36 nm and resonance wavelengths between 810 and 1,550 nm, far below the optical gap of both donor and acceptor. The broad spectral tunability via a simple variation of the cavity thickness makes this innovative, flexible and potentially visibly transparent device principle highly suitable for integrated low-cost spectroscopic near-infrared photodetection.

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

    KAUST Repository

    Gruenewald, Marco

    2015-02-11

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

  7. Resonant core spectroscopies of the charge transfer interactions between C60 and the surfaces of Au(111), Ag(111), Cu(111) and Pt(111)

    Science.gov (United States)

    Gibson, Andrew J.; Temperton, Robert H.; Handrup, Karsten; O'Shea, James N.

    2017-03-01

    Charge transfer interactions between C60 and the metal surfaces of Ag(111), Cu(111), Au(111) and Pt(111) have been studied using synchrotron-based photoemission, resonant photoemission and X-ray absorption spectroscopies. By placing the X-ray absorption and valence band spectra on a common binding energy scale, the energetic overlap of the unoccupied molecular orbitals with the density of states of the underlying metal surface have been assessed in the context of possible charge transfer pathways. Resonant photoemission and resonant Auger data, measuring the valence region as a function of photon energy for C60 adsorbed on Au(111) reveals three constant high kinetic energy features associated with Auger-like core-hole decay involving an electron transferred from the surface to the LUMO of the molecule and electrons from the three highest occupied molecular orbitals, respectively and in the presence of ultra-fast charge transfer of the originally photoexcited molecule to the surface. Data for the C60/Ag(111) surface reveals an additional Auger-like feature arising from a core-hole decay process involving more than one electron transferred from the surface into the LUMO. An analysis of the relative abundance of these core-hole decay channels estimates that on average 2.4 ± 0.3 electrons are transferred from the Ag(111) surface into the LUMO. A core-hole clock analysis has also been applied to assess the charge transfer coupling in the other direction, from the molecule to the Au(111) and Ag(111) surfaces. Resonant photoemission and resonant Auger data for C60 molecules adsorbed on the Pt(111) and Cu(111) surfaces are shown to exhibit no super-Auger features, which is attributed to the strong modification of the unoccupied molecular orbitals arising from stronger chemical coupling of the molecule to the surface.

  8. Stability analysis of fractional-order Hopfield neural networks with time delays.

    Science.gov (United States)

    Wang, Hu; Yu, Yongguang; Wen, Guoguang

    2014-07-01

    This paper investigates the stability for fractional-order Hopfield neural networks with time delays. Firstly, the fractional-order Hopfield neural networks with hub structure and time delays are studied. Some sufficient conditions for stability of the systems are obtained. Next, two fractional-order Hopfield neural networks with different ring structures and time delays are developed. By studying the developed neural networks, the corresponding sufficient conditions for stability of the systems are also derived. It is shown that the stability conditions are independent of time delays. Finally, numerical simulations are given to illustrate the effectiveness of the theoretical results obtained in this paper. Copyright © 2014 Elsevier Ltd. All rights reserved.

  9. Single and double charge transfer of He(2+) ions with molecules at near-thermal energies

    Science.gov (United States)

    Tosh, R. E.; Johnsen, R.

    1993-01-01

    Rate coefficients were measured for charge-transfer reactions of He(2+) ions with H2, N2, O2, CO, CO2, and H2O. The experiments were carried out using a selected-ion drift-tube mass spectrometer. Total rate coefficients are found to be very large and are generally close to the limiting Langevin capture rate coefficients or the corresponding ADO-model (Su and Bowers, 1973) coefficients. The product-ion spectra indicate that both single and double charge transfer and possibly transfer ionization occur in these reactions.

  10. Multivariate Cryptography Based on Clipped Hopfield Neural Network.

    Science.gov (United States)

    Wang, Jia; Cheng, Lee-Ming; Su, Tong

    2018-02-01

    Designing secure and efficient multivariate public key cryptosystems [multivariate cryptography (MVC)] to strengthen the security of RSA and ECC in conventional and quantum computational environment continues to be a challenging research in recent years. In this paper, we will describe multivariate public key cryptosystems based on extended Clipped Hopfield Neural Network (CHNN) and implement it using the MVC (CHNN-MVC) framework operated in space. The Diffie-Hellman key exchange algorithm is extended into the matrix field, which illustrates the feasibility of its new applications in both classic and postquantum cryptography. The efficiency and security of our proposed new public key cryptosystem CHNN-MVC are simulated and found to be NP-hard. The proposed algorithm will strengthen multivariate public key cryptosystems and allows hardware realization practicality.

  11. Hopfield neural network implementation of the optimal CDMA multiuser detector.

    Science.gov (United States)

    Kechriotis, G I; Manolakos, E S

    1996-01-01

    We investigate the application of Hopfield neural networks (HNN's) to the problem of multiuser detection in spread spectrum/CDMA (code division multiple access) communication systems. It is shown that the NP-complete problem of minimizing the objective function of the optimal multiuser detector (OMD) can be translated into minimizing an HNN "energy" function, thus allowing to take advantage of the ability of HNN's to perform very fast gradient descent algorithms in analog hardware and produce in real-time suboptimal solutions to hard combinatorial optimization problems. The performance of the proposed HNN receiver is evaluated via computer simulations and compared to that of other suboptimal schemes as well as to that of the OMD for both the synchronous and the asynchronous CDMA transmission cases. It is shown that the HNN detector exhibits a number of attractive properties and that it provides a powerful generalization of a well-known and extensively studied suboptimal scheme, namely the multistage detector.

  12. Reptation Quantum Monte Carlo calculation of charge transfer: The Na-Cl dimer

    Science.gov (United States)

    Yao, Yi; Kanai, Yosuke

    2015-01-01

    The phenomenon of ion pairing in aqueous solutions is of widespread importance in chemistry and physics, and charge transfer between the ions plays a significant role. We examine the performance of quantum Monte Carlo (QMC) calculations for describing the charge transfer behavior in a NaCl dimer. The influence of the fermion nodes is investigated by obtaining the electron density using the reptation Monte Carlo approach. The fermion nodes are given by single-particle orbitals in Slater-Jastrow trial wavefunctions. We consider the single-particle orbitals from Hartree-Fock and density functional theory calculations with several exchange-correlation approximations. Appreciable dependence of the charge transfer on the fixed-node approximation was found although the total energy was found to be rather insensitive. Our work shows that a careful examination of the fixed-node approximation is necessary for quantifying charge transfer in QMC calculations even when other properties such as reaction energetics are insensitive to the approximation.

  13. On the relation between local and charge-transfer exciton bindingenergies in organic photovoltaic materials

    NARCIS (Netherlands)

    de Gier, Hilde Dorothea; Braam, Henderika; Havenith, Remco

    2015-01-01

    In organic photovoltaic devices two types of excitons can be generated for which different binding energies can be defined: the binding energy of the local exciton generated immediately after light absorption on the polymer and the binding energy of the charge-transfer exciton generated through the

  14. The synthesis of organic charge transfer hetero-microtubules by crack welding.

    Science.gov (United States)

    Kim, J; Chung, J; Hyon, J; Kwon, T; Seo, C; Nam, J; Kang, Y

    2014-09-14

    The strain-induced cracks in organic microtubules composed of an organic charge transfer (CT) complex of 1,2,4,5-tetracyanobenzene (TCNB) and naphthalene were selectively welded via the formation of secondary CT complexes; this process, in turn, led to the formation of organic hetero-microtubules consisting of multiple segments of two organic CT complexes.

  15. Charge-Transfer Complex of p-Aminodiphenylamine with Maleic Anhydride: Spectroscopic, Electrochemical, and Physical Properties.

    Science.gov (United States)

    Karaca, Erhan; Kaplan Can, Hatice; Bozkaya, Uğur; Özçiçek Pekmez, Nuran

    2016-07-04

    A new charge-transfer complex and the amide formed by the interaction between the electron donor of the p-aminodiphenylamine and the electron acceptor of maleic anhydride are investigated by spectroscopic methods. The amidation reaction is caused by proton and charge transfer between the maleic anhydride and p-aminodiphenylamine molecules. The Benesi-Hildebrand equation is used to determine the formation constant, the molar extinction coefficient and the standard Gibbs free energy of the complex by using UV/Vis spectroscopy. To reveal the electronic and spectroscopic properties of these molecules, theoretical computations are performed on the structures of maleic anhydride, p-aminodiphenylamine and the conformers of their charge-transfer complex. The charge-transfer complex and amidation reaction mechanism are also confirmed by IR and NMR spectroscopy and HRMS. The nature of the maleic anhydride-p-aminodiphenylamine complex is characterized by cyclic voltammetry, thermogravimetric analysis, XRD and SEM. Solid microribbons of this complex show higher thermal stability than p-aminodiphenylamine. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Vibronic coupling in Frenkel and charge-transfer states of oligothiophene crystals

    NARCIS (Netherlands)

    Stradomska, Anna; Kulig, Waldemar; Petelenz, Piotr

    A novel approach, recently proposed to describe exciton phonon coupling in Frenkel states of an infinite molecular crystal, is generalized to incorporate charge-transfer (CT) excitons. Both types of electronic excitations are treated on the same footing. The corresponding Hamiltonian in the Lang

  17. Charge transfer and association of Na+ with 87Rb atoms from extremely low to intermediate energies

    Science.gov (United States)

    Yan, L. L.; Liu, L.; Wu, Y.; Qu, Y. Z.; Wang, J. G.; Buenker, R. J.

    2013-07-01

    The nonradiative charge-transfer processes in Na++87Rb(5s) collisions have been investigated by using the quantum-mechanical molecular-orbital close-coupling method and the two-center atomic-orbital close-coupling method for the energy range of 10-4-5 and 0.3-100 keV/u, respectively. The radiative charge-transfer, radiative-decay, and radiative-association processes have been investigated by using the fully quantum, optical-potential, and semiclassical methods for the energy range of 10-18-0.2 eV/u. The nonradiative charge-transfer processes dominate the collisions for energies above 0.2 eV/u and radiative-decay processes dominate in the lower-energy region. At the very low collision energies of 10-18-10-3 eV/u, the radiative-association process is more important than the radiative charge-transfer process. Most importantly, it is found that the radiative cross sections exhibit Langevin behavior as E-1/2 for energies less than 10-2 eV/u.

  18. Dynamic self-assembly of charge-transfer nanofibers of tetrathiafulvalene derivatives with F4TCNQ.

    Science.gov (United States)

    Jain, Ankit; Rao, K Venkata; Mogera, Umesha; Sagade, Abhay A; George, Subi J

    2011-10-24

    One-dimensional charge-transfer nanostructures were constructed by the supramolecular coassembly of amphiphilic (Amph-TTF) and hydrophobic (TDD-TTF) tetrathiafulvalene (TTF) donor derivatives with the acceptor 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F(4)TCNQ), in appropriate solvent composition mixtures. Microscopic analyses show that TDD-TTF retains its self-assembled fibrillar morphology even in the charge-transfer state, whereas Amph-TTF undergoes a spherical to nanorod transition upon coassembly. Time-dependent optical spectroscopy studies have shown a spontaneous change in molecular organization in TDD-TTF-based donor-acceptor costacks, which suggests a dynamic behavior, in contrast to the kinetically stable amphiphilic TTF assemblies. We have also tried to get an insight into the observed time-dependent change in molecular packing of these nanostructures through spectroscopic analyses by commenting on whether the TTF-TCNQ pair is cofacially arranged or present in the classical herringbone (orthogonal) fashion. Furthermore, our two-probe electrical measurements showed that these charge-transfer fibers are conducting. A supramolecular approach that yields 1D charge-transfer nanostructures of donor and acceptor molecules will be an alternative to existing crystalline substances with high conductivity and hence can be a viable tool for nanoelectronics. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Photoinduced energy and charge transfer in layered porphyrin-gold nanoparticle thin films

    NARCIS (Netherlands)

    Kotiaho, Anne; Lahtinen, Riikka; Lehtivuori, Heli; Tkachenko, Nikolai V.; Lemmetyinen, Helge

    2008-01-01

    In thin films of porphyrin (H2P) and gold nanoparticles (AuNPs), photoexcitation of porphyrins leads to energy and charge transfer to the gold nanoparticles. Alternating layers of porphyrins and octanethiol protected gold nanoparticles (dcore ∼3 nm) were deposited on solid substrates via the

  20. Correlation between charge transfer exciton recombination and photocurrent in polymer/fullerene solar cells

    NARCIS (Netherlands)

    Hallermann, Markus; Da Como, Enrico; Feldmann, Jochen; Izquierdo, Marta; Filippone, Salvatore; Martin, Nazario; Juechter, Sabrina; von Hauff, Elizabeth

    2010-01-01

    We correlate carrier recombination via charge transfer excitons (CTEs) with the short circuit current, J sc, in polymer/fullerene solar cells. Near infrared photoluminescence spectroscopy of CTE in three blends differing for the fullerene acceptor, gives unique insights into solar cell

  1. Spectral signatures of charge transfer in assemblies of molecularly-linked plasmonic nanoparticles

    Science.gov (United States)

    Lerch, Sarah; Reinhard, Björn M.

    2017-09-01

    Self-assembly of functionalized nanoparticles (NPs) provides a unique class of nanomaterials for exploring and utilizing quantum-plasmonic effects that occur if the interparticle separation between NPs approaches a few nanometers and below. We review recent theoretical and experimental studies of plasmon coupling in self-assembled NP structures that contain molecular linkers between the NPs. Charge transfer through the interparticle gap of an NP dimer results in a significant blue-shift of the bonding dipolar plasmon (BDP) mode relative to classical electromagnetic predictions, and gives rise to new coupled plasmon modes, the so-called charge transfer plasmon (CTP) modes. The blue-shift of the plasmon spectrum is accompanied by a weakening of the electromagnetic field in the gap of the NPs. Due to an optical far-field signature that is sensitive to charge transfer across the gap, plasmonic molecules represent a sensor platform for detecting and characterizing gap conductivity in an optical fashion and for characterizing the role of molecules in facilitating the charge transfer across the gap.

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

    DEFF Research Database (Denmark)

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

    2008-01-01

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

  3. Laboratory Measurements of Charge Transfer on Atomic Hydrogen at Thermal Energies

    Science.gov (United States)

    Havener, C. C.; Vane, C. R.; Krause, H. F.; Stancil, P. C.; Mroczkowski, T.; Savin, D. W.

    2002-01-01

    We describe our ongoing program to measure velocity dependent charge transfer (CT) cross sections for selected ions on atomic hydrogen using the ion-aloin merged-beams apparatus at Oak Ridge Natioiial Laboralory. Our focus is on those ions for which CT plays an important role in determining the ionization structure, line emis sion, and thermal structure of observed cosmic photoionized plasmas.

  4. Fullerene-Based Photoactive Layers for Heterojunction Solar Cells: Structure, Absorption Spectra and Charge Transfer Process

    Directory of Open Access Journals (Sweden)

    Yuanzuo Li

    2014-12-01

    Full Text Available The electronic structure and optical absorption spectra of polymer APFO3, [70]PCBM/APFO3 and [60]PCBM/APFO3, were studied with density functional theory (DFT, and the vertical excitation energies were calculated within the framework of the time-dependent DFT (TD-DFT. Visualized charge difference density analysis can be used to label the charge density redistribution for individual fullerene and fullerene/polymer complexes. The results of current work indicate that there is a difference between [60]PCBM and [70]PCBM, and a new charge transfer process is observed. Meanwhile, for the fullerene/polymer complex, all calculations of the twenty excited states were analyzed to reveal all possible charge transfer processes in depth. We also estimated the electronic coupling matrix, reorganization and Gibbs free energy to further calculate the rates of the charge transfer and the recombination. Our results give a clear picture of the structure, absorption spectra, charge transfer (CT process and its influencing factors, and provide a theoretical guideline for designing further photoactive layers of solar cells.

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

    DEFF Research Database (Denmark)

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

    2016-01-01

    We study, within Marcus theory, the possibility of the charge-transfer (CT) state splitting at organic interfaces and a subsequent transport of the free charge carriers to the electrodes. As a case study we analyze model anthracene-C60 interfaces. Kinetic Monte Carlo (KMC) simulations on the cold...

  6. Femtosecond charge transfer dynamics of a modified DNA base: 2-aminopurine in complexes with nucleotides.

    Science.gov (United States)

    Fiebig, Torsten; Wan, Chaozhi; Zewail, Ahmed H

    2002-09-16

    As a fluorescent isomer of adenine, 2-aminopurine (Ap) is a powerful probe of DNA dynamics and DNA-mediated charge transfer processes. Here, we report studies with femtosecond resolution of the excited-state dynamics of Ap in various solvents and in bimolecular complexes with nucleotides. Using time-resolved transient absorption and fluorescence up-conversion methods we identify charge transfer as the origin for the quenching of the Ap fluorescence by all four DNA nucleotides. The direction of the redox process is, however, dependent on the base, and from the rates we deduce the nature of the transfer, hole versus electron transfer. The pH and the kinetic isotope effects of these charge transfer reactions revealed no evidence for proton transfer involvement in the rate-determining step. From the measured rates and using electron transfer theory we estimate the driving force for charge transfer between all four nucleobases and Ap. The results are important for the studies of dynamics using Ap in DNA assemblies.

  7. Elastic, excitation, ionization and charge transfer cross sections of current interest in fusion energy research

    Energy Technology Data Exchange (ETDEWEB)

    Schultz, D.R.; Krstic, P.S. [Oak Ridge National Lab. TN (United States). Physics Div.

    1997-01-01

    Due to the present interest in modeling and diagnosing the edge and divertor plasma regions in magnetically confined fusion devices, we have sought to provide new calculations regarding the elastic, excitation, ionization, and charge transfer cross sections in collisions among relevant ions, neutrals, and isotopes in the low-to intermediate-energy regime. We summarize here some of our recent work. (author)

  8. Symmetry-breaking intramolecular charge transfer in the excited state of meso-linked BODIPY dyads

    KAUST Repository

    Whited, Matthew T.

    2012-01-01

    We report the synthesis and characterization of symmetric BODIPY dyads where the chromophores are attached at the meso position, using either a phenylene bridge or direct linkage. Both molecules undergo symmetry-breaking intramolecular charge transfer in the excited state, and the directly linked dyad serves as a visible-light-absorbing analogue of 9,9′-bianthryl.

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

    NARCIS (Netherlands)

    Gorczak-Vos, N.

    2016-01-01

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

  10. Comparison of Simulation Algorithms for the Hopfield Neural Network: An Application of Economic Dispatch

    OpenAIRE

    Altun, Tankut Yalçınöz and Halis

    2014-01-01

    This paper is mainly concerned with an investigation of the suitability of Hopfield neural network structures in solving the power economic dispatch problem. For Hopfield neural network applications to this problem three important questions have been answered: what the size of the power system is; how efficient the computational method; and how to handle constraints. A new mapping process is formulated and a computational method for obtaining the weights and biases is described. A few simulat...

  11. Some properties of asymmetric Hopfield neural networks with finite time of transition between states

    Science.gov (United States)

    Suleimenov, Ibragim; Mun, Grigoriy; Panchenko, Sergey; Pak, Ivan

    2016-11-01

    There were implemented samples of asymmetric Hopfield neural networks which have finite time of transition from one state to another. It was shown that in such systems, various oscillation modes could occur. It was revealed that the oscillation of the output signal of certain neuron could be treated as extra logical variable, which describes the state of the neuron. Asymmetric Hopfield neural networks are described in terms of ternary logic. Such logic may be employed in image recognition procedure.

  12. Charge transfer effect for the La0.7Ca0.3MnO3/NiO heterostructure and novel interfacial ferromagnetism

    Science.gov (United States)

    Ning, Xingkun; Chen, Mingjing; Wang, Shufang; Fu, Guangsheng

    2017-12-01

    We report the formation of new ferromagnetic (FM) states in antiferromagnetic (AFM) NiO at the interface with FM La0.7Ca0.3MnO3 (LCMO). The LCMO/NiO heterostructures exhibit an exchange bias field of 209 Oe that vanishes as the temperature rises above 90 K. A new magnetization temperature at 90 K is observed and can be ascribed to Ni3+-O-Mn3+ superexchange interactions. Mn 3 s and Ni 3p core-level spectra, measured by X-ray photoelectron spectroscopy, show a direct evidence of charge transfer effects of the type Mn4+-Ni2+ → Mn3+-Ni3+ at the interface region. The valence band offset (VBO) at the LCMO/NiO interface can be determined to be ΔEVBO ∼ 0.77 eV. The valence band of LCMO is shifted to higher binding energy compared with NiO. Thus, charge transfer occurred because of the shifting of the valence band edge at the heterostructure interfaces. We speculate that the superexchange interactions of the Ni3+ and Mn3+ at the interface give rise to the novel low-temperature FM order and the magnetic regions that pin the FM LCMO layer as the temperature decreases.

  13. Coupling of electrons to intermolecular phonons in molecular charge transfer dimers: A resonance Raman study

    Science.gov (United States)

    Pedron, D.; Speghini, A.; Mulloni, V.; Bozio, R.

    1995-08-01

    We report resonance Raman scattering (RRS) spectra and Raman excitation profiles (REP) of a system containing π dimers of identical molecular radical ions measured with laser excitation in resonance with the charge transfer (CT) transition. A Peierls-Hubbard (PH) Hamiltonian has been used to model the investigated system and to calculate its optical and RRS properties. Results are reported for two polyoxometallate salts of tetrathiafulvalene (TTF), namely (TTF)2(W6O19) and (TTF)2(Mo6O19) whose structures contain almost isolated (TTF+)2 dimers. The RRS spectra of (TTF)2(W6O19), measured in resonance with the CT absorption band centered at 832 nm, show three phonon modes located at 55, 90, and 116 cm-1 which are strongly resonance enhanced. These modes have been associated to the out-of-phase combinations of the translational motions of the two molecules composing the dimer. Such modes are effective in modulating the intradimer transfer integral, thus providing an efficient mechanism for coupling with the electronic system and for enhancement of the scattering intensity at resonance with the CT transition. The REP for the three strongly coupled modes of (TTF)2(W6O19) have been measured with laser excitation wavelengths ranging from 740 to 930 nm. Quantitative analysis of the REP data has been performed based on a perturbative solution of the PH model to second order in the electron-molecular-vibration (EMV) and electron-intermolecular-phonon (EIP) interactions. The CT absorption profile and the REP's have been calculated using a time correlator technique and the model parameters have been optimized in order to fit the experimental REP data. Infrared vibronic absorptions of (TTF)2(W6O19), originated by the EMV coupling, have been measured and independent information on the electronic parameters of the PH model have been derived. This has made the choice of the fitting parameters used for the REP calculations rather unambiguous and has allowed us to obtain, for the

  14. Failures of TDDFT in describing the lowest intramolecular charge-transfer excitation in para-nitroaniline

    DEFF Research Database (Denmark)

    Eriksen, Janus J.; Sauer, Stephan P. A.; Mikkelsen, Kurt V.

    2013-01-01

    for charge{transfer character, we furthermore conrm that the di¿erence between excitation energies calculated with TDDFT and with the Tamm-Danco¿ approximation (TDA) to TDDFT is indeed correlated with the charge-transfer character of a given electronic transition both in vacuo and in solution...

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

    DEFF Research Database (Denmark)

    Chabera, Pavel; Liu, Yizhu; Prakash, Om

    2017-01-01

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

  16. Charge-Transfer Phase Transition of a Cyanide-Bridged Fe(II) /Fe(III) Coordination Polymer.

    Science.gov (United States)

    Zhang, Kuirun; Kang, Soonchul; Yao, Zi-Shuo; Nakamura, Kazusa; Yamamoto, Takashi; Einaga, Yasuaki; Azuma, Nobuaki; Miyazaki, Yuji; Nakano, Motohiro; Kanegawa, Shinji; Sato, Osamu

    2016-05-10

    Heterometallic Prussian blue analogues are known to exhibit thermally induced charge transfer, resulting in switching of optical and magnetic properties. However, charge-transfer phase transitions have not been reported for the simplest FeFe cyanide-bridged systems. A mixed-valence Fe(II) /Fe(III) cyanide-bridged coordination polymer, {[Fe(Tp)(CN)3 ]2 Fe(bpe)⋅5 H2 O}n , which demonstrates a thermally induced charge-transfer phase transition, is described. As a result of the charge transfer during this phase transition, the high-spin state of the whole system does not change to a low-spin state. This result is in contrast to FeCo cyanide-bridged systems that exhibit charge-transfer-induced spin transitions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Facile Access to Twisted Intramolecular Charge-Transfer Fluorogens Bearing Highly Pretwisted Donor-Acceptor Systems Together with Readily Fine-Tuned Charge-Transfer Characters.

    Science.gov (United States)

    Luo, Yanju; Wang, Yan; Chen, Shiqi; Wang, Ning; Qi, Yige; Zhang, Xiaogen; Yang, Minghui; Huang, Yan; Li, Ming; Yu, Junsheng; Luo, Daibing; Lu, Zhiyun

    2017-05-01

    Twisted intramolecular charge-transfer (TICT) fluorogens bearing highly pretwisted geometries and readily-fine-tuned charge-transfer characters are quite promising sensor and electroluminescence (EL) materials. In this study, by using 4-aryloxy-1,8-naphthalimide derivatives as the molecular framework, it is demonstrated for the first time that a CO bond could serve as the central bond to construct new TICT D-A systems. Photophysical and quantum chemical studies confirm that rotation around central CO bonds is responsible for the formation of a stable TICT state in these compounds. More importantly, owing to the structural adjustability of the aryl moiety and the strong steric interactions between the naphthalimide and the aryl ring systems, these compounds can display readily-fine-tuned TICT characters, hence exhibiting an adjustable solvent polarity threshold for aggregation-induced emission (AIE) activity, and could be AIE-active even in less-polar toluene and nonpolar cyclohexane. Furthermore, these compounds could possess highly-pretwisted ground-state geometries, hence could show good EL performance. The findings reveal a facile but effective molecular constructive strategy for versatile, high-performance optoelectronic TICT compounds. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Charge transfer complex in diketopyrrolopyrrole polymers and fullerene blends: Implication for organic solar cell efficiency

    Science.gov (United States)

    Moghe, D.; Yu, P.; Kanimozhi, C.; Patil, S.; Guha, S.

    2012-02-01

    Copolymers based on diketopyrrolopyrrole (DPP) have recently gained potential in organic photovoltaics. When blended with another acceptor such as PCBM, intermolecular charge transfer occurs which may result in the formation of charge transfer (CT) states. We present here the spectral photocurrent characteristics of two donor-acceptor DPP based copolymers, PDPP-BBT and TDPP-BBT, blended with PCBM to identify the CT states. The spectral photocurrent measured using Fourier-transform photocurrent spectroscopy (FTPS) and monochromatic photocurrent (PC) methods are compared with P3HT:PCBM, where the CT state is well known. PDPP-BBT:PCBM shows a stable CT state while TDPP-BBT does not. Our analysis shows that the larger singlet state energy difference between TDPP-BBT and PCBM along with the lower optical gap of TDPP-BBT obliterates the formation of a midgap CT state resulting in an enhanced photovoltaic efficiency over PDPP-BBT:PCBM.

  19. Quantum Charge Transfer Study of Triply Charged Ions in the Adiabatic Representation: the (BHe3+ System

    Directory of Open Access Journals (Sweden)

    López-Castillo A.

    1998-01-01

    Full Text Available Full quantum charge transfer study of the process B3+ + He -> B2+ + He+ has been investigated in the collision energy range 1-102 eV using an ab-initio interaction potential. A new method to solve the Schrödinger equation in an adiabatic basis was used, where the radial and rotational coupling were taken into account, and the importance of the coupling between states of different symmetry was discussed. Moreover, by using the well known Landau-Zener model, it was concluded that the two state model cannot be applied for the present system, and this might indicate that such a model should be applied carefully for other systems when a charge transfer process is considered. Finally, the quantum total cross sections were compared with the previous published work of Gargaud and co-workers and a fair agreement was achieved.

  20. WO3-reduced graphene oxide composites with enhanced charge transfer for photoelectrochemical conversion.

    Science.gov (United States)

    Wu, Haoyu; Xu, Ming; Da, Peimei; Li, Wenjie; Jia, Dingsi; Zheng, Gengfeng

    2013-10-14

    Hybrid structures between semiconducting metal oxides and carbon with rational synthesis represent unique device building blocks to optimize the light absorption and charge transfer process for the photoelectrochemical conversion. Here we demonstrate the realization of a WO3-reduced graphene oxide (RGO) nanocomposite via hydrothermal growth of ultrathin WO3 nanoplates directly on fluorine-doped tin oxide (FTO) substrates, followed by in situ photo-reduction to deposit RGO layers on WO3 nanoplate surface. Photoanodes made of the WO3-RGO nanocomposites have achieved a photocurrent density of 2.0 mA cm(-2) at 1.23 V vs. reversible hydrogen electrode (RHE), which is among the highest reported values for photoanodes based on hydrothermally grown WO3. Electrochemical impedance spectroscopy reveals that the increase of photoactivity is attributed to the enhanced charge transfer by the incorporation of RGO, thus suggesting a general approach for designing other metal oxide-RGO hybrid architectures.

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

    Science.gov (United States)

    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.

  2. Charge-transfer electronic absorption spectra of 1-ethylpyridinium cation and halogen anion pairs in dichloromethane and as neat ionic liquids.

    Science.gov (United States)

    Ogura, Takahiro; Akai, Nobuyuki; Shibuya, Kazuhiko; Kawai, Akio

    2013-07-18

    The charge-transfer (CT) absorption bands of ion pairs composed of 1-ethylpyridinium (Epy(+)) and halogen anions (X(-): Cl, Br, or I) were measured in dichloromethane solutions of EpyX. The CT band of the Epy(+)I(-) ion pair shows clear splitting because of spin-orbit interaction in the excited state. The CT transition energy of an Epy(+)X(-) ion pair in a dichloromethane solution is related to electron affinity of X, which is in accordance with the Mulliken theory for CT bands. Extinction coefficients for the CT bands of the Epy(+)X(-) ion pairs in dichloromethane were determined using the measured absorbance, and the ion-pair concentration was estimated on the basis of electroconductivity. Structures of Epy(+)X(-) ion pairs were also evaluated on the basis of both quantum-chemical calculations and NMR spectroscopy. In addition, in the absorption spectrum measured for neat EpyI liquid, a broad band appeared at a longer wavelength side of the S1(ππ*) band. This new band has been assigned to the CT band of the Epy(+)I(-) ion pair formed in neat EpyI liquid.

  3. Interfacial Charge Transfer and Recombination Dynamics in van der Waals Heterojunctions of 2D Semiconductors

    Science.gov (United States)

    Wang, Jue; Zhu, Haiming; Gong, Zizhou; Kim, Young Duck; Gustafsson, Martin; Hone, James; Zhu, Xiaoyang

    Heterojunctions of transition metal dichalcogenides (TMDC) are being explored for optoelectronics, photovoltaics and spin-valleytronics at the 2D limit. Using time-resolved microscopic transient reflectance spectroscopy, we measured the interfacial charge transfer and recombination dynamics in two dimensional MoS2/WSe2 heterojunctions as a function of interlayer momentum mismatch. The observed ultrafast (Science Foundation Grant DMR 1608437 and Grant DMR 1420634 (Materials Research Science and Engineering Center).

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

    Science.gov (United States)

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

    2008-01-01

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

  5. Extended Holstein small polaron model for charge transfer in dry DNA.

    Science.gov (United States)

    Wang, Yi; Fu, Liang; Wang, Ke-Lin

    2006-01-20

    In this paper, the charge transfer problem in dry DNA was investigated by employing an extended Holstein small polaron model with external potential traps being involved in consideration. The ground state energy and the probability amplitude of polaron in various DNA chains with different external trap potentials were obtained by variational method with the trial function being taken in coherent state form. The stability of transfered charges in various circumstances was discussed accordingly.

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

    Directory of Open Access Journals (Sweden)

    Shutthanandan V

    2008-06-01

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

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

    Science.gov (United States)

    Sun, Baichuan; Barnard, Amanda S.

    2016-07-01

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

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

    KAUST Repository

    Van Regemorter, Tanguy

    2012-09-15

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

  9. Observation of Ground- and Excited-State Charge Transfer at the C60/Graphene Interface.

    Science.gov (United States)

    Jnawali, Giriraj; Rao, Yi; Beck, Jonathan H; Petrone, Nicholas; Kymissis, Ioannis; Hone, James; Heinz, Tony F

    2015-07-28

    We examine charge transfer interactions in the hybrid system of a film of C60 molecules deposited on single-layer graphene using Raman spectroscopy and Terahertz (THz) time-domain spectroscopy. In the absence of photoexcitation, we find that the C60 molecules in the deposited film act as electron acceptors for graphene, yielding increased hole doping in the graphene layer. Hole doping of the graphene film by a uniform C60 film at a level of 5.6 × 10(12)/cm(2) or 0.04 holes per interfacial C60 molecule was determined by the use of both Raman and THz spectroscopy. We also investigate transient charge transfer occurring upon photoexcitation by femtosecond laser pulses with a photon energy of 3.1 eV. The C60/graphene hybrid exhibits a short-lived (ps) decrease in THz conductivity, followed by a long-lived increase in conductivity. The initial negative photoconductivity transient, which decays within 2 ps, reflects the intrinsic photoresponse of graphene. The longer-lived positive conductivity transient, with a lifetime on the order of 100 ps, is attributed to photoinduced hole doping of graphene by interfacial charge transfer. We discuss possible microscopic pathways for hot carrier processes in the hybrid system.

  10. Negative Resistance Effect and Charge Transfer Mechanisms in the lon Beam Deposited Diamond Like Carbon Superlattices

    Directory of Open Access Journals (Sweden)

    Andrius VASILIAUSKAS

    2011-03-01

    Full Text Available In the present study DLC:SiOx/DLC/DLC:SiOx/nSi and DLC:SiOx/DLC/DLC:SiOx/pSi structures were fabricated by ion beam deposition using a closed drift ion source. Current-voltage (I-V characteristics of the multilayer samples were measured at room temperature. The main charge transfer mechanisms were considered. Unstable negative resistance effect was observed for some DLC:SiOx/DLC/DLC:SiOx/nSi and DLC:SiOx/DLC/DLC:SiOx/pSi structures. In the case of the diamond like carbon superlattices fabricated on nSi it was observed only during the first measurement. In the case of the some DLC:SiOx/DLC/DLC:SiOx/pSi negative resistance "withstood" several measurements. Changes of the charge carrier mechanisms were observed along with the dissapear of the negative resistance peaks. It seems, that in such a case influence of the bulk related charge transfer mechanisms such as Poole-Frenkel emission increased, while the influence of the contact limited charge transfer mechanisms such as Schottky emission decreased. Observed results were be explained by current flow through the local microconducting channels and subsequent destruction of the localized current pathways as a result of the heating by flowing electric current.http://dx.doi.org/10.5755/j01.ms.17.1.240

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

    Science.gov (United States)

    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.

  12. Defect passivation of transition metal dichalcogenides via a charge transfer van der Waals interface.

    Science.gov (United States)

    Park, Jun Hong; Sanne, Atresh; Guo, Yuzheng; Amani, Matin; Zhang, Kehao; Movva, Hema C P; Robinson, Joshua A; Javey, Ali; Robertson, John; Banerjee, Sanjay K; Kummel, Andrew C

    2017-10-01

    Integration of transition metal dichalcogenides (TMDs) into next-generation semiconductor platforms has been limited due to a lack of effective passivation techniques for defects in TMDs. The formation of an organic-inorganic van der Waals interface between a monolayer (ML) of titanyl phthalocyanine (TiOPc) and a ML of MoS 2 is investigated as a defect passivation method. A strong negative charge transfer from MoS 2 to TiOPc molecules is observed in scanning tunneling microscopy. As a result of the formation of a van der Waals interface, the I ON / I OFF in back-gated MoS 2 transistors increases by more than two orders of magnitude, whereas the degradation in the photoluminescence signal is suppressed. Density functional theory modeling reveals a van der Waals interaction that allows sufficient charge transfer to remove defect states in MoS 2 . The present organic-TMD interface is a model system to control the surface/interface states in TMDs by using charge transfer to a van der Waals bonded complex.

  13. Mechanism of Charge Transfer from Plasmonic Nanostructures to Chemically Attached Materials.

    Science.gov (United States)

    Boerigter, Calvin; Aslam, Umar; Linic, Suljo

    2016-06-28

    Plasmonic metal nanoparticles can efficiently convert the energy of visible photons into the energy of hot charge carriers within the nanoparticles. These energetic charge carriers can transfer to molecules or semiconductors, chemically attached to the nanoparticles, where they can induce photochemical transformations. Classical models of photoinduced charge excitation and transfer in metals suggest that the majority of the energetic charge carriers rapidly decay within the metal nanostructure before they are transferred into the neighboring molecule or semiconductor, and therefore, the efficiency of charge transfer is low. Herein, we present experimental evidence that calls into question this conventional picture. We demonstrate a system where the presence of a molecule, adsorbed on the surface of a plasmonic nanoparticle, significantly changes the flow of charge within the excited plasmonic system. The nanoparticle-adsorbate system experiences high rates of direct, resonant flow of charge from the nanoparticle to the molecule, bypassing the conventional charge excitation and thermalization process taking place in the nanoparticle. This picture of charge transfer suggests that the yield of extracted hot electrons (or holes) from plasmonic nanoparticles can be significantly higher than the yields expected based on conventional models. We discuss a conceptual physical framework that allows us to explain our experimental observations. This analysis points us in a direction toward molecular control of the charge transfer process using interface and local field engineering strategies.

  14. The impact of size and shape distributions on the electron charge transfer properties of silver nanoparticles.

    Science.gov (United States)

    Sun, Baichuan; Barnard, Amanda S

    2017-08-31

    Many applications of silver nanoparticles are moderated by the electron charge transfer properties, such as the ionization potential, electron affinity and Fermi energy, which may be tuned by controlling the size and shape of individual particles. However, since producing samples of silver nanoparticles that are perfectly monodispersed in terms of both size and shape can be prohibitive, it is important to understand how these properties are impacted by polydispersivity, and ideally be able to predict the tolerance for variation of different geometric features. In this study, we use straightforward statistical methods, together with electronic structure simulations, to predict the electron charge transfer properties of different types of ensembles of silver nanoparticles and how restricting the structural diversity in different ways can improve or retard performance. In agreement with previous reports, we confirm that restricting the shape distribution will tune the charge transfer properties toward specific reactions, but by including the quality factors for each case we go beyond this assessment and show how targeting specific classes of morphologies and restricting the distribution of size can impact sensitivity.

  15. Route Selection Problem Based on Hopfield Neural Network

    Directory of Open Access Journals (Sweden)

    N. Kojic

    2013-12-01

    Full Text Available Transport network is a key factor of economic, social and every other form of development in the region and the state itself. One of the main conditions for transport network development is the construction of new routes. Often, the construction of regional roads is dominant, since the design and construction in urban areas is quite limited. The process of analysis and planning the new roads is a complex process that depends on many factors (the physical characteristics of the terrain, the economic situation, political decisions, environmental impact, etc. and can take several months. These factors directly or indirectly affect the final solution, and in combination with project limitations and requirements, sometimes can be mutually opposed. In this paper, we present one software solution that aims to find Pareto optimal path for preliminary design of the new roadway. The proposed algorithm is based on many different factors (physical and social with the ability of their increase. This solution is implemented using Hopfield's neural network, as a kind of artificial intelligence, which has shown very good results for solving complex optimization problems.

  16. Non-adiabatic processes in the charge transfer reaction of O{sub 2} molecules with potassium surfaces without dissociation

    Energy Technology Data Exchange (ETDEWEB)

    Krix, David; Nienhaus, Hermann, E-mail: hermann.nienhaus@uni-due.de [Faculty of Physics, University of Duisburg-Essen and Center of Nanointegration Duisburg-Essen (CENIDE), Lotharstr. 1, D-47048 Duisburg (Germany)

    2014-08-21

    Thin potassium films grown on Si(001) substrates are used to measure internal chemicurrents and the external emission of exoelectrons simultaneously during adsorption of molecular oxygen on K surfaces at 120 K. The experiments clarify the dynamics of electronic excitations at a simple metal with a narrow valence band. X-ray photoemission reveals that for exposures below 5 L almost exclusively peroxide K{sub 2}O{sub 2} is formed, i.e., no dissociation of the molecule occurs during interaction. Still a significant chemicurrent and a delayed exoelectron emission are detected due to a rapid injection of unoccupied molecular levels below the Fermi level. Since the valence band width of potassium is approximately equal to the potassium work function (2.4 eV) the underlying mechanism of exoemission is an Auger relaxation whereas chemicurrents are detected after resonant charge transfer from the metal valence band into the injected level. The change of the chemicurrent and exoemission efficiencies with oxygen coverage can be deduced from the kinetics of the reaction and the recorded internal and external emission currents traces. It is shown that the non-adiabaticity of the reaction increases with coverage due to a reduction of the electronic density of states at the surface while the work function does not vary significantly. Therefore, the peroxide formation is one of the first reaction systems which exhibits varying non-adiabaticity and efficiencies during the reaction. Non-adiabatic calculations based on model Hamiltonians and density functional theory support the picture of chemicurrent generation and explain the rapid injection of hot hole states by an intramolecular motion, i.e., the expansion of the oxygen molecule on the timescale of a quarter of a vibrational period.

  17. Note: Charge transfer in a hydrated peptide group is determined mainly by its intrinsic hydrogen-bond energetics

    Energy Technology Data Exchange (ETDEWEB)

    Mirkin, Noemi G.; Krimm, Samuel [LSA Biophysics, University of Michigan, 930 N. University Ave., Ann Arbor, Michigan 48109-1055 (United States)

    2014-01-28

    Charge transfer in a hydrogen-bonded N-methylacetamide(H{sub 2}O){sub 3} system is obtained from ωB97X-D/6-31++G** and CHelpG atomic charge calculations of individual peptide-water interactions as well as that of the entire complex. In the latter, the electron transfer to water is 0.19 e, influenced primarily by the hydrogen bonds to the C=O group. The values of such charge transfer are paralleled by the corresponding intrinsic hydrogen-bond energies. These results support the desirability of incorporating charge transfer in molecular mechanics energy functions.

  18. Performance of the M06 family of functionals in prediction of the charge transfer transition energies of the naphthalene-TCNE and pyrene-TCNE molecular complexes

    Science.gov (United States)

    Tiwary, Amit S.; Mukherjee, Asok K.

    2014-08-01

    The B3LYP and the M06 family of functionals were found to be of nearly equal efficiency for predicting the 13C and 15N NMR chemical shifts (which are ground state properties) of molecular complexes of TCNE with naphthalene and pyrene. But the B3LYP functional could not find any charge transfer (CT) absorption band of the complexes. The M06, M06-2X, M06-HF and M06-L functionals could find two CT absorption bands in CCl4 medium by a TDDFT calculation under the PCM formalism for solvation; the calculated CT transition energies are comparable with the reported experimental values, M06-2X and M06-L agreeing best with experiment.

  19. Femtosecond insights into direct electron injection in dye anchored ZnO QDs following charge transfer excitation.

    Science.gov (United States)

    Kumar, Pushpendra; Kumar, Sunil; Ghosh, Subrata; Pal, Suman Kalyan

    2016-07-27

    The role of the charge transfer (CT) state in interfacial electron transfer in dye-sensitized semiconductor nanocrystals is still poorly understood. To address this problem, femtosecond transient absorption (TA) spectroscopy is used as a probe to investigate the electron injection across a newly synthesized coumarin dye (8-hydroxy-2-oxo-4-phenyl-2 benzo[h]chromene-3-carbonitrile, coded BC5) and ZnO quantum dots (QDs). Steady state and time-resolved spectroscopic measurements reveal that BC5 dye interacts strongly with ZnO QDs in the ground state forming a CT complex. The BC5-ZnO QD complex absorbs more towards red compared to only the dye and QDs, and emits fluorescence due to radiative recombination of photogenerated charges. The formation of charges following the excitation of the CT complex has been demonstrated by observing the signature of dye radical cations and electrons in the conduction band (CB) of the QDs in the TA spectra. The TA signals of these charges grow sharply as a result of ultrafast direct electron injection into the QD. We have monitored the complete dynamics of photogenerated charges by measuring the TA signals of the charges up to a couple of nanoseconds. The injected electrons that are free or shallowly trapped recombine with a time constant of 625 fs, whereas deeply trapped electrons disappear slowly (526 ps) via radiative recombination. Furthermore, theoretical studies based on ab initio calculations have been carried out to complement the experimental findings.

  20. Charge-transfer complex formation between TiO2 nanoparticles and thiosalicylic acid: A comprehensive experimental and DFT study

    Science.gov (United States)

    Milićević, Bojana; Đorđević, Vesna; Lončarević, Davor; Dostanić, Jasmina M.; Ahrenkiel, S. Phillip; Dramićanin, Miroslav D.; Sredojević, Dušan; Švrakić, Nenad M.; Nedeljković, Jovan M.

    2017-11-01

    Under normal conditions, titanium dioxide does not absorb visible light photons due to large band gap. Nevertheless, when titanium dioxide nanoparticles (TiO2 NPs) are surface-modified with thiosalicylic acid (TSA), their optical properties are altered owing to the formation of charge transfer complex that initiates absorption in the visible spectral range. Colloidal and sol-gel techniques were used to synthesize uniform TiO2 NPs of different sizes (average diameters in the range 4-15 nm), and effects of their subsequent modification by TSA molecules were compared with effect of modification of commercial Degussa TiO2 powder. Thorough microstructural characterization of TiO2 nanoparticulates was performed including transmission electron microscopy (TEM) and X-ray diffraction (XRD) analysis, as well as nitrogen adsorption-desorption isotherms. Optical measurements revealed that all surface-modified TiO2 samples with TSA have similar spectral features independent of their morphological differences, and, more importantly, absorption onset of modified TiO2 samples was found to be red-shifted by 1.0 eV compared to the unmodified ones. The mode of binding between TSA and surface Ti atoms was analyzed by infrared spectroscopy. Finally, the quantum chemical calculations, based on density functional theory, were performed to support optical characterization of surface-modified TiO2 with TSA.

  1. Hybrid genetic algorithm in the Hopfield network for maximum 2-satisfiability problem

    Science.gov (United States)

    Kasihmuddin, Mohd Shareduwan Mohd; Sathasivam, Saratha; Mansor, Mohd. Asyraf

    2017-08-01

    Heuristic method was designed for finding optimal solution more quickly compared to classical methods which are too complex to comprehend. In this study, a hybrid approach that utilizes Hopfield network and genetic algorithm in doing maximum 2-Satisfiability problem (MAX-2SAT) was proposed. Hopfield neural network was used to minimize logical inconsistency in interpretations of logic clauses or program. Genetic algorithm (GA) has pioneered the implementation of methods that exploit the idea of combination and reproduce a better solution. The simulation incorporated with and without genetic algorithm will be examined by using Microsoft Visual 2013 C++ Express software. The performance of both searching techniques in doing MAX-2SAT was evaluate based on global minima ratio, ratio of satisfied clause and computation time. The result obtained form the computer simulation demonstrates the effectiveness and acceleration features of genetic algorithm in doing MAX-2SAT in Hopfield network.

  2. Simulation tests of the optimization method of Hopfield and Tank using neural networks

    Science.gov (United States)

    Paielli, Russell A.

    1988-01-01

    The method proposed by Hopfield and Tank for using the Hopfield neural network with continuous valued neurons to solve the traveling salesman problem is tested by simulation. Several researchers have apparently been unable to successfully repeat the numerical simulation documented by Hopfield and Tank. However, as suggested to the author by Adams, it appears that the reason for those difficulties is that a key parameter value is reported erroneously (by four orders of magnitude) in the original paper. When a reasonable value is used for that parameter, the network performs generally as claimed. Additionally, a new method of using feedback to control the input bias currents to the amplifiers is proposed and successfully tested. This eliminates the need to set the input currents by trial and error.

  3. A Generalized Hopfield Network for Nonsmooth Constrained Convex Optimization: Lie Derivative Approach.

    Science.gov (United States)

    Li, Chaojie; Yu, Xinghuo; Huang, Tingwen; Chen, Guo; He, Xing

    2016-02-01

    This paper proposes a generalized Hopfield network for solving general constrained convex optimization problems. First, the existence and the uniqueness of solutions to the generalized Hopfield network in the Filippov sense are proved. Then, the Lie derivative is introduced to analyze the stability of the network using a differential inclusion. The optimality of the solution to the nonsmooth constrained optimization problems is shown to be guaranteed by the enhanced Fritz John conditions. The convergence rate of the generalized Hopfield network can be estimated by the second-order derivative of the energy function. The effectiveness of the proposed network is evaluated on several typical nonsmooth optimization problems and used to solve the hierarchical and distributed model predictive control four-tank benchmark.

  4. Defense Against Chip Cloning Attacks Based on Fractional Hopfield Neural Networks.

    Science.gov (United States)

    Pu, Yi-Fei; Yi, Zhang; Zhou, Ji-Liu

    2017-06-01

    This paper presents a state-of-the-art application of fractional hopfield neural networks (FHNNs) to defend against chip cloning attacks, and provides insight into the reason that the proposed method is superior to physically unclonable functions (PUFs). In the past decade, PUFs have been evolving as one of the best types of hardware security. However, the development of the PUFs has been somewhat limited by its implementation cost, its temperature variation effect, its electromagnetic interference effect, the amount of entropy in it, etc. Therefore, it is imperative to discover, through promising mathematical methods and physical modules, some novel mechanisms to overcome the aforementioned weaknesses of the PUFs. Motivated by this need, in this paper, we propose applying the FHNNs to defend against chip cloning attacks. At first, we implement the arbitrary-order fractor of a FHNN. Secondly, we describe the implementation cost of the FHNNs. Thirdly, we propose the achievement of the constant-order performance of a FHNN when ambient temperature varies. Fourthly, we analyze the electrical performance stability of the FHNNs under electromagnetic disturbance conditions. Fifthly, we study the amount of entropy of the FHNNs. Lastly, we perform experiments to analyze the pass-band width of the fractor of an arbitrary-order FHNN and the defense against chip cloning attacks capability of the FHNNs. In particular, the capabilities of defense against chip cloning attacks, anti-electromagnetic interference, and anti-temperature variation of a FHNN are illustrated experimentally in detail. Some significant advantages of the FHNNs are that their implementation cost is considerably lower than that of the PUFs, their electrical performance is much more stable than that of the PUFs under different temperature conditions, their electrical performance stability of the FHNNs under electromagnetic disturbance conditions is much more robust than that of the PUFs, and their amount of

  5. Spectroscopic and physical measurements on charge-transfer complexes: Interactions between norfloxacin and ciprofloxacin drugs with picric acid and 3,5-dinitrobenzoic acid acceptors

    Science.gov (United States)

    Refat, Moamen S.; Elfalaky, A.; Elesh, Eman

    2011-03-01

    Charge-transfer complexes formed between norfloxacin (nor) or ciprofloxacin (cip) drugs as donors with picric acid (PA) and/or 3,5-dinitrobenzoic acid (DNB) as π-acceptors have been studied spectrophotometrically in methanol solvent at room temperature. The results indicated the formation of CT-complexes with molar ratio1:1 between donor and acceptor at maximum CT-bands. In the terms of formation constant ( KCT), molar extinction coefficient ( ɛCT), standard free energy (Δ Go), oscillator strength ( f), transition dipole moment (μ), resonance energy ( RN) and ionization potential ( ID) were estimated. IR, H NMR, UV-Vis techniques, elemental analyses (CHN) and TG-DTG investigations were used to characterize the structural of charge-transfer complexes. It indicates that the CT interaction was associated with a proton migration from each acceptor to nor or cip donors which followed by appearing intermolecular hydrogen bond. In addition, X-ray investigation was carried out to scrutinize the crystal structure of the resulted CT-complexes.

  6. Charge transfer of edge states in zigzag silicene nanoribbons with Stone–Wales defects from first-principles

    Energy Technology Data Exchange (ETDEWEB)

    Ting, Xie [College of Mathematics and Statistics, Chongqing University, Chongqing 401331 (China); School of Mathematics and Statistic, Chongqing University of Technology, Chongqing 400054 (China); Rui, Wang, E-mail: rcwang@cqu.edu.cn [Institute for Structure and Function and Department of Physics, Chongqing University, Chongqing 400044 (China); State Key Laboratory of Theoretical Physics, Institute of Theoretical Physics, Chinese Academy of Science, Beijing 100190 (China); Shaofeng, Wang [Institute for Structure and Function and Department of Physics, Chongqing University, Chongqing 400044 (China); Xiaozhi, Wu, E-mail: xiaozhiwu@cqu.edu.cn [Institute for Structure and Function and Department of Physics, Chongqing University, Chongqing 400044 (China)

    2016-10-15

    Highlights: • The properties of SW defects in silicene and ZSNRs are obtained. • The SW defects at the edge of ZSNRs induce a sizable gap. • The charge transfer of edge states is resulted from SW defects in ZSNRS. - Abstract: Stone–Wales (SW) defects are favorably existed in graphene-like materials with honeycomb lattice structure and potentially employed to change the electronic properties in band engineering. In this paper, we investigate structural and electronic properties of SW defects in silicene sheet and its nanoribbons as a function of their concentration using the methods of periodic boundary conditions with first-principles calculations. We first calculate the formation energy, structural properties, and electronic band structures of SW defects in silicene sheet, with dependence on the concentration of SW defects. Our results show a good agreement with available values from the previous first-principles calculations. The energetics, structural aspects, and electronic properties of SW defects with dependence on defect concentration and location in edge-hydrogenated zigzag silicene nanoribbons are obtained. For all calculated concentrations, the SW defects prefer to locate at the edge due to the lower formation energy. The SW defects at the center of silicene nanoribbons slightly influence on the electronic properties, whereas the SW defects at the edge of silicene nanoribbons split the degenerate edge states and induce a sizable gap, which depends on the concentration of defects. It is worth to find that the SW defects produce a perturbation repulsive potential, which leads the decomposed charge of edge states at the side with defect to transfer to the other side without defect.

  7. Cluster Dependent Charge-Transfer Dynamics in Iron-Sulfur Proteins.

    Science.gov (United States)

    Mao, Ziliang; Liou, Shu-Hao; Khadka, Nimesh; Jenney, Francis E; Goodin, David B; Seefeldt, Lance C; Adams, Michael W W; Cramer, Stephen; Larsen, Delmar S

    2018-01-05

    Photo-induced charge-transfer dynamics and the influence of cluster size on the dynamics were investigated using five iron-sulfur clusters: the 1Fe-4S cluster in Pyrococcos furiosus rubredoxin, the 2Fe-2S cluster in Pseudomonas putida putidaredoxin, the 4Fe-4S cluster in nitrogenase iron protein, and the 8Fe-7S P-cluster and the 7Fe-9S-1Mo FeMo cofactor in nitrogenase MoFe protein. Laser excitation promotes the iron-sulfur clusters to excited electronic states that relax to lower states. The electronic relaxation lifetimes of the 1Fe-4S, the 8Fe-7S, and the 7Fe-9S-1Mo clusters are in the picoseconds timescale, although the dynamics of the MoFe protein is a mixture of the dynamics of the later two clusters. The lifetimes of the 2Fe-2S and the 4Fe-4S clusters, however, extend to several nanoseconds. A competition between reorganization energies and density of electronic states (thus electronic coupling between states) mediates the charge-transfer lifetimes, with the 2Fe-2S cluster of Pdx and the 4Fe-4S cluster of Fe protein lying at the optimum leading to them having significantly longer lifetimes. Their long lifetimes make them the optimal candidates for long-range electron transfer and as external photosensitizers for other photo-activated chemical reactions like solar hydrogen production. Potential electron-transfer and hole-transfer pathways are proposed that possibly facilitate these charge transfers.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1983-11-01

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

  9. Strain-induced charge transfer and polarity control of a heterosheet comprising C60 and graphene

    Science.gov (United States)

    Saucier, Yamato A.; Okada, Susumu; Maruyama, Mina

    2017-09-01

    Using density functional theory combined with the effective screening medium method, the energetics and electronic structure of a C60 molecular sheet adsorbed on graphene were studied in terms of biaxial strains. The optimum spacing and interlayer interaction monotonically decreases and increases, respectively, with an increasing biaxial tensile strain. The biaxial compressive strain induces electron transfer from the graphene to C60 at a 2% lateral compression, leading to an all-carbon charge transfer complex. The heterosheet possesses an intrinsic dipole moment along the graphene-to-C60 molecular layer direction.

  10. Molecular distortion and charge transfer effects in ZnPc/Cu(111)

    KAUST Repository

    Amin, B.

    2013-04-23

    The adsorption geometry and electronic properties of a zinc-phthalocyanine molecule on a Cu(111) substrate are studied by density functional theory. In agreement with experiment, we find remarkable distortions of the molecule, mainly as the central Zn atom tends towards the substrate to minimize the Zn-Cu distance. As a consequence, the Zn-N chemical bonding and energy levels of the molecule are significantly modified. However, charge transfer induces metallic states on the molecule and therefore is more important for the ZnPc/Cu(111) system than the structural distortions.

  11. Fullerenes - how 25 years of charge transfer chemistry have shaped our understanding of (interfacial) interactions.

    Science.gov (United States)

    Zieleniewska, A; Lodermeyer, F; Roth, A; Guldi, D M

    2017-11-29

    In this review article, we highlight over 25 years of fullerene research in charge transfer chemistry. The major thrust of this work is to illustrate interfacial interactions between fullerenes and porphyrins in electron donor-acceptor conjugates as well as self-assembled associates and co-crystallites all the way to organic photovoltaics. Hereby, the analysis of the fundamental proceses, namely, energy transfer, charge shift, charge separation as well as charge recombination stand at the forefront. Our examples, illustrate on how fine-tuning the structure leads to substantial alteration of interfacial interactions.

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

    DEFF Research Database (Denmark)

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

    2016-01-01

    The bc1 complex is a critical enzyme for the ATP production in photosynthesis and cellular respiration. Its biochemical function relies on the so-called Q-cycle, which is well established and operates via quinol substrates that bind inside the protein complex. Despite decades of research, the qui...... the conclusion. Finally, key structural elements of the bc1 complex that trigger the charge transfer reactions were established, manifesting the importance of the environment in the process, which is furthermore evidenced by free energy calculations....

  13. Coloration of tyrosine by organic-semiconductor interfacial charge-transfer transitions

    Science.gov (United States)

    Fujisawa, Jun-ichi; Kikuchi, Natsumi; Hanaya, Minoru

    2016-11-01

    L-tyrosine (Tyr) plays a crucial role as a proteinogenic amino acid and also as a precursor to several neurotransmitters and hormones. Here we demonstrate coloration of Tyr based on organic-semiconductor interfacial charge-transfer (ICT) transitions. The ICT transitions from Tyr to TiO2 are induced by the chemisorption of Tyr on TiO2 surfaces via the hydroxy group of the phenol moiety. Because other amino acids possess no chemical group to induce ICT transitions, this coloration method enables to detect Tyr selectively without drastic structural change in contrast to the conventional coloration methods.

  14. Photoinduced charge transfer involving a MoMo quadruply bonded complex to a perylene diimide.

    Science.gov (United States)

    Alberding, Brian G; Brown-Xu, Samantha E; Chisholm, Malcolm H; Epstein, Arthur J; Gustafson, Terry L; Lewis, Sharlene A; Min, Yong

    2013-04-21

    Evidence, based on femtosecond transient absorption and time resolved infrared spectroscopy, is presented for photoinduced charge transfer from the Mo2δ orbital of the quadruply bonded molecule trans-Mo2(T(i)PB)2(BTh)2, where T(i)PB = 2,4,6-triisopropyl benzoate and BTh = 2,2'-bithienylcarboxylate, to di-n-octyl perylene diimide and di-n-hexylheptyl perylene diimide in thin films and solutions of the mixtures. The films show a long-lived charge separated state while slow back electron transfer, τBET ~ 500 ps, occurs in solution.

  15. Charge transfer in energetic Li2+-H and He+-He+ collisions

    Science.gov (United States)

    Mančev, I.

    2009-02-01

    The total cross sections for charge transfer in Li2+-H and He+-He+ collisions have been calculated, using the four body first Born approximation with correct boundary conditions (CB1-4B) and four body continuum distorted wave method (CDW-4B) in the energy range 10-5000 keV/amu. The role of dynamic electron correlations is examined as a function of the impact energy. The present results call for additional experimental data at higher impact energies than presently available.

  16. The 1:1 charge-transfer complex dibenzotetrathiafulvalene–pyromellitic dianhydride (DBTTF–PMDA

    Directory of Open Access Journals (Sweden)

    Margaret E. Payne

    2014-08-01

    Full Text Available The title charge-transfer (CT complex, C10H2O6·C14H8S4, composed of donor dibenzotetrathiafulvalene (DBTTF and acceptor pyromellitic dianhydride (PMDA, forms a mixed stacking pattern along the [-110] direction. The constituent molecules occupy crystallographic inversion centers. They are nearly parallel and lie ca.3.41 Å from each other. The crystals exhibit a high degree of donor/acceptor overlap [88.20 (4%] in the long direction of the DBTTF and PMDA molecules as compared with 51.27 (5% in the shortest direction of the molecules.

  17. Polarization and charge-transfer effects in aqueous solution via ab initio QM/MM simulations.

    Science.gov (United States)

    Mo, Yirong; Gao, Jiali

    2006-02-23

    Combined ab initio quantum mechanical and molecular mechanical (QM/MM) simulations coupled with the block-localized wave function energy decomposition (BLW-ED) method have been conducted to study the solvation of two prototypical ionic systems, acetate and methylammonium ions in aqueous solution. Calculations reveal that the electronic polarization between the targeted solutes and water is the primary many-body effect, whereas the charge-transfer term only makes a small fraction of the total solute-solvent interaction energy. In particular, the polarization effect is dominated by the solvent (water) polarization.

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

    Science.gov (United States)

    Hendrickson, Heidi Phillips

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

  19. Conjugated iminopyridine based Azo dye derivatives with efficient charge transfer for third order nonlinearities

    Science.gov (United States)

    Kerasidou, A. P.; Khammar, F.; Iliopoulos, K.; Ayadi, A.; El-Ghayoury, A.; Zouari, N.; Mhiri, T.; Sahraoui, B.

    2014-03-01

    The third order nonlinearities of two azobenzene-iminopyridine molecular systems have been investigated employing the Z-scan technique at 532 nm, 30 ps. The objective of the work has been to study and to compare the nonlinearity of two iminopyridine based ligands substituted with one (NO2AzoIminoPy, A) and two azobenzene units ((NO2Azo)2IminoPy, B). The ligand B exhibits an extended conjugated structure and higher charge transfer within the molecule. Our results show high dependence of the nonlinearity on both the conjugation length within the molecule and on the number of the electron accepting units.

  20. Coherent Dynamics of Mixed Frenkel and Charge-Transfer Excitons in Dinaphtho[2,3-b:2'3'-f]thieno[3,2-b]-thiophene Thin Films: The Importance of Hole Delocalization.

    Science.gov (United States)

    Fujita, Takatoshi; Atahan-Evrenk, Sule; Sawaya, Nicolas P D; Aspuru-Guzik, Alán

    2016-04-07

    Charge-transfer states in organic semiconductors play crucial roles in processes such as singlet fission and exciton dissociation at donor/acceptor interfaces. Recently, a time-resolved spectroscopy study of dinaphtho[2,3-b:2'3'-f]thieno[3,2-b]-thiophene (DNTT) thin films provided evidence for the formation of mixed Frenkel and charge-transfer excitons after the photoexcitation. Here, we investigate optical properties and excitation dynamics of the DNTT thin films by combining ab initio calculations and a stochastic Schrödinger equation. Our theory predicts that the low-energy Frenkel exciton band consists of 8-47% CT character. The quantum dynamics simulations show coherent dynamics of Frenkel and CT states in 50 fs after the optical excitation. We demonstrate the role of charge delocalization and localization in the mixing of CT states with Frenkel excitons as well as the role of their decoherence.

  1. Intramolecular charge transfer and dielectric solvent relaxation in n-propyl cyanide. N-phenylpyrrole and 4-dimethylamino-4'-cyanostilbene.

    Science.gov (United States)

    Druzhinin, Sergey I; Galievsky, Victor A; Yoshihara, Toshitada; Zachariasse, Klaas A

    2006-11-30

    Fast intramolecular charge transfer (ICT) accompanied by dual fluorescence from a locally excited (LE) and an ICT state taking place with N-phenylpyrrole (PP) in the solvent n-propyl cyanide (PrCN) is investigated as a function of temperature between 25 and -112 degrees C. The LE and ICT fluorescence decays from -45 to -70 degrees C can be adequately fitted with two exponentials, in accordance with a two state (LE + ICT) reaction mechanism, similar to what has been observed with PP in the more polar and less viscous alkyl cyanides acetonitrile (MeCN) and ethyl cyanide (EtCN). At lower temperatures, triple-exponential fits are required for the LE and ICT decays. The ICT emission band maximum of the time-resolved fluorescence spectra of PP in PrCN at -100 degrees C displays a spectral shift from 29 230 cm-1 at t = 0 to 27 780 cm-1 at infinite time, which equilibration process is attributed to dielectric solvent relaxation. From the time dependence of this shift, in global analysis with that of the band integrals BI(LE) and BI(ICT) of the time-resolved LE and ICT fluorescence bands, the decay times 119 and 456 ps are obtained. Dielectric relaxation times of 20 and 138 ps are determined from the double-exponential spectral solvation response function C(t) of the probe molecule 4-dimethylamino-4'-cyanostilbene in PrCN at -100 degrees C. It is concluded from the similarity of the times 119 ps (PP) and 138 ps (DCS) that the deviation from double-exponential character for the fluorescence decays of PP in PrCN below -70 degrees C is due to the interference of dielectric solvent relaxation with the ICT reaction. This fact complicates the kinetic analysis of the LE and ICT fluorescence decays. The kinetic analysis for PP in PrCN is hence restricted to temperatures between -70 and -45 degrees C. From this analysis, the forward and backward ICT activation energies Ea (12 kJ/mol) and Ed (17 kJ/mol) are obtained, giving an ICT stabilization enthalpy -DeltaH of 5 kJ/mol. A

  2. Intramolecular photoassociation and photoinduced charge transfer in bridged diaryl compounds. 2. Charge-transfer interactions in the lowest excited singlet state of dinaphthylamines

    Energy Technology Data Exchange (ETDEWEB)

    Dresner, J.; Modiano, S.H.; Lim, E.C. [Univ. of Akron, OH (United States)

    1992-05-28

    The formation of an intramolecular charge-transfer (CT) exciplex is demonstrated for 1,1{prime}-dinaphthylamine (1,1{prime}-DNA) and 2,2{prime}-dinaphthylamine (2,2{prime}-DNA) in the lowest excited singlet state using steady-state and picosecond time-resolved fluorescence spectroscopy. The exciplex is formed through a mutual reorientation of the two naphthalene rings. Differences in the rate of formation and relaxation of the CT state for 1,1{prime}-DNA and 2,2{prime}-DNA indicate the importance of the bridge position in this process. The comparison of the steady-state fluorescence of 2,2{prime}-DNA with that of its protonated form, as well as the fluorescence of 2,2{prime}-dinaphthyl ether and 2,2{prime}-dinaphthylmethane, show the role of the lone-pair electrons of the nitrogen atom in the exciplex formation. 18 refs., 20 figs., 5 tabs.

  3. Charge transfer in high velocity C{sub n}{sup +} + He collisions

    Energy Technology Data Exchange (ETDEWEB)

    Chabot, M [Institut de Physique Nucleaire, Universite Paris Sud et CNRS, 91406 Orsay Cedex (France); Martinet, G [Institut de Physique Nucleaire, Universite Paris Sud et CNRS, 91406 Orsay Cedex (France); Mezdari, F [Laboratoire des Collisions Atomiques et Moleculaires, UMR 8625, Universite Paris Sud et CNRS, 91405 Orsay Cedex (France); Diaz-Tendero, S [Departamento de Quimica, Universidad Autonoma de Madrid, 28049 Madrid (Spain); Beroff-Wohrer, K [Laboratoire des Collisions Atomiques et Moleculaires, UMR 8625, Universite Paris Sud et CNRS, 91405 Orsay Cedex (France); Desesquelles, P [Centre de Spectrometrie Nucleaire et de Spectrometrie de Masse, Universite Paris Sud et CNRS, 91405 Orsay Cedex (France); Della-Negra, S [Institut de Physique Nucleaire, Universite Paris Sud et CNRS, 91406 Orsay Cedex (France); Hamrita, H [Institut de Physique Nucleaire, Universite Paris Sud et CNRS, 91406 Orsay Cedex (France); LePadellec, A [IRSAMC, Universite Paul Sabatier et CNRS, 31062 Toulouse Cedex 4 (France); Tuna, T [Institut de Physique Nucleaire, Universite Paris Sud et CNRS, 91406 Orsay Cedex (France); Montagnon, L [IRSAMC, Universite Paul Sabatier et CNRS, 31062 Toulouse Cedex 4 (France); Barat, M [Laboratoire des Collisions Atomiques et Moleculaires, UMR 8625, Universite Paris Sud et CNRS, 91405 Orsay Cedex (France); Simon, M [Laboratoire de Chimie Physique-Matiere et Rayonnement, UMR 7614, Universite Paris 6 et CNRS, 11 rue P et M Curie, 75231 Paris Cedex 05 (France); Ismail, I [Laboratoire des Collisions Atomiques et Moleculaires, UMR 8625, Universite Paris Sud et CNRS, 91405 Orsay Cedex (France)

    2006-06-14

    Dissociative and non-dissociative charge transfer cross sections in high velocity (v = 2.6 au) collisions between ionic carbon clusters C{sub n}{sup +} (n 2-10) and helium atoms have been measured. The sum of the cross sections has been found to increase significantly with n. Measurements of branching ratios for all fragmentation channels of excited C{sub n} clusters are reported. The summed branching ratios associated with a given number of emitted fragments exhibit odd-even alternations reflecting the higher stability of the species having an odd number of atoms. From an analysis of the summed branching ratios within the statistical microcanonical metropolis Monte Carlo model, and knowing the temperature of the incident clusters, deposited energy distributions due to the charge transfer process are deduced (n = 5-9). These distributions, of similar characteristics whatever n, peak around 4-5 eV and exhibit a large percentage of superexcited states situated above the continuum.

  4. On the morphology of a discotic liquid crystalline charge transfer complex.

    Science.gov (United States)

    Haverkate, Lucas A; Zbiri, Mohamed; Johnson, Mark R; Deme, Bruno; de Groot, Huub J M; Lefeber, Fons; Kotlewski, Arkadiusz; Picken, Stephen J; Mulder, Fokko M; Kearley, Gordon J

    2012-11-01

    Discotic liquid crystalline (DLC) charge transfer (CT) complexes, which combine visible light absorption with rapid charge transfer characteristics within the CT complex, can have a great potential for photovoltaic applications when they can be made to self-assemble in a bulk heterojunction arrangement with separate channels for electron and hole conduction. However, the morphology of some liquid crystalline CT complexes has been under debate for many years. In particular, the liquid crystalline CT complex built from the electron acceptor 2,4,7-trinitro-9-fluorenone (TNF) and discotic molecules has been reported to have the TNF "sandwiched" either between the discotic molecules within the same column or between the columns within the aliphatic tails of the discotic molecules. We present a detailed structural study of the prototypic 1:1 mixture of the discotic 2,3,6,7,10,11-hexakis(hexyloxy)triphenylene (HAT6) and TNF. Nuclear magnetic resonance (NMR) line widths and cross-polarization rates are consistent with the picosecond time scale anisotropic thermal motions of the HAT6 and TNF molecules previously observed. By computational integration of Rietveld refinement analyses of neutron diffraction patterns with density experiments and short-range structural constraints from heteronuclear 2D NMR, we determine that the TNF molecules are vertically oriented between HAT6 columns. The data provide the insight that a morphology of separate hole conducting channels of HAT6 molecules can be realized in the liquid crystalline CT complex.

  5. Excited State Structural Dynamics of Carotenoids and ChargeTransfer Systems

    Energy Technology Data Exchange (ETDEWEB)

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

    2006-01-01

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

  6. Charge Transfer Dynamics in Complexes of Light-Absorbing CdS Nanorods and Redox Catalysts

    Science.gov (United States)

    Wilker, Molly Bea

    The use of photoexcited electrons and holes in semiconductor nanocrystals as reduction and oxidation reagents is an intriguing way of harvesting photon energy to drive chemical reactions. This dissertation describes research efforts to understand the photoexcited charge transfer kinetics in complexes of colloidal CdS nanorods coupled with either a water oxidation or reduction catalyst. The first project focuses on the charge transfer interactions between photoexcited CdS nanorods and a mononuclear water oxidation catalyst derived from the [Ru(bpy)(tpy)Cl]+ parent structure. The second project details the electron transfer kinetics in complexes of CdS nanorods coupled with [FeFe]-hydrogenase, which catalyzes H+ reduction. These complexes photochemically produce H2 with quantum yields of up to 20%. Kinetics of electron transfer from CdS nanorods to hydrogenase play a critical role in the overall photochemical reactivity, as the quantum efficiency of electron transfer defines the upper limit on the quantum yield of H 2 generation. Insights from these time-resolved spectroscopic studies are used to discuss the intricate kinetic pathways involved in photochemical H2 generation and the mechanism for electron transfer from photoexcited nanorods to hydrogenase in photocatalytic complexes.

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

    KAUST Repository

    Vandewal, Koen

    2013-11-17

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

  8. Charge Transfer Mechanism in Titanium-Doped Microporous Silica for Photocatalytic Water-Splitting Applications

    Directory of Open Access Journals (Sweden)

    Wendi Sapp

    2016-02-01

    Full Text Available Solar energy conversion into chemical form is possible using artificial means. One example of a highly-efficient fuel is solar energy used to split water into oxygen and hydrogen. Efficient photocatalytic water-splitting remains an open challenge for researchers across the globe. Despite significant progress, several aspects of the reaction, including the charge transfer mechanism, are not fully clear. Density functional theory combined with density matrix equations of motion were used to identify and characterize the charge transfer mechanism involved in the dissociation of water. A simulated porous silica substrate, using periodic boundary conditions, with Ti4+ ions embedded on the inner pore wall was found to contain electron and hole trap states that could facilitate a chemical reaction. A trap state was located within the silica substrate that lengthened relaxation time, which may favor a chemical reaction. A chemical reaction would have to occur within the window of photoexcitation; therefore, the existence of a trapping state may encourage a chemical reaction. This provides evidence that the silica substrate plays an integral part in the electron/hole dynamics of the system, leading to the conclusion that both components (photoactive materials and support of heterogeneous catalytic systems are important in optimization of catalytic efficiency.

  9. Oscillatory Noncollinear Magnetism Induced by Interfacial Charge Transfer in Superlattices Composed of Metallic Oxides

    Directory of Open Access Journals (Sweden)

    Jason D. Hoffman

    2016-11-01

    Full Text Available Interfaces between correlated complex oxides are promising avenues to realize new forms of magnetism that arise as a result of charge transfer, proximity effects, and locally broken symmetries. We report on the discovery of a noncollinear magnetic structure in superlattices of the ferromagnetic metallic oxide La_{2/3}Sr_{1/3}MnO_{3} (LSMO and the correlated metal LaNiO_{3} (LNO. The exchange interaction between LSMO layers is mediated by the intervening LNO, such that the angle between the magnetization of neighboring LSMO layers varies in an oscillatory manner with the thickness of the LNO layer. The magnetic field, temperature, and spacer thickness dependence of the noncollinear structure are inconsistent with the bilinear and biquadratic interactions that are used to model the magnetic structure in conventional metallic multilayers. A model that couples the LSMO layers to a helical spin state within the LNO fits the observed behavior. We propose that the spin-helix results from the interaction between a spatially varying spin susceptibility within the LNO and interfacial charge transfer that creates localized Ni^{2+} states. Our work suggests a new approach to engineering noncollinear spin textures in metallic oxide heterostructures.

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

    KAUST Repository

    Zheng, Zilong

    2017-05-08

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

  11. Charge transfer in the electron donor-acceptor complex BH3NH3.

    Science.gov (United States)

    Mo, Yirong; Song, Lingchun; Wu, Wei; Zhang, Qianer

    2004-03-31

    As a simple yet strongly binding electron donor-acceptor (EDA) complex, BH(3)NH(3) serves as a good example to study the electron pair donor-acceptor complexes. We employed both the ab initio valence bond (VB) and block-localized wave function (BLW) methods to explore the electron transfer from NH(3) to BH(3). Conventionally, EDA complexes have been described by two diabatic states: one neutral state and one ionic charge-transferred state. Ab initio VB self-consistent field (VBSCF) computations generate the energy profiles of the two diabatic states together with the adiabatic (ground) state. Our calculations evidently demonstrated that the electron transfer between NH(3) and BH(3) falls in the abnormal regime where the reorganization energy is less than the exoergicity of the reaction. The nature of the NH(3)-BH(3) interaction is probed by an energy decomposition scheme based on the BLW method. We found that the variation of the charge-transfer energy with the donor-acceptor distance is insensitive to the computation levels and basis sets, but the estimation of the amount of electron transferred heavily depends on the population analysis procedures. The recent resurgence of interest in the nature of the rotation barrier in ethane prompted us to analyze the conformational change of BH(3)NH(3), which is an isoelectronic system with ethane. We found that the preference of the staggered structure over the eclipsed structure of BH(3)NH(3) is dominated by the Pauli exchange repulsion.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-01-13

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2009-01-01

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

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    Bai, Peng; Bazant, Martin Z

    2014-04-03

    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-Li(x)FePO4) 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.

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

    Science.gov (United States)

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

    2016-09-01

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

  17. Robust Artificial Immune System in the Hopfield network for Maximum k-Satisfiability

    Directory of Open Access Journals (Sweden)

    Mohd Asyraf Bin Mansor

    2017-08-01

    Full Text Available Artificial Immune System (AIS algorithm is a novel and vibrant computational paradigm, enthused by the biological immune system. Over the last few years, the artificial immune system has been sprouting to solve numerous computational and combinatorial optimization problems. In this paper, we introduce the restricted MAX-kSAT as a constraint optimization problem that can be solved by a robust computational technique. Hence, we will implement the artificial immune system algorithm incorporated with the Hopfield neural network to solve the restricted MAX-kSAT problem. The proposed paradigm will be compared with the traditional method, Brute force search algorithm integrated with Hopfield neural network. The results demonstrate that the artificial immune system integrated with Hopfield network outperforms the conventional Hopfield network in solving restricted MAX-kSAT. All in all, the result has provided a concrete evidence of the effectiveness of our proposed paradigm to be applied in other constraint optimization problem. The work presented here has many profound implications for future studies to counter the variety of satisfiability problem.

  18. Infinitely many states and stochastic symmetry in a Gaussian Potts-Hopfield model

    NARCIS (Netherlands)

    van Enter, ACD; Schaap, HG

    2002-01-01

    We study a Gaussian Potts-Hopfield model. Whereas for Ising spins and two disorder variables per site the chaotic pair scenario is realized, we find that for q-state Potts spins q (q - 1)-tuples occur. Beyond the breaking of a continuous stochastic symmetry, we study the fluctuations and obtain the

  19. Bifurcation and Hybrid Control for A Simple Hopfield Neural Networks with Delays

    Directory of Open Access Journals (Sweden)

    Zisen Mao

    2013-01-01

    Full Text Available A detailed analysis on the Hopf bifurcation of a delayed Hopfield neural network is given. Moreover, a new hybrid control strategy is proposed, in which time-delayed state feedback and parameter perturbation are used to control the Hopf bifurcation of the model. Numerical simulation results confirm that the new hybrid controller using time delay is efficient in controlling Hopf bifurcation.

  20. Effects of inter-molecular charge-transfer excitons on the external quantum efficiency of zinc-porphyrin/C{sub 60} heterojunction photovoltaic cells

    Energy Technology Data Exchange (ETDEWEB)

    Ryuzaki, Sou; Kai, Toshihiro; Onoe, Jun [Department of Nuclear Engineering, Tokyo Institute of Technology, Tokyo 152-8550 (Japan); Toda, Yasunori; Adachi, Satoru, E-mail: jonoe@nr.titech.ac.jp [Department of Applied Physics, Hokkaido University, Sapporo, Hokkaido 060-8628 (Japan)

    2011-04-13

    We have examined the structural effects of zinc-octaethylporphyrin [Zn(OEP)] films used as a donor on the external quantum efficiency (EQE) of organic heterojunction photovoltaic (OPV) cells [ITO/Zn(OEP)/C{sub 60}/Al], and investigated what exactly causes the improvement of EQE. When the structure of the Zn(OEP) films changed from amorphous to crystalline, the maximum EQE increased from 36% to 42%, which is greater than that of around 35% for previously reported OPV cells using buffer materials (Peumans and Forrest 2001 Appl. Phys. Lett. 79 126). The crystallization of Zn(OEP) films is found to increase the number of inter-molecular charge-transfer (IMCT) excitons and to enlarge the mobility of carriers and IMCT excitons, thus significantly improving the EQE of the photoabsorption band under illumination due to the IMCT excitons.

  1. Quantum confinement-tunable ultrafast charge transfer at the PbS quantum dot and phenyl-C61-butyric acid methyl ester interface

    KAUST Repository

    El-Ballouli, AlA'A O.

    2014-05-14

    Quantum dot (QD) solar cells have emerged as promising low-cost alternatives to existing photovoltaic technologies. Here, we investigate charge transfer and separation at PbS QDs and phenyl-C61-butyric acid methyl ester (PCBM) interfaces using a combination of femtosecond broadband transient absorption (TA) spectroscopy and steady-state photoluminescence quenching measurements. We analyzed ultrafast electron injection and charge separation at PbS QD/PCBM interfaces for four different QD sizes and as a function of PCBM concentration. The results reveal that the energy band alignment, tuned by the quantum size effect, is the key element for efficient electron injection and charge separation processes. More specifically, the steady-state and time-resolved data demonstrate that only small-sized PbS QDs with a bandgap larger than 1 eV can transfer electrons to PCBM upon light absorption. We show that these trends result from the formation of a type-II interface band alignment, as a consequence of the size distribution of the QDs. Transient absorption data indicate that electron injection from photoexcited PbS QDs to PCBM occurs within our temporal resolution of 120 fs for QDs with bandgaps that achieve type-II alignment, while virtually all signals observed in smaller bandgap QD samples result from large bandgap outliers in the size distribution. Taken together, our results clearly demonstrate that charge transfer rates at QD interfaces can be tuned by several orders of magnitude by engineering the QD size distribution. The work presented here will advance both the design and the understanding of QD interfaces for solar energy conversion. © 2014 American Chemical Society.

  2. Boosting surface charge-transfer doping efficiency and robustness of diamond with WO3 and ReO3

    Science.gov (United States)

    Tordjman, Moshe; Weinfeld, Kamira; Kalish, Rafi

    2017-09-01

    An advanced charge-transfer yield is demonstrated by employing single monolayers of transition-metal oxides—tungsten trioxide (WO3) and rhenium trioxide (ReO3)—deposited on the hydrogenated diamond surface, resulting in improved p-type sheet conductivity and thermal stability. Surface conductivities, as determined by Hall effect measurements as a function of temperature for WO3, yield a record sheet hole carrier concentration value of up to 2.52 × 1014 cm-2 at room temperature for only a few monolayers of coverage. Transfer doping with ReO3 exhibits a consistent narrow sheet carrier concentration value of around 3 × 1013 cm-2, exhibiting a thermal stability of up to 450 °C. This enhanced conductivity and temperature robustness exceed those reported for previously exposed surface electron acceptor materials used so far on a diamond surface. X-ray photoelectron spectroscopy measurements of the C1s core level shift as a function of WO3 and ReO3 layer thicknesses are used to determine the respective increase in surface band bending of the accumulation layers, leading to a different sub-surface two-dimensional hole gas formation efficiency in both cases. This substantial difference in charge-exchange efficiency is unexpected since both surface acceptors have very close work functions. Consequently, these results lead us to consider additional factors influencing the transfer doping mechanism. Transfer doping with WO3 reveals the highest yet reported transfer doping efficiency per minimal surface acceptor coverage. This improved surface conductivity performance and thermal stability will promote the realization of 2D diamond-based electronic devices facing process fabrication challenges.

  3. Optical properties of poly(3-hexylthiophene) and interfacial charge transfer between poly(3-hexylthiophene) and titanium dioxide in composites

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, Long; Zhang, Jianling [State Key Laboratory of Polymer Materials Engineering of China, Sichuan University, Polymer Research Institute of Sichuan University, Chengdu 610065 (China); Wang, Weiwei [State Key Laboratory of Polymer Materials Engineering of China, Sichuan University, Polymer Research Institute of Sichuan University, Chengdu 610065 (China); Institut des Matériaux Jean Rouxel, University of Nantes, CNRS, 2 rue de la Houssinière, 44322 Nantes (France); Yang, Haigang [State Key Laboratory of Polymer Materials Engineering of China, Sichuan University, Polymer Research Institute of Sichuan University, Chengdu 610065 (China); Reisdorffer, Frederic [Institut des Matériaux Jean Rouxel, University of Nantes, CNRS, 2 rue de la Houssinière, 44322 Nantes (France); Nguyen, Thien-Phap, E-mail: Thien-Phap.Nguyen@cnrs-imn.fr [Institut des Matériaux Jean Rouxel, University of Nantes, CNRS, 2 rue de la Houssinière, 44322 Nantes (France); Dan, Yi, E-mail: danyi@scu.edu.cn [State Key Laboratory of Polymer Materials Engineering of China, Sichuan University, Polymer Research Institute of Sichuan University, Chengdu 610065 (China)

    2015-03-15

    The optical properties of poly(3-hexylthiophene) (P3HT), in pristine form or with added anatase titanium dioxide (TiO{sub 2}) nanoparticles have been investigated, and the interfacial charge transfer between P3HT and TiO{sub 2} have been studied by steady-state luminescence spectroscopy analysis. The photoluminescence results revealed that incorporation of TiO{sub 2} nanoparticles in concentrations up to 0.3 mM significantly enhanced the luminescence intensity of P3HT when exposing to light of energy higher than TiO{sub 2} bandgap. The observed variation suggested an energy transfer from TiO{sub 2} nanoparticles to P3HT. Meanwhile, when P3HT/TiO{sub 2} composites were exposed to light of energy below TiO{sub 2} bandgap, TiO{sub 2} nanoparticles gradually quench the fluorescence of P3HT, demonstrating the injection of excited electrons from lowest unoccupied molecular orbit of P3HT to the conduction band of TiO{sub 2}. - Highlights: • Optical properties of P3HT, in pristine form or with added TiO{sub 2} were investigated. • Excitation above TiO{sub 2} bandgap produces a remarkable increase in P3HT emission. • The enhancement is attributed to transfer of excitation energy from TiO{sub 2} to P3HT. • TiO{sub 2} quenches P3HT emission when composites are excited below TiO{sub 2} bandgap. • The quench is due to the injection of excitons from LUMO of P3HT to CB of TiO{sub 2}.

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

    KAUST Repository

    Alsam, Amani Abdu

    2017-03-14

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

  5. The thermodynamics of charge transfer in DNA photolyase: using thermodynamic integration calculations to analyse the kinetics of electron transfer reactions.

    Science.gov (United States)

    Krapf, Sebastian; Koslowski, Thorsten; Steinbrecher, Thomas

    2010-08-28

    DNA Photolyases are light sensitive oxidoreductases present in many organisms that participate in the repair of photodamaged DNA. They are capable of electron transfer between a bound cofactor and a chain of tryptophan amino acid residues. Due to their unique mechanism and important function, photolyases have been subject to intense study in recent times, with both experimental and computational efforts. In this work, we present a novel application of classical molecular dynamics based free energy calculations, combined with quantum mechanical computations, to biomolecular charge transfer. Our approach allows for the determination of all reaction parameters in Marcus' theory of charge transport. We were able to calculate the free energy profile for the movement of a positive charge along protein sidechains involved in the biomolecule's function as well as charge-transfer rates that are in good agreement with experimental results. Our approach to simulate charge-transfer reactions explicitly includes the influence of protein flexibility and solvent dynamics on charge-transfer energetics. As applied here to a biomolecular system of considerable scientific interest, we believe the method to be easily adaptable to the study of charge-transfer phenomena in biochemistry and other fields.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-11-16

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

  7. Fe2+-Ti4+ vs. Fe2+-Fe3+ charge-transfer and short-range order in single chains of face-sharing octahedra: ellenbergerite and dumortierite

    Science.gov (United States)

    Chopin, C.; Langer, K.; Khomenko, V.

    2009-04-01

    In zoned pyrope megacrysts from the Dora-Maira UHP terrane, new, dark-violet colour varieties of the hexagonal, high-pressure silicate ellenbergerite extend the range of known Fe contents for this mineral from 0-0.1 to 0-0.4 atom pfu, for Ti contents commonly in the range 0.2-0.4 pfu. The new varieties show an extremely intense pleochroism, colourless for E perpendicular to c to deep Prussian blue for E//c, as compared to colourless to lilac or reddish purple for classical Fe-poor ellenbergerite. These features were the incentive for an electronic absorption spectroscopic study and a reappraisal of the interpretation of the charge transfers (CT), colour and ordering schemes in this group and the structurally related borosilicate dumortierite. Both structures are characterized by the presence of infinite single chains of face-sharing, partly vacant octahedra along the 6-fold screw axis and pseudo-hexad axis, respectively, in which the Fe and Ti atoms are partitioned. In the spectra of Fe-poor ellenbergerite, the presence of a single Fe2+-Ti4+ CT band near 19000 cm˘1 was taken as evidence for complete short-range ordering of Mg(Fe), Ti and vacancies in the octahedral single chain [1]. The E//c spectra of Fe-rich ellenbergerite show the same absorption band near 19000 cm˘1 but consistently flanked by another CT band near 14000 cm˘1 , the intensity of which increases with total Fe content. The latter is similar to the 12400 cm˘1 CT band observed as the single feature in E//c spectra of the isotructural (Ti-free and Fe-bearing) phosphoellenbergerite, and clearly assigned to Fe2+-Fe3+ CT in the octahedral single chain [1]. The same colour pattern occurs in the dumortierite group, with red Fe-poor, Ti-rich crystals showing a single CT band near 20000 cm˘1, blue Ti-poor crystals showing a single CT band near 16500 cm˘1, and violet Fe- and Ti-rich crystals showing a combination of the two bands [2]. In the light of the new data, we reinterpret the dumortierite colour

  8. Enhanced Three-Photon Absorption by Symmetric Twisted Intramolecular Charge Transfer

    Science.gov (United States)

    Guo, Fu-Quan; Yang, Jun; Zhang, Qi-Jin; Ming, Hai

    2005-06-01

    We report on a novel organic chromophore with symmetric twisted intramolecular charge transfer (TICT) state on excitation. The properties of nonlinear transmission induced by three-photon absorption (3 PA) are demonstrated pumped with nanosecond laser pulse. Large 3 PA cross sections as high as the order of 10-74 cm6s2 have been obtained for nanosecond and picosecond laser pulses at 1064 nm from intensity-dependent transmission measurements. Similar two emissive behaviours from one-photon and three-photon excited fluorescence spectra indicate that the linear and nonlinear fluorescences share the same TICT relaxation process from the excited states. The intensity dependence of upconversion fluorescence on the incident intensity obeys the cubic law that characterizes the three-photon absorption.

  9. Charge transfer state in DBP:C70 organic solar cells

    DEFF Research Database (Denmark)

    Sherafatipour, Golenaz; Benduhn, Johannes; Spoltore, Donato

    Organic solar cells (OSC) are green solar energy technology, which can be fabricated from organic compounds with cheep techniques and on flexible or transparent substrates such as plastic or glass. OSCs are cost efficient, and lightweight devices that can exhibit high power conversion efficiency...... of the CT states from which the maximum open circuit can be calculated and will set the base for modeling and optimizing the stability of the solar cells. 1. Cao, H. et al. Recent progress in degradation and stabilization of organic solar cells. J. Power Sources 264, 168–183 (2014). 2. Tvingstedt, K. et al....... Electroluminescence from charge transfer states in polymer solar cells. J. Am. Chem. Soc. 131, 11819–11824 (2009)....

  10. Sodium dodecyl benzene sulphonate mediated tautomerism of Eriochrome Black-T: Effect of charge transfer interaction

    Science.gov (United States)

    Ghosh, Sumit

    2010-11-01

    Interaction between anionic surfactant, sodium dodecyl benzene sulphonate, (SDBS) and an anionic dye Eriochrome Black-T, (EBT) has been investigated by visible spectroscopy, conductometry, dynamic light scattering and zeta potential measurements. Spectral changes of EBT observed on addition of SDBS indicate formation of quinone-hydrazone tautomer at pH 7.0, whereas in absence of SDBS this change appears at pH ˜ 9.45. However, at pH 7.0 this change in tautomerism is not observed in presence of sodium dodecyl sulphate (SDS). Experimental results indicate presence of charge transfer interaction between less stable quinone-hydrazone tautomer of EBT and SDBS molecules, which is confirmed using Benesi-Hildebrand and Scott equations.

  11. Laser-induced charge transfer in the CH/sup 6 +/ quasimolecule

    Energy Technology Data Exchange (ETDEWEB)

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

    1985-05-15

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

  12. Restoration of Conductivity with TTF-TCNQ Charge-Transfer Salts

    Energy Technology Data Exchange (ETDEWEB)

    Odom, Susan A.; Caruso, Mary M.; Finke, Aaron D.; Prokup, Alex M.; Ritchey, Joshua A.; Leonard, Francois; White, Scott R.; Sottos, Nancy R.; Moore, Jeffrey S.

    2010-05-03

    The formation of the conductive TTF-TCNQ (tetrathiafulvalene–tetracyanoquinodimethane) charge-transfer salt via rupture of microencapsulated solutions of its individual components is reported. Solutions of TTF and TCNQ in various solvents are separately incorporated into poly(urea-formaldehyde) core–shell microcapsules. Rupture of a mixture of TTF-containing microcapsules and TCNQ-containing microcapsules results in the formation of the crystalline salt, as verified by FTIR spectroscopy and powder X-ray diffraction. Preliminary measurements demonstrate the partial restoration of conductivity of severed gold electrodes in the presence of TTF-TCNQ derived in situ. This is the first microcapsule system for the restoration of conductivity in mechanically damaged electronic devices in which the repairing agent is not conductive until its release.

  13. Electroluminescence from charge transfer states in Donor/Acceptor solar cells

    DEFF Research Database (Denmark)

    Sherafatipour, Golenaz; Madsen, Morten

    Charge photocurrent generation is a key process in solar energy conversion systems. Effective dissociation of the photo-generated electron-hole pairs (excitons) has a strong influence on the efficiency of the organic solar cells. Charge dissociation takes place at the donor/acceptor interface via...... charge transfer (CT) excitons, which is Coulombically bound interfacial electron- hole pairs residing at the donor/acceptor heterojunctions. The CT state represents an intermediate state between the exciton dissociation and recombination back to the ground state. Since the recombination of photo-generated...... charges is a major limitation for the efficiency of the organic solar cells, a thorough understanding of this loss mechanism is crucial to improve the performance of the devices. Furthermore, examining this interfacial state is of great importance in order to maximize open-circuit voltage and photocurrent...

  14. Charge-Transfer within Zr-Based MOF: The Role of Polar Node.

    Science.gov (United States)

    Van Wyk, Andrea; Smith, Tanner; Park, Jaehong; Deria, Pravas

    2018-02-09

    Metal-organic frameworks (MOFs) are emerging materials for electro- and photo- chemical applications, where understanding of underlying charge-transfer (CT) process will facilitate designing new materials. However, involvement of counter-ions in traditional electrochemical experiments complicates the probe on the role of various components during a CT event. A CT reaction between photo-excited MOF linker and a node-anchored ferrocene, within mesoporous framework NU-1000, was spectroscopically probed without the involvement of electrolyte based counter ions. Dielectric dependent CT kinetics indicate that the process involves a high reorganization energy that is required to polarize the node bound hydroxyl/aqua ligands. The findings have clear implication on the design of MOF-based electrocatalysis and photoelectrochemical devices.

  15. Charge-transfer excited states in aqueous DNA: Insights from many-body Green's function theory.

    Science.gov (United States)

    Yin, Huabing; Ma, Yuchen; Mu, Jinglin; Liu, Chengbu; Rohlfing, Michael

    2014-06-06

    Charge-transfer (CT) excited states play an important role in the excited-state dynamics of DNA in aqueous solution. However, there is still much controversy on their energies. By ab initio many-body Green's function theory, together with classical molecular dynamics simulations, we confirm the existence of CT states at the lower energy side of the optical absorption maximum in aqueous DNA as observed in experiments. We find that the hydration shell can exert strong effects (∼1  eV) on both the electronic structure and CT states of DNA molecules through dipole electric fields. In this case, the solvent cannot be simply regarded as a macroscopic screening medium as usual. The influence of base stacking and base pairing on the CT states is also discussed.

  16. Charge-transfer interaction mediated organogels from 18β-glycyrrhetinic acid appended pyrene

    Directory of Open Access Journals (Sweden)

    Jun Hu

    2013-12-01

    Full Text Available We describe herein the two-component charge-transfer (CT interaction induced organogel formation with 18β-glycyrrhetinic acid appended pyrene (GA-pyrene, 3 as the donor, and 2,4,7-trinitrofluorenone (TNF, 4 as the acceptor. The use of TNF (4 as a versatile electron acceptor in the formation of CT gels is demonstrated through the formation of gels in a variety of solvents. Thermal stability, stoichiometry, scanning electron microscopy (SEM, optical micrographs, and circular dichroism (CD are performed on these CT gels to investigate their thermal and assembly properties. UV–vis, fluorescence, mass spectrometric as well as variable-temperature 1H NMR experiments on these gels suggest that the CT interaction is one of the major driving forces for the formation of these organogels.

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

    Directory of Open Access Journals (Sweden)

    Rebecca Boll

    2016-07-01

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

  18. Ultrafast Charge Transfer Processes Accompanying K L L Auger Decay in Aqueous KCl Solution

    Science.gov (United States)

    Céolin, D.; Kryzhevoi, N. V.; Nicolas, Ch.; Pokapanich, W.; Choksakulporn, S.; Songsiriritthigul, P.; Saisopa, T.; Rattanachai, Y.; Utsumi, Y.; Palaudoux, J.; Öhrwall, G.; Rueff, J.-P.

    2017-12-01

    X-ray photoelectron and K L L Auger spectra were measured for the K+ and Cl- ions in aqueous KCl solution. While the XPS spectra of these ions have similar structures, both exhibiting only weak satellites near the main line, the Auger spectra differ dramatically. Contrary to the chloride case, a very strong extra peak was found in the Auger spectrum of K+ at the low kinetic energy side of the D 1 state. Using the equivalent core model and ab initio calculations this spectral feature was assigned to electron transfer processes from solvent water molecules to the solvated cation. The observed charge transfer processes are suggested to play an important role in charge redistribution following single and multiple core-hole creation in atoms and molecules placed into environment.

  19. Three-dimensional effects in resonant charge transfer between atomic particles and nanosystems

    Science.gov (United States)

    Gainullin, I. K.; Sonkin, M. A.

    2015-08-01

    Resonant charge transfer (RCT) between negative ions and a metallic nanosystem was investigated by means of a high-performance ab initio three-dimensional (3D) numerical solver. During RCT, an electron was shown to occupy succesively nanosystem eigenstates along the z , ρ , and φ coordinates. Electron tunneling into a nanosystem is a reversible process, because after some time the electron propagates back to the ion. RCT efficiency in a nanosystem was found to exhibit quantum-size effects as well as lateral ion position dependence. This means that during ion-surface interaction, the nanosystem's size and the ion trajectory strongly influence the final charge state of the ion. In the case of real 3D systems (without cylindrical symmetry), the electron density currents form quantum vortices; this result is rather nontrivial for static systems. In addition, the limits of the adiabatic approximation (rate equation) for the RCT calculation with nanosystems are defined.

  20. Mutual Charge Transfer for Estimating Salinity Ratio for Offshore Icing Sensors

    Directory of Open Access Journals (Sweden)

    Umair N. Mughal

    2015-11-01

    Full Text Available For offshore measurements in Cold Regions, salinity of ice is also a critical parameter (together with many other parameters such as icing type, load, icing rate and melting rate to be identified in order to optimize the performance of anti/de icing systems. Although there are some available sensory solutions in the market to measure real time salinity levels of water, however there are still not many real time techniques or solutions to measure the salinity of ice. In this research task, mutual charge transfer technique is utilized to measure the zero crossover values of different samples of ice and water with varying salt ratios. An analytical relation between percentage salinity ratio of ice and zero crossover values is established. The aim of this paper is therefore a feasibility study to discuss the testing methodology and testing results.

  1. Mechanisms for charge-transfer processes at electrode/solid-electrolyte interfaces.

    Energy Technology Data Exchange (ETDEWEB)

    Chueh, William; El Gabaly Marquez, Farid; Whaley, Josh A.; McCarty, Kevin F.; McDaniel, Anthony H.; Farrow, Roger L.

    2011-11-01

    This report summarizes the accomplishments of a Laboratory-Directed Research and Development (LDRD) project focused on developing and applying new x-ray spectroscopies to understand and improve electric charge transfer in electrochemical devices. Our approach studies the device materials as they function at elevated temperature and in the presence of sufficient gas to generate meaningful currents through the device. We developed hardware and methods to allow x-ray photoelectron spectroscopy to be applied under these conditions. We then showed that the approach can measure the local electric potentials of the materials, identify the chemical nature of the electrochemical intermediate reaction species and determine the chemical state of the active materials. When performed simultaneous to traditional impedance-based analysis, the approach provides an unprecedented characterization of an operating electrochemical system.

  2. Charge transfer in carbon composites based on fullerenes and exfoliated graphite

    Science.gov (United States)

    Berezkin, V. I.

    2017-07-01

    Kinetic processes have been studied in composites based on fullerenes and exfoliated graphite at the initial proportions of components from 1: 16 to 16: 1 in mass. The samples are produced by heat treatment of initial dispersed mixtures in vacuum in the diffusion-adsorption process, their further cold pressing, and annealing. It is shown that the annealing almost does not influence the conduction mechanisms and only induces additional structural defects acting as electron traps. As a whole, the results obtained at the noted proportions of components make it possible to consider the material as a compensated metallic system with a structural disorder in which the charge transfer at temperatures from 4.2 K to room temperature is controlled by quantum interference phenomena. At low temperatures, the effect of a weak localization is observed, and the electron-electron interactions take place at medium and high temperatures.

  3. Correlation between the Open-Circuit Voltage and Charge Transfer State Energy in Organic Photovoltaic Cells.

    Science.gov (United States)

    Zou, Yunlong; Holmes, Russell J

    2015-08-26

    In order to further improve the performance of organic photovoltaic cells (OPVs), it is essential to better understand the factors that limit the open-circuit voltage (VOC). Previous work has sought to correlate the value of VOC in donor-acceptor (D-A) OPVs to the interface energy level offset (EDA). In this work, measurements of electroluminescence are used to extract the charge transfer (CT) state energy for multiple small molecule D-A pairings. The CT state as measured from electroluminescence is found to show better correlation to the maximum VOC than EDA. The difference between EDA and the CT state energy is attributed to the Coulombic binding energy of the CT state. This correlation is demonstrated explicitly by inserting an insulating spacer layer between the donor and acceptor materials, reducing the binding energy of the CT state and increasing the measured VOC. These results demonstrate a direct correlation between maximum VOC and CT state energy.

  4. Dynamics of charge-transfer excited states relevant to photochemical energy conversion

    Energy Technology Data Exchange (ETDEWEB)

    Lim, E.C.

    1993-01-01

    A systematic study of intramolecular photoassociation and photoinduced charge transfer (CT) was initiated in bichromophoric systems of M-X-M, where two identical aromatic hydrocarbons M are joined by X=CH[sub 2], O, NH, etc. Dinaphthylamines, dinaphthylethers, and dinaphthylmethanes in nonpolar solvents form triplet excimers, following inter system crossing of singlets to the triplet manifold; in polar solvents, the molecule forms an intramolecular CT state. The interchromophore interaction study was extended to N-phenyl-2-naphthylamine. The lowest excited singlet states of the dinaphthylamines were studied by semiempirical quantum chemical methods. Exciplex formation was studied in excited states of jet-cooled van der Waals complexes, such as fluorene/substituted benzenes and 1-cyanonaphthalene-aliphatic amines.

  5. Photoinduced charge-transfer dynamics of sequentially aligned donor-acceptor systems in an ionic liquid.

    Science.gov (United States)

    Muramatsu, Masayasu; Katayama, Tetsuro; Ito, Syoji; Nagasawa, Yutaka; Matsuo, Daisuke; Suzuma, Yoshinori; Peng, Lifen; Orita, Akihiro; Otera, Junzo; Miyasaka, Hiroshi

    2013-10-01

    Photoinduced charge separation processes of linear phenyleneethynylene derivatives (PEN) with different sequences of electron-withdrawing perfluorophenyl groups (A) and electron-donating phenyl groups (D) were investigated in an ionic liquid (IL), BmimTFSI, by picosecond time-resolved fluorescence (TRF) and transient absorption (TA) spectroscopies. Very rapid photoinduced charge separation within 10 ps in AADD was followed by the stabilization of the charge-transfer (CT) state by the solvation, while the excited states in ADAD and ADDA were ascribable to the locally excited (LE) state. Equilibrium between the LE and CT states was established for DAAD with time constants of forward and backward processes much faster than the solvation time. The relative population of the CT state increases with time owing to the dynamic stabilization of the CT state by the solvation. The elementary charge separation process, the increase in the CT population, and their relation to the solvation time were discussed.

  6. Charge transfer and magnetization of a MoS2 monolayer at the Co(0001)/MoS2 interface

    Science.gov (United States)

    Garandel, T.; Arras, R.; Marie, X.; Renucci, P.; Calmels, L.

    2017-10-01

    The Co/MoS2 system may constitute a fundamental building block for future spintronic devices based on a single MoS2 transition metal dichalcogenide monolayer. Here, the hcp Co(0001)/MoS2 interface electronic structure as well as magnetic properties are investigated by first principles calculations based on the density functional theory. The charge transfer due to covalent bonding between S and Co atoms at the interface has been calculated for the lowest energy configuration obtained after optimization of the atomic coordinates. This charge transfer is different for majority and minority spin electrons, which induces a magnetization of the MoS2 layer bellow the Cobalt contact. The connection between the charge transfers at the interface and the modification of the magnetic properties is discussed.

  7. Analytical study for the charge-transfer complexes of losartan potassium

    Energy Technology Data Exchange (ETDEWEB)

    Darwish, Ibrahim A. [Department of Pharmaceutical Analytical Chemistry, Faculty of Pharmacy, Assiut University, Assiut 71526 (Egypt)]. E-mail: iadarwish@yahoo.com

    2005-09-06

    Studies were carried out, for the first time, to investigate the charge-transfer reactions of losartan potassium (LOS-K) as n-electron donor with the {sigma}-acceptor iodine and various {pi}-acceptors: 7,7,8,8-tetracyanoquinodimethane, 1,3,5-trinitrobenzene, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, p-chloranilic acid, tetracyanoethylene, 2,3,5,6-tetrabromo-1,4-benzoquinone, 2,3,5,6-tetrachloro-1,4-benzoquinone, and 2,4,7-trinitro-9-fluorenone. Different colored charge-transfer complexes and radical anions were obtained. Different variables affecting the reactions were studied and optimized. The formed complexes and the site of interaction were examined by UV-vis, IR, and {sup 1}H NMR techniques, and computational molecular modeling. The formation of the colored complexes were utilized in the development of simple, rapid and accurate spectrophotometric methods for the analysis of LOS-K in pure form as well as in its pharmaceutical tablets. Under the optimum reaction conditions, linear relationships with good correlation coefficients (0.9985-0.9998) were found between the absorbances and the concentrations of LOS-K in the range of 2-200 {mu}g ml{sup -1}. The limits of assays detection ranged from 0.61 to 19.65 {mu}g ml{sup -1}. No interference could be observed from the co-formulated hydrochlorothiazide (HCTZ), as well as from the additives commonly present in the tablets. The methods were successfully applied to the analysis of tablets from different manufacturers that contain LOS-K, alone or combined with HCTZ, with good accuracy and precision; the recovery percentages ranged from 98.96 {+-} 1.62% to 101.58 {+-} 1.29%. The results were compared favourably with the reported method.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-08-15

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

  9. Synthesis, single-crystal, DNA interaction, spectrophotometric and spectroscopic characterization of the hydrogen-bonded charge transfer complex of 2-aminopyrimidine with π-acceptor chloranilic acid at different temperature in acetonitrile.

    Science.gov (United States)

    Zulkarnain; Miyan, Lal; Ahmad, Afaq; Fazle Alam, Md; Younus, Hina

    2017-09-01

    The charge transfer (CT) interaction of 2-aminopyrimidine (AP) with chloranilic acid (CLA) as π-acceptor was investigated spectrophotometrically in acetonitrile at different temperatures in the range of 25-50°C. The 1:1 stoichiometry of the synthesized CT complex was detected using straight line method. Benesi-Hildebrand equation was used to determine the association constant (KCT), molar extinction coefficient (ε) and other physical parameters. Various thermodynamics parameters such as enthalpy (ΔH), entropy (ΔS) and free energy (ΔG) were determined using UV-Visible spectrophotometry in acetonitrile at different temperatures. (1)H NMR, FTIR, ESI-MS, elemental analyses, and UV-Visible techniques were used to characterize the hydrogen-bonded CT complex. (1)H NMR spectroscopy was also used for the analysis of the CT complex where both hydrogen bond and charge transfer were present in its molecular composition. The interaction of the selected organic compound with Ct-DNA was well investigated using fluorescence spectroscopic method. Stern-Volmer constant (Ksv) was used to estimate the fluorescence quenching efficiency. Circular dichroism (CD) spectroscopy was employed to measure the conformational change of DNA in the presence of CT complex. Furthermore, the drug CT complex detected changes in its viscosity. The charge transfer complex was formed as a result of the transfer of the lone pair of electrons from donor to the acceptor and exhibits well resolved charge transfer bands in the regions where absorption by both donor and acceptor were absent. The thermal composition and stability of the CT complex were analyzed using thermogravimetric and differential thermal analysis (TGA and DTA) studies. The X-ray crystal structure was used for the interpretation of the structure of the [(AP)(+) (CLA)(-)] CT complex. The crystal structure indicated that cation and anion are linked through strong N(+)H----O(-) type of hydrogen bond. Copyright © 2017 Elsevier B.V. All

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

    Science.gov (United States)

    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.

  11. Assignment of the Charge-Transfer Excited States of Bis(N-Heterocyclic) Complexes of Copper(I)

    Science.gov (United States)

    1989-03-21

    Excited States of Bis (N-Heterocyclic) Complexes of Copper ( I) 12 PERSONAL AUTHOR(S( W. L. Parker and G. A. Crosby 3a 7YPE OF REPORT i b ’!ME COVERED ~ aDATE...Assignment of the Charge-Transfer Excited States of Bis (N-Heterocyclic) Complexes of Copper (I) by W. L. Parker and G. A. Crosby Prepared for Publication in...IHmited. Assignment of the Charge-Transfer Excited States of Bis (N-Heterocycl ic) Complexes of Copper (I) W. L. Parker and G. A. Crosby* Chemical

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

    Science.gov (United States)

    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.

  13. Ultrafast intramolecular charge transfer with N-(4-cyanophenyl)carbazole. Evidence for a LE precursor and dual LE + ICT fluorescence.

    Science.gov (United States)

    Galievsky, Victor A; Druzhinin, Sergey I; Demeter, Attila; Mayer, Peter; Kovalenko, Sergey A; Senyushkina, Tamara A; Zachariasse, Klaas A

    2010-12-09

    The photophysics of N-(4-cyanophenyl)carbazole (NP4CN) was investigated by using absorption and fluorescence spectra, picosecond fluorescence decays, and femtosecond transient absorption. In the nonpolar n-hexane as well as in the polar solvent acetonitrile (MeCN), a locally excited (LE) state is detected, as a precursor for the intramolecular charge transfer (ICT) state. A LE → ICT reaction time τ(2) at 22 °C of 0.95 ps in ethyl cyanide (EtCN) and 0.32 ps in MeCN is determined from the decay of the LE excited state absorption (ESA) maximum around 620 nm. In the ESA spectrum of NP4CN in n-hexane at a pump-probe delay time of 100 ps, an important contribution of the LE band remains alongside the ICT band, in contrast to what is observed in EtCN and MeCN. This shows that a LE ⇄ ICT equilibrium is established in this solvent and the ICT reaction time of 0.5 ps is equal to the reciprocal of the sum of the forward and backward ICT rate constants 1/(k(a) + k(d)). In the photostationary S(0) → S(n) absorption spectrum of NP4CN in n-hexane and MeCN, an additional CT absorption band appears, absent in the sum of the spectra of its electron donor (D) and acceptor (A) subgroups carbazole and benzonitrile. This CT band is located at an energy of ∼4000 cm(-1) lower than for N-phenylcarbazole (NPC), due to the larger electron affinity of the benzonitrile moiety of NP4CN than the phenyl subunit of NPC. The fluorescence spectrum of NP4CN in n-hexane at 25 °C mainly consists of a structured LE emission, with a small ICT admixture, indicating that a LE → ICT reaction just starts to occur under these conditions. In di-n-pentyl ether (DPeE) and di-n-butyl ether (DBE), a LE emission is found upon cooling at the high-energy edge of the ICT fluorescence band, caused by the onset of dielectric solvent relaxation. This is not the case in more polar solvents, such as diethyl ether (DEE) and MeCN, in which a structureless ICT emission band fully overlaps the strongly quenched LE

  14. Fast Recall for Complex-Valued Hopfield Neural Networks with Projection Rules

    Directory of Open Access Journals (Sweden)

    Masaki Kobayashi

    2017-01-01

    Full Text Available Many models of neural networks have been extended to complex-valued neural networks. A complex-valued Hopfield neural network (CHNN is a complex-valued version of a Hopfield neural network. Complex-valued neurons can represent multistates, and CHNNs are available for the storage of multilevel data, such as gray-scale images. The CHNNs are often trapped into the local minima, and their noise tolerance is low. Lee improved the noise tolerance of the CHNNs by detecting and exiting the local minima. In the present work, we propose a new recall algorithm that eliminates the local minima. We show that our proposed recall algorithm not only accelerated the recall but also improved the noise tolerance through computer simulations.

  15. Stability Analysis of Discrete Hopfield Neural Networks with the Nonnegative Definite Monotone Increasing Weight Function Matrix

    Directory of Open Access Journals (Sweden)

    Jun Li

    2009-01-01

    Full Text Available The original Hopfield neural networks model is adapted so that the weights of the resulting network are time varying. In this paper, the Discrete Hopfield neural networks with weight function matrix (DHNNWFM the weight changes with time, are considered, and the stability of DHNNWFM is analyzed. Combined with the Lyapunov function, we obtain some important results that if weight function matrix (WFM is weakly (or strongly nonnegative definite function matrix, the DHNNWFM will converge to a stable state in serial (or parallel model, and if WFM consisted of strongly nonnegative definite function matrix and column (or row diagonally dominant function matrix, DHNNWFM will converge to a stable state in parallel model.

  16. Theory of chemical kinetics and charge transfer based on nonequilibrium thermodynamics.

    Science.gov (United States)

    Bazant, Martin Z

    2013-05-21

    Advances in the fields of catalysis and electrochemical energy conversion often involve nanoparticles, which can have kinetics surprisingly different from the bulk material. Classical theories of chemical kinetics assume independent reactions in dilute solutions, whose rates are determined by mean concentrations. In condensed matter, strong interactions alter chemical activities and create variations that can dramatically affect the reaction rate. The extreme case is that of a reaction coupled to a phase transformation, whose kinetics must depend not only on the order parameter but also on its gradients at phase boundaries. Reaction-driven phase transformations are common in electrochemistry, when charge transfer is accompanied by ion intercalation or deposition in a solid phase. Examples abound in Li-ion, metal-air, and lead-acid batteries, as well as metal electrodeposition-dissolution. Despite complex thermodynamics, however, the standard kinetic model is the Butler-Volmer equation, based on a dilute solution approximation. The Marcus theory of charge transfer likewise considers isolated reactants and neglects elastic stress, configurational entropy, and other nonidealities in condensed phases. The limitations of existing theories recently became apparent for the Li-ion battery material LixFePO4 (LFP). It has a strong tendency to separate into Li-rich and Li-poor solid phases, which scientists believe limits its performance. Chemists first modeled phase separation in LFP as an isotropic "shrinking core" within each particle, but experiments later revealed striped phase boundaries on the active crystal facet. This raised the question: What is the reaction rate at a surface undergoing a phase transformation? Meanwhile, dramatic rate enhancement was attained with LFP nanoparticles, and classical battery models could not predict the roles of phase separation and surface modification. In this Account, I present a general theory of chemical kinetics, developed over

  17. Mechanism of charge transfer/disproportionation in LnCu3Fe4O12 (Ln = lanthanides)

    Science.gov (United States)

    Rezaei, N.; Hansmann, P.; Bahramy, M. S.; Arita, R.

    2014-03-01

    The Fe-Cu intersite charge transfer and Fe charge disproportionation are interesting phenomena observed in some LnCu3Fe4O12 (Ln = lanthanides) compounds containing light and heavy Ln atoms, respectively. We show that a change in the spin state is responsible for the intersite charge transfer in the light Ln compounds. At the high-spin state, such systems prefer an unusual Cu d8 configuration, whereas at the low-spin state they retreat to the normal Cu d9 configuration through a charge transfer from Fe to the Cu 3dxy orbital. We find that the strength of the crystal-field splitting and the relative energy ordering between Cu 3dxy and Fe 3d states are the key parameters determining the intersite charge transfer (charge disproportionation) in light (heavy) Ln compounds. It is further proposed that the size of Ln affects the on-site interaction strength of Cu 3d states, leading to a strong modification of the Cu L3-edge spectrum, as observed by the x-ray-absorption spectroscopy.

  18. Coherence, energy and charge transfers in de-excitation pathways of electronic excited state of biomolecules in photosynthesis

    DEFF Research Database (Denmark)

    Bohr, Henrik; Malik, F. Bary

    2013-01-01

    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 F¨orster–Dexter th...

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

    KAUST Repository

    Chen, Xian Kai

    2016-09-05

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

  20. High storage capacity in the Hopfield model with auto-interactions—stability analysis

    Science.gov (United States)

    Rocchi, Jacopo; Saad, David; Tantari, Daniele

    2017-11-01

    Recent studies point to the potential storage of a large number of patterns in the celebrated Hopfield associative memory model, well beyond the limits obtained previously. We investigate the properties of new fixed points to discover that they exhibit instabilities for small perturbations and are therefore of limited value as associative memories. Moreover, a large deviations approach also shows that errors introduced to the original patterns induce additional errors and increased corruption with respect to the stored patterns.

  1. Hopfield neural network and optical fiber sensor as intelligent heart rate monitor

    Science.gov (United States)

    Mutter, Kussay Nugamesh

    2018-01-01

    This paper presents a design and fabrication of an intelligent fiber-optic sensor used for examining and monitoring heart rate activity. It is found in the literature that the use of fiber sensors as heart rate sensor is widely studied. However, the use of smart sensors based on Hopfield neural networks is very low. In this work, the sensor is a three fibers without cladding of about 1 cm, fed by laser light of 1550 nm of wavelength. The sensing portions are mounted with a micro sensitive diaphragm to transfer the pulse pressure on the left radial wrist. The influenced light intensity will be detected by a three photodetectors as inputs into the Hopfield neural network algorithm. The latter is a singlelayer auto-associative memory structure with a same input and output layers. The prior training weights are stored in the net memory for the standard recorded normal heart rate signals. The sensors' heads work on the reflection intensity basis. The novelty here is that the sensor uses a pulse pressure and Hopfield neural network in an integrity approach. The results showed a significant output measurements of heart rate and counting with a plausible error rate.

  2. Enhanced storage capacity with errors in scale-free Hopfield neural networks: An analytical study.

    Science.gov (United States)

    Kim, Do-Hyun; Park, Jinha; Kahng, Byungnam

    2017-01-01

    The Hopfield model is a pioneering neural network model with associative memory retrieval. The analytical solution of the model in mean field limit revealed that memories can be retrieved without any error up to a finite storage capacity of O(N), where N is the system size. Beyond the threshold, they are completely lost. Since the introduction of the Hopfield model, the theory of neural networks has been further developed toward realistic neural networks using analog neurons, spiking neurons, etc. Nevertheless, those advances are based on fully connected networks, which are inconsistent with recent experimental discovery that the number of connections of each neuron seems to be heterogeneous, following a heavy-tailed distribution. Motivated by this observation, we consider the Hopfield model on scale-free networks and obtain a different pattern of associative memory retrieval from that obtained on the fully connected network: the storage capacity becomes tremendously enhanced but with some error in the memory retrieval, which appears as the heterogeneity of the connections is increased. Moreover, the error rates are also obtained on several real neural networks and are indeed similar to that on scale-free model networks.

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

    Science.gov (United States)

    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.

  4. Complexes with Tunable Intramolecular Ferrocene to Ti(IV) Electronic Transitions: Models for Solid State Fe(II) to Ti(IV) Charge Transfer.

    Science.gov (United States)

    Turlington, Michael D; Pienkos, Jared A; Carlton, Elizabeth S; Wroblewski, Karlee N; Myers, Alexis R; Trindle, Carl O; Altun, Zikri; Rack, Jeffrey J; Wagenknecht, Paul S

    2016-03-07

    Iron(II)-to-titanium(IV) metal-to-metal-charge transfer (MMCT) is important in the photosensitization of TiO2 by ferrocyanide, charge transfer in solid-state metal-oxide photocatalysts, and has been invoked to explain the blue color of sapphire, blue kyanite, and some lunar material. Herein, a series of complexes with alkynyl linkages between ferrocene (Fc) and Ti(IV) has been prepared and characterized by UV-vis spectroscopy and electrochemistry. Complexes with two ferrocene substituents include Cp2Ti(C2Fc)2, Cp*2Ti(C2Fc)2, and Cp2Ti(C4Fc)2. Complexes with a single ferrocene utilize a titanocene with a trimethylsilyl derivatized Cp ring, (TMS)Cp, and comprise the complexes (TMS)Cp2Ti(C2Fc)(C2R), where R = C6H5, p-C6H4CF3, and CF3. The complexes are compared to Cp2Ti(C2Ph)2, which lacks the second metal. Cyclic voltammetry for all complexes reveals a reversible Ti(IV/III) reduction wave and an Fe(II/III) oxidation that is irreversible for all complexes except (TMS)Cp2Ti(C2Fc)(C2CF3). All of the complexes with both Fc and Ti show an intense absorption (4000 M(-1)cm(-1) ferrocene donor. The energy of the absorption tracks with the difference between the Ti(IV/III) and Fe(III/II) reduction potentials, shifting to lower energy as the difference in potentials decreases. Reorganization energies, λ, have been determined using band shape analysis (2600 cm(-1) ferrocene donor. Marcus-Hush-type analysis of the electrochemical and spectroscopic data are consistent with the assignment of the low-energy absorption as a MMCT band. TD-DFT analysis also supports this assignment. Solvatochromism is apparent for the MMCT band of all complexes, there being a bathochromic shift upon increasing polarizability of the solvent. The magnitude of the shift is dependent on both the electron density at Ti(IV) and the identity of the linker between the titanocene and the Fc. Complexes with a MMCT are photochemically stable, whereas Cp2Ti(C2Ph)2 rapidly decomposes upon photolysis.

  5. A Low-Molecular-Weight Gelator Composed of Pyrene and Fluorene Moieties for Effective Charge Transfer in Supramolecular Ambidextrous Gel.

    Science.gov (United States)

    Reddy, Samala Murali Mohan; Dorishetty, Pramod; Augustine, George; Deshpande, Abhijit P; Ayyadurai, Niraikulam; Shanmugam, Ganesh

    2017-11-28

    Charge-transfer (CT) gel materials obtained from low-molecular-weight (LMW) compounds through a supramolecular self-assembly approach have received fascinating attention by many researchers because of their interesting material property and potential applications. However, most of the CT gel materials constructed were of organogels while the construction of CT gels in the form of a hydrogel is a challenge because of the solubility issue in water, which considerably limits the use of CT hydrogels. Herein, for the first time, we report a new LMW gelator [Nα-(fluorenylmethoxycarbonyl)-Nε-(δ-butyric-1-pyrenyl)-l-lysine, (FmKPy)], composed of two functional moieties such as fluorenylmethoxycarbonyl and pyrene, which not only parade both hydro and organo (ambidextrous) supramolecular gel formation but also exhibit CT ambidextrous gels when mixed with an electron acceptor such as 2,4,7-trinitro-9-fluorenone (TNF). This finding is significant as the established CT organogelator in the literature did not form an organogel in the absence of an electron acceptor or lose their gelation property upon the addition of the acceptor. CT between pyrene and TNF was confirmed by the color change as well as the appearance of the CT band in the visible region of the absorption spectrum. CT between FmKPy and TNF was supported by the solvent dilution method using tetrahydrofuran as the gel breaker and pyrene fluorescence quenching in the case compound containing pyrene and TNF. The morphology of FmKPy ambidextrous gels indicates the fibrous nature while the self-assembled structure is primarily stabilized by π-π stacking among fluorenyl and pyrenyl moieties and hydrogen bonding between amide groups. The FmKPy-TNF CT ambidextrous gel retains the fibrous nature; however, the size of the fibers changed. In FmKPy-TNF CT gels, TNF is intercalated between pyrene moieties in the self-assembled structure as confirmed by fluorescence quenching and powder X-ray diffraction. The Fm

  6. Influence of the energy of charge transfer on non-covalent interactions between fullerenes and a designed bisporphyrin.

    Science.gov (United States)

    Pal, Debabrata; Ray, Anamika; Bhattacharya, Sumanta

    2012-09-01

    The present paper reports the spectroscopic and theoretical investigations on the formation of supramolecular complexes of a designed bisporphyrin (1) with C(60) and C(70) in toluene. Absorption spectrophotometric studies establish appreciable amount of ground state electronic interaction between fullerenes and 1. The interaction is facilitated through charge transfer (CT) transition as evidenced from well defined CT absorption bands in the visible region of the electronic spectra. In our present case, the CT interaction may be claimed as one of the rare findings, especially on account of interaction between fullerenes and bisporphyrin in a non-polar solvent. Other than fullerenes C(60) and C(70), various other electron acceptors, viz., 2,3-dichloro-5,6-dicyano-p-benzoquinone, tetracyanoethylene, o-chloranil and p-chloranil form CT complexes with 1. Utilizing the CT transition energies for various electron donor-acceptor complexes of 1, vertical ionization potential (I(D)(v)) of 1 is determined to be 6.37 eV in solution. Estimation of degrees of CT, oscillator and transition dipole strengths evoke that the fullerene-1 non-covalent complexes are of neutral character in ground state. Higher magnitude of electronic coupling elements for the C(70)-1 complex compared to C(60)-1 complex indicates strong binding between C(70) and 1. Steady state fluorescence studies elicit efficient quenching of the fluorescence of 1 in presence of fullerenes. Both UV-Vis and steady state fluorescence measurements reveal large value of binding constant (K) for C(70)-1 system (∼6.94 × 10(4)dm(3)mol(-1)) than that of C(60)-1 system (K∼2.1 × 10(4)dm(3)mol(-1)). Time resolved emission studies establish charge-separated state for the fullerene-1 systems. Transient absorption measurements in the visible region establish the formation of 1(+) and fullerene(-) in toluene medium. Molecular mechanics calculations employing force field method in vacuo evoke the single projection structures of

  7. Ultrafast Charge Transfer in Nickel Phthalocyanine Probed by Femtosecond Raman-Induced Kerr Effect Spectroscopy

    Science.gov (United States)

    2015-01-01

    The recently developed technique of femtosecond stimulated Raman spectroscopy, and its variant, femtosecond Raman-induced Kerr effect spectroscopy (FRIKES), offer access to ultrafast excited-state dynamics via structurally specific vibrational spectra. We have used FRIKES to study the photoexcitation dynamics of nickel(II) phthalocyanine with eight butoxy substituents, NiPc(OBu)8. NiPc(OBu)8 is reported to have a relatively long-lived ligand-to-metal charge-transfer (LMCT) state, an essential characteristic for efficient electron transfer in photocatalysis. Following photoexcitation, vibrational transitions in the FRIKES spectra, assignable to phthalocyanine ring modes, evolve on the femtosecond to picosecond time scales. Correlation of ring core size with the frequency of the ν10 (asymmetric C–N stretching) mode confirms the identity of the LMCT state, which has a ∼500 ps lifetime, as well as that of a precursor d-d excited state. An even earlier (∼0.2 ps) transient is observed and tentatively assigned to a higher-lying Jahn–Teller-active LMCT state. This study illustrates the power of FRIKES spectroscopy in elucidating ultrafast molecular dynamics. PMID:24841906

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

    KAUST Repository

    El-Ballouli, Ala'a O.

    2015-11-17

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

  9. Electronic coupling effects and charge transfer between organic molecules and metal surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Forker, Roman

    2010-07-01

    We employ a variant of optical absorption spectroscopy, namely in situ differential reflectance spectroscopy (DRS), for an analysis of the structure-properties relations of thin epitaxial organic films. Clear correlations between the spectra and the differently intense coupling to the respective substrates are found. While rather broad and almost structureless spectra are obtained for a quaterrylene (QT) monolayer on Au(111), the spectral shape resembles that of isolated molecules when QT is grown on graphite. We even achieve an efficient electronic decoupling from the subjacent Au(111) by inserting an atomically thin organic spacer layer consisting of hexa-peri-hexabenzocoronene (HBC) with a noticeably dissimilar electronic behavior. These observations are further consolidated by a systematic variation of the metal substrate (Au, Ag, and Al), ranging from inert to rather reactive. For this purpose, 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) is chosen to ensure comparability of the molecular film structures on the different metals, and also because its electronic alignment on various metal surfaces has previously been studied with great intensity. We present evidence for ionized PTCDA at several interfaces and propose the charge transfer to be related to the electronic level alignment governed by interface dipole formation on the respective metals. (orig.)

  10. Electrostatic Potential-Based Method of Balancing Charge Transfer Across ONIOM QM:QM Boundaries.

    Science.gov (United States)

    Jovan Jose, K V; Raghavachari, Krishnan

    2014-10-14

    The inability to describe charge redistribution effects between different regions in a large molecule can be a source of error in an ONIOM hybrid calculation. We propose a new and an inexpensive method for describing such charge-transfer effects and for improving reaction energies obtained with the ONIOM method. Our method is based on matching the electrostatic potential (ESP) between the model system and the real system. The ESP difference arising due to charge redistribution is overcome by placing an optimum one electron potential at a defined buffer region. In our current implementation, the link atom nuclear charge is optimized iteratively to produce a model low ESP distribution equal to that in the real low calculation. These optimum charges are relatively small in magnitude and corroborate physical intuition. This new ESP-ONIOM-CT method is independent of any arbitrary definition of charges, is defined on the basis of a physical observable, and is less basis set dependent than previous approaches. The method is easily extended for studying reactions involving multiple link atoms. We present a thorough benchmark of this method on test sets consisting of one- and two-link atom reactions. Using reaction energies of four different test sets each with four different combinations of high:low levels of theory, the accuracy of ESP-ONIOM-CT improved by 40-60% over the ONIOM method.

  11. Frequency dependent magneto-transport in charge transfer Co(II) complex

    Energy Technology Data Exchange (ETDEWEB)

    Shaw, Bikash Kumar; Saha, Shyamal K., E-mail: cnssks@iacs.res.in

    2014-09-01

    A charge transfer chelated system containing ferromagnetic metal centers is the ideal system to investigate the magneto-transport and magneto-dielectric effects due to the presence of both electronic as well as magnetic properties and their coupling. Magneto-transport properties in materials are usually studied through dc charge transport under magnetic field. As frequency dependent conductivity is an essential tool to understand the nature of carrier wave, its spatial extension and their mutual interaction, in the present work, we have investigated frequency dependent magneto-transport along with magnetization behavior in [Co{sub 2}(II)-(5-(4-PhMe)-1,3,4-oxadiazole-H{sup +}-2-thiolate){sub 5}](OAc){sub 4} metal complex to elucidate the nature of above quantities and their response under magnetic field in the transport property. We have used the existing model for ac conduction incorporating the field dependence to explain the frequency dependent magneto-transport. It is seen that the frequency dependent magneto-transport could be well explained using the existing model for ac conduction. -Highlights: • Chelated Co(II) complex is synthesized for magneto-transport applications. • Frequency dependent magneto-transport and magnetization behavior are studied. • Nature of carrier wave, its spatial extension is investigated under magnetic field. • Existing model for ac conduction is used with magnetic field dependence.

  12. Charge Transfer Molecular Rotor DCVJ Investigated by Coherent Anti-Stokes Raman Spectroscopy

    Science.gov (United States)

    Ujj, Laszlo; Miller, Scott; Welch, Jonathan; Amos, Charles; Prayaga, Chandra

    2009-05-01

    Coherent anti-Stokes Raman Spectroscopy (CARS) has been shown to be one of the most powerful experimental methodologies for obtaining vibrational information from both stable and transient molecular species^1. The electronically enhanced polarization sensitive version of CARS is even more effective for measuring molecular vibrational information not easily reachable by spontaneous Raman spectroscopy. Theoretical and experimental principles associated with CARS with an emphasis on points relevant to the interpretation of experimental spectra will be presented. The method is applied to measure the vibrational manifold of DCVJ for the first time. DCVJ is a charge transfer molecular rotor showing a viscosity dependent fluorescence quantum yield. Based upon the measured CARS spectra, the effect of inhibition of the internal rotation on the vibrational motion of the molecule will be discussed. The design and operation of an all solid-state broadband nanosecond CARS system will be also presented. An overview of applications of molecular rotors in biology and information technology will be outlined. Ref.: 1. L. Ujj and G. H. Atkinson, ``Coherent Anti-Stokes Raman Spectroscopy'', in Handbook of Vibr. Spect., Wiley & Sons, Ltd., (2002).

  13. Pseudocapacitive hausmannite nanoparticles with (101) facets: synthesis, characterization, and charge-transfer mechanism.

    Science.gov (United States)

    Yeager, Matthew P; Du, Wenxin; Wang, Qi; Deskins, N Aaron; Sullivan, Matthew; Bishop, Brendan; Su, Dong; Xu, Wenqian; Senanayake, Sanjaya D; Si, Rui; Hanson, Jonathan; Teng, Xiaowei

    2013-10-01

    Hausmannite Mn3 O4 octahedral nanoparticles of 18.3 ± 7.0 nm with (101) facets have been prepared by an oxygen-mediated growth. The electrochemical properties of the Mn3 O4 particles as pseudocapacitive cathode materials were characterized both in half-cells and in button-cells. The Mn3 O4 nanoparticles exhibited a high mass-specific capacitance of 261 F g(-1), which was calculated from cyclic voltammetry analyses, and a capacitive retention of 78% after 10,000 galvanostatic charge-discharge cycles. The charge-transfer mechanisms of the Mn3 O4 nanoparticles were further studied by using synchrotron-based in situ X-ray absorption near edge spectroscopy and XRD. Both measurements showed concurrently that throughout the potential window of 0-1.2 V (vs. Ag/AgCl), a stable spinel structure of Mn3 O4 remained, and a reversible electrochemical conversion between tetrahedral [Mn(II) O4 ] and octahedral [Mn(III) O6 ] units accounted for the redox activity. Density functional theory calculations further corroborated this mechanism by confirming the enhanced redox stability afforded by the abundant and exposed (101) facets of Mn3 O4 octahedra. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Dissociation of charge-transfer states at donor-acceptor interfaces of organic heterojunctions

    Science.gov (United States)

    Inche Ibrahim, M. L.

    2017-02-01

    The dissociation of charge-transfer (CT) states into free charge carriers at donor-acceptor (DA) interfaces is an important step in the operation of organic solar cells and related devices. In this paper, we show that the effect of DA morphology and architecture means that the directions of CT states (where a CT state’s direction is defined as the direction from the electron to the hole of the CT state) may deviate from the direction of the applied electric field. The deviation means that the electric field is not fully utilized to assist, and could even hinder the dissociation process. Furthermore, we show that the correct charge carrier mobilities that should be used to describe CT state dissociation are the actual mobilites at DA interfaces. The actual mobilities are defined in this paper, and in general are not the same as the mobilities that are used to calculate electric currents which are the mobilites along the direction of the electric field. Then, to correctly describe CT state dissociation, we modify the widely used Onsager-Braun (OB) model by including the effect of DA morphology and architecture, and by employing the correct mobilities. We verify that when the modified OB model is used to describe CT state dissociation, the fundamental issues that concern the original OB model are resolved. This study demonstrates that DA morphology and architecture play an important role by strongly influencing the CT state dissociation as well as the mobilites along the direction of the electric field.

  15. Charge transfer of He2 + with H in a strong magnetic field

    Science.gov (United States)

    Liu, Chun-Lei; Zou, Shi-Yang; He, Bin; Wang, Jian-Guo

    2015-09-01

    By solving a time-dependent Schrödinger equation (TDSE), we studied the electron capture process in the He2 + +H collision system under a strong magnetic field in a wide projectile energy range. The strong enhancement of the total charge transfer cross section is observed for the projectile energy below 2.0 keV/u. With the projectile energy increasing, the cross sections will reduce a little and then increase again, compared with those in the field-free case. The cross sections to the states with different magnetic quantum numbers are presented and analyzed where the influence due to Zeeman splitting is obviously found, especially in the low projectile energy region. The comparison with other models is made and the tendency of the cross section varying with the projectile energy is found closer to that from other close coupling models. Project supported by the National Natural Science Foundation of China (Grants Nos. 11104017, 11025417, 11275029, and 11474032), the National Basic Research Programm of China (Grant No. 2013CB922200), and the Foundation for the Development of Science and Technology of the Chinese Academy of Engineering Physics (Grant Nos. 2014B09036 and 2013A0102005).

  16. Crystalline structure of the marketed form of Rifampicin: a case of conformational and charge transfer polymorphism

    Science.gov (United States)

    de Pinho Pessoa Nogueira, Luciana; de Oliveira, Yara S.; de C. Fonseca, Jéssica; Costa, Wendell S.; Raffin, Fernanda N.; Ellena, Javier; Ayala, Alejandro Pedro

    2018-03-01

    Rifampicin is a semi-synthetic drug derived from rifamycin B, and currently integrates the fixed dose combination tablet formulations used in the treatment of tuberculosis. It is also used in the leprosy polychemotherapy and prophylaxis, which are diseases classified as neglected according to the World Health Organization. Rifampicin is a polymorphic drug and its desirable polymorphic form is labeled as II, being the main goal of this study the elucidation of its crystalline structure. Polymorph II is characterized by two molecules with different conformations in the asymmetric unit and the following lattice parameters: a = 14.0760 (10) Å, b = 17.5450 (10) Å, c = 17.5270 (10) Å, β = 92.15°. Differently to the previously reported structures, a charge transference from the hydroxyl group of the naphthoquinone of one conformer to the nitrogen of the piperazine group of the second conformer was observed. The relevance of the knowledge of this crystalline structure, which is the preferred polymorph for pharmaceutical formulations, was evidenced by analyzing raw materials with polymorphic mixtures. Thus, the results presented in this contribution close an old information gap allowing the complete solid-state characterization of rifampicin.

  17. The Effects of Stoichiometry on the Optical Properties of PTZ-TCNQ Charge Transfer Crystals

    Science.gov (United States)

    Stone, Iris; Joshi, Jaydeep; Smith, Robert; Melis, Scott; van Keuren, Edward; Vora, Patrick

    Charge transfer (CT) crystals are two-component organic materials formed by stacked pairs of donor and acceptor molecules. Depending on the choice of donor and acceptor molecules it is possible to achieve semiconducting, insulating, or metallic characteristics, making the CT crystal platform potentially transformative for applications in low-cost flexible electronics. The use of phenothiazine (PTZ) donors and tetracyanoquinodimethane (TCNQ) acceptors is predicted to result in a semiconducting state with high electron and hole mobilities, properties that are ideal for ambipolar transistors. Here, we seek to understand the effect of stoichiometry on the optical and electronic properties of PTZ:TCNQ CT crystals by comparing nanowires with 1:1 stoichiometry to a novel 3:1 stoichiometry using temperature-dependent optical spectroscopy. Ensemble photoluminescence and absorption measurements indicate that a CT state forms in the 1:1 sample, whereas the 3:1 sample exhibits weaker coupling between TCNQ and PTZ. These results support a strong correlation between stoichiometry and optical properties. Our observations give important insight into how the intermolecular coupling varies with stoichiometry and are crucial to future efforts to realize an organic ambipolar transistor.

  18. Lead methylammonium triiodide perovskite-based solar cells: an interfacial charge-transfer investigation.

    Science.gov (United States)

    Xu, Xiaobao; Zhang, Hua; Cao, Kun; Cui, Jin; Lu, Jianfeng; Zeng, Xianwei; Shen, Yan; Wang, Mingkui

    2014-11-01

    This work reports on an investigation into interfacial charge transfer in CH3NH3PbI3 perovskite solar cells by using anatase TiO2 nanocuboids enclosed by active {100} and {001} facets. The devices show 6.0 and 8.0% power conversion efficiency with and without hole-transport material. Transient photovoltage/photocurrent decay and charge extraction, as well as impedance spectroscopy measurements, reveal that carbon materials are effective counter electrodes in perovskite solar cells. The photogenerated charges are observed to be stored in mesoporous TiO2 film under illumination and in the CH3NH3PbI3 layer in the dark. The use of 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamine)-9,9-spirobifluorene (spiro-MeOTAD) as a hole-transport material accelerates interfacial charge recombination between the photogenerated electrons and holes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Spectrophotometric determination and thermodynamic studies of the charge transfer complexes of azelastine-HCl

    Directory of Open Access Journals (Sweden)

    Nahla N. Salama

    2011-06-01

    Full Text Available Three charge transfer complexes of azelastine as n-donor with π acceptors, dichloro-dicyanobenzoquinone (DDQ, chloranilic acid (CA and tetracyanoquinodimethane (TCNQ were prepared in acetonitrile. They yield a radical anions measured at 456, 520 and 841 nm within concentration ranges of 8.0–72, 40–320 and 1.6–14.4 μg mL−1 with good correlation coefficients (r = 0.9996–0.9998. The molar absorptivities and association constants for the colored products were evaluated using the Benesi–Hildebrand equation. The free energy change (ΔG0 and the enthalpy of formation (ΔH0 as well as the entropy (ΔS0 were determined for the reaction product with TCNQ. The methods were successfully applied to the analysis of azelastine in its pharmaceutical preparations, where no interferences could be observed from the additives commonly present in the eye drops or nasal spray as proved by good mean recoveries of 98.89 ± 1.06–99.54 ± 1.84%. The results were compared, favorably with the manufacturer method and validated according to ICH guidelines.

  20. A charge transfer complex nematic liquid crystalline gel with high electrical conductivity

    Science.gov (United States)

    Bhargavi, R.; Nair, Geetha G.; Krishna Prasad, S.; Majumdar, R.; Bag, Braja G.

    2014-10-01

    We describe the rheological, dielectric and elastic properties of a nematic liquid crystal gel created using an anthrylidene derivative of arjunolic acid, a chiral triterpenoid, obtained from the extracts of the wood of Terminalia arjuna. In this novel gel, having the electron-donor and acceptor components as minority constituents, the gelation and strengthening of charge-transfer complex (CTC) formation are seen to be occurring concomitantly. In addition to being mechanically strong with a large storage modulus, the gel with the maximized CTC exhibits Frank bend elastic constant values that approach nanonewton levels. The highlight of the study is the observation of 4-5 orders of magnitude increase in electrical conductivity for this gel, a value that is higher than even in the CT complexes of 2-d ordered columnar structures. A further important advantage of the present system over the columnar complex is that the high conductivity is seen for ac probing also, and owing to the nematic nature can be switched between its anisotropic limits. Some of these features are ascribed to a specific molecular packing architecture, which reduces the trapping of the charge carriers.

  1. A charge transfer complex nematic liquid crystalline gel with high electrical conductivity

    Energy Technology Data Exchange (ETDEWEB)

    Bhargavi, R.; Nair, Geetha G., E-mail: geeraj88@gmail.com, E-mail: skpras@gmail.com; Krishna Prasad, S., E-mail: geeraj88@gmail.com, E-mail: skpras@gmail.com [Centre for Nano and Soft Matter Sciences, Jalahalli, Bangalore 560013 (India); Majumdar, R.; Bag, Braja G. [Department of Chemistry and Chemical Technology, Vidyasagar University, Midnapore (W) 721 102 (India)

    2014-10-21

    We describe the rheological, dielectric and elastic properties of a nematic liquid crystal gel created using an anthrylidene derivative of arjunolic acid, a chiral triterpenoid, obtained from the extracts of the wood of Terminalia arjuna. In this novel gel, having the electron-donor and acceptor components as minority constituents, the gelation and strengthening of charge-transfer complex (CTC) formation are seen to be occurring concomitantly. In addition to being mechanically strong with a large storage modulus, the gel with the maximized CTC exhibits Frank bend elastic constant values that approach nanonewton levels. The highlight of the study is the observation of 4–5 orders of magnitude increase in electrical conductivity for this gel, a value that is higher than even in the CT complexes of 2-d ordered columnar structures. A further important advantage of the present system over the columnar complex is that the high conductivity is seen for ac probing also, and owing to the nematic nature can be switched between its anisotropic limits. Some of these features are ascribed to a specific molecular packing architecture, which reduces the trapping of the charge carriers.

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

    Science.gov (United States)

    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.

  3. Charge-transfer-based terbium MOF nanoparticles as fluorescent pH sensor for extreme acidity.

    Science.gov (United States)

    Qi, Zewan; Chen, Yang

    2017-01-15

    Newly emerged metal organic frameworks (MOFs) have aroused the great interest in designing functional materials by means of its flexible structure and component. In this study, we used lanthanide Tb 3+ ions and small molecular ligands to design and assemble a kind of pH-sensitive MOF nanoparticle based on intramolecular-charge-transfer effect. This kind of made-to-order MOF nanoparticle for H + is highly specific and sensitive and could be used to fluorescently indicate pH value of strong acidic solution via preset mechanism through luminescence of Tb 3+ . The long luminescence lifetime of Tb 3+ allows eliminating concomitant non-specific fluorescence by time-revised fluorescence techniques, processing an advantage in sensing H + in biological media with strong autofluorescence. Our method showed a great potential of MOF structures in designing and constructing sensitive sensing materials for specific analytes directly via the assembly of functional ions/ligands. Copyright © 2016 Elsevier B.V. All rights reserved.

  4. Correlation between charge transfer and exchange coupling in carbon-based magnetic materials

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen, Anh Tuan, E-mail: tuanna@hus.edu.vn [Faculty of Physics, VNU University of Science, 334 Nguyen Trai, Thanh Xuan, Ha Noi (Viet Nam); Science and Technology Department, Vietnam National University, Hanoi, 144 Xuan Thuy, Cau Giay, Hanoi (Viet Nam); Japan Advanced Institute of Science and Technology, 1-1, Asahidai, Nomi, Ishikawa, 923-1292 Japan (Japan); Nguyen, Van Thanh; Nguyen, Huy Sinh [Faculty of Physics, VNU University of Science, 334 Nguyen Trai, Thanh Xuan, Ha Noi (Viet Nam); Pham, Thi Tuan Anh [Faculty of Physics, VNU University of Science, 334 Nguyen Trai, Thanh Xuan, Ha Noi (Viet Nam); Faculty of Science, College of Hai Duong, Nguyen Thi Due, Hai Duong (Viet Nam); Do, Viet Thang [Faculty of Physics, VNU University of Science, 334 Nguyen Trai, Thanh Xuan, Ha Noi (Viet Nam); Faculty of Science, Haiphong University, 171 Phan Dang Luu, Kien An, Hai Phong (Viet Nam); Dam, Hieu Chi [Japan Advanced Institute of Science and Technology, 1-1, Asahidai, Nomi, Ishikawa, 923-1292 Japan (Japan)

    2015-10-15

    Several forms of carbon-based magnetic materials, i.e. single radicals, radical dimers, and alternating stacks of radicals and diamagnetic molecules, have been investigated using density-functional theory with dispersion correction and full geometry optimization. Our calculated results demonstrate that the C{sub 31}H{sub 15} (R{sub 4}) radical has a spin of ½. However, in its [R{sub 4}]{sub 2} dimer structure, the net spin becomes zero due to antiferromagnetic spin-exchange between radicals. To avoid antiferromagnetic spin-exchange of identical face-to-face radicals, eight alternating stacks, R{sub 4}/D{sub 2m}/R{sub 4} (with m = 3-10), were designed. Our calculated results show that charge transfer (Δn) between R{sub 4} radicals and the diamagnetic molecule D{sub 2m} occurs with a mechanism of spin exchange (J) in stacks. The more electrons that transfer from R{sub 4} to D{sub 2m}, the stronger the ferromagnetic spin-exchange in stacks. In addition, our calculated results show that Δn can be tailored by adjusting the electron affinity (E{sub a}) of D{sub 2m}. The correlation between Δn, E{sub a}, m, and J is discussed. These results give some hints for the design of new ferromagnetic carbon-based materials.

  5. Correlation between charge transfer and exchange coupling in carbon-based magnetic materials

    Directory of Open Access Journals (Sweden)

    Anh Tuan Nguyen

    2015-10-01

    Full Text Available Several forms of carbon-based magnetic materials, i.e. single radicals, radical dimers, and alternating stacks of radicals and diamagnetic molecules, have been investigated using density-functional theory with dispersion correction and full geometry optimization. Our calculated results demonstrate that the C31H15 (R4 radical has a spin of ½. However, in its [R4]2 dimer structure, the net spin becomes zero due to antiferromagnetic spin-exchange between radicals. To avoid antiferromagnetic spin-exchange of identical face-to-face radicals, eight alternating stacks, R4/D2m/R4 (with m = 3-10, were designed. Our calculated results show that charge transfer (Δn between R4 radicals and the diamagnetic molecule D2m occurs with a mechanism of spin exchange (J in stacks. The more electrons that transfer from R4 to D2m, the stronger the ferromagnetic spin-exchange in stacks. In addition, our calculated results show that Δn can be tailored by adjusting the electron affinity (Ea of D2m. The correlation between Δn, Ea, m, and J is discussed. These results give some hints for the design of new ferromagnetic carbon-based materials.

  6. Controllable Charge Transfer in Ag-TiO2 Composite Structure for SERS Application

    Directory of Open Access Journals (Sweden)

    Yaxin Wang

    2017-06-01

    Full Text Available The nanocaps array of TiO2/Ag bilayer with different Ag thicknesses and co-sputtering TiO2-Ag monolayer with different TiO2 contents were fabricated on a two-dimensional colloidal array substrate for the investigation of Surface enhanced Raman scattering (SERS properties. For the TiO2/Ag bilayer, when the Ag thickness increased, SERS intensity decreased. Meanwhile, a significant enhancement was observed when the sublayer Ag was 10 nm compared to the pure Ag monolayer, which was ascribed to the metal-semiconductor synergistic effect that electromagnetic mechanism (EM provided by roughness surface and charge-transfer (CT enhancement mechanism from TiO2-Ag composite components. In comparison to the TiO2/Ag bilayer, the co-sputtered TiO2-Ag monolayer decreased the aggregation of Ag particles and led to the formation of small Ag particles, which showed that TiO2 could effectively inhibit the aggregation and growth of Ag nanoparticles.

  7. Antibacterial activity of large-area monolayer graphene film manipulated by charge transfer

    Science.gov (United States)

    Li, Jinhua; Wang, Gang; Zhu, Hongqin; Zhang, Miao; Zheng, Xiaohu; di, Zengfeng; Liu, Xuanyong; Wang, Xi

    2014-03-01

    Graphene has attracted increasing attention for potential applications in biotechnology due to its excellent electronic property and biocompatibility. Here we use both Gram-positive Staphylococcus aureus (S. aureus) and Gram-negative Escherichia coli (E. coli) to investigate the antibacterial actions of large-area monolayer graphene film on conductor Cu, semiconductor Ge and insulator SiO2. The results show that the graphene films on Cu and Ge can surprisingly inhibit the growth of both bacteria, especially the former. However, the proliferation of both bacteria cannot be significantly restricted by the graphene film on SiO2. The morphology of S. aureus and E. coli on graphene films further confirms that the direct contact of both bacteria with graphene on Cu and Ge can cause membrane damage and destroy membrane integrity, while no evident membrane destruction is induced by graphene on SiO2. From the viewpoint of charge transfer, a plausible mechanism is proposed here to explain this phenomenon. This study may provide new insights for the better understanding of antibacterial actions of graphene film and for the better designing of graphene-based antibiotics or other biomedical applications.

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

    Science.gov (United States)

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

    2017-09-01

    The intramolecular charge transfer properties of a phenyl-end-capped aniline tetramer (ANIH) and a chloro-substituted derivative (ANICl) as organic semiconductors were theoretically studied through the first-principles calculation based on the Marcus-Hush theory. The reorganization energies, intermolecular electronic couplings, angular resolution anisotropic mobilities, and density of states of the two crystals were evaluated. The calculated results demonstrate that both ANIH and ANICl crystals show the higher electron transfer mobilities than the hole-transfer mobilities, which means that the two crystals should prefer to function as n-type organic semiconductors. Furthermore, the angle dependence mobilities of the two crystals show remarkable anisotropic character. The maximum mobility μmax of ANIH and ANICl crystals is 1.3893 and 0.0272 cm2 V-1 s-1, which appear at the orientation angles near 176°/356° and 119°/299° of a conducting channel on the a-b reference plane. It is synthetically evaluated that the ANIH crystal possesses relatively lower reorganization energy, higher electronic coupling, and electron transfer mobility, which means that the ANIH crystal may be the more ideal candidate as a high performance n-type organic semiconductor material. The systematic theoretical studies on organic crystals should be conducive to evaluating the charge-transport properties and designing higher performance organic semiconductor materials.

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

    Science.gov (United States)

    Fujisawa, Jun-ichi

    2015-05-14

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

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

    DEFF Research Database (Denmark)

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

    2010-01-01

    ). The formation of an intermolecular charge-transfer (CT) compound is evident from the appearance of new reflexes in XRD (d =0.894nm and d =0.677nm). A softening of the CN stretching vibration (redshift by 7 cm⊃-1) of TCNQ is visible in the IR spectra, being indicative of a CT on the order of 0.3e from TMP...... to TCNQ in the complex. Characteristic shifts in the electronic level positions occur in UPS and STS that are in reasonable agreement with the prediction of density-functional theory (DFT) calculations (GAUSSIAN03 with hybrid functional B3LYP). STS reveals a highest occupied molecular orbital (HOMO......)-lowest unoccupied molecular orbital (LUMO) gap of the CT complex of about 1.25 eV being much smaller than the gaps (>3.0eV) of the pure moieties. The electron-injection and hole-injection barriers are 0.3 eV and 0.5 eV, respectively. Systematic differences in the positions of the HOMOs determined by UPS and STS...

  11. Charge transfer dissociation (CTD) mass spectrometry of peptide cations using kiloelectronvolt helium cations.

    Science.gov (United States)

    Hoffmann, William D; Jackson, Glen P

    2014-11-01

    A kiloelectronvolt beam of helium ions is used to ionize and fragment precursor peptide ions starting in the 1+ charge state. The electron affinity of helium cations (24.6 eV) exceeds the ionization potential of protonated peptides and can therefore be used to abstract an electron from--or charge exchange with--the isolated precursor ions. Kiloelectronvolt energies are used, (1) to overcome the Coulombic repulsion barrier between the cationic reactants, (2) to overcome ion-defocussing effects in the ion trap, and (3) to provide additional activation energy. Charge transfer dissociation (CTD) of the [M+H](+) precursor of Substance P gives product ions such as [M+H](2+•) and a dominant series of a ions in both the 1+ and 2+ charge states. These observations, along with the less-abundant a + 1 ions, are consistent with ultraviolet photodissociation (UVPD) results of others and indicate that C-C(α) cleavages are possible through charge exchange with helium ions. Although the efficiencies and timescale of CTD are not yet suitable for on-line chromatography, this new approach to ion activation provides an additional potential tool for the interrogation of gas phase ions.

  12. Defect-Mediated Molecular Interaction and Charge Transfer in Graphene Mesh-Glucose Sensors.

    Science.gov (United States)

    Kwon, Sun Sang; Shin, Jae Hyeok; Choi, Jonghyun; Nam, SungWoo; Park, Won Il

    2017-04-26

    We report the role of defects in enzymatic graphene field-effect transistor sensors by introducing engineered defects in graphene channels. Compared with conventional graphene sensors (Gr sensors), graphene mesh sensors (GM sensors), with an array of circular holes, initially exhibited a higher irreversible response to glucose, involving strong chemisorption to edge defects. However, after immobilization of glucose oxidase, the irreversibility of the responses was substantially diminished, without any reduction in the sensitivity of the GM sensors (i.e., -0.53 mV/mM for the GM sensor vs -0.37 mV/mM for Gr sensor). Furthermore, multiple cycle operation led to rapid sensing and improved the reversibility of GM sensors. In addition, control tests with sensors containing a linker showed that sensitivity was increased in Gr sensors but decreased in GM sensors. Our findings indicate that edge defects can be used to replace linkers for immobilization of glucose oxidase and improve charge transfer across glucose oxidase-graphene interfaces.

  13. Antibacterial activity of large-area monolayer graphene film manipulated by charge transfer

    Science.gov (United States)

    Li, Jinhua; Wang, Gang; Zhu, Hongqin; Zhang, Miao; Zheng, Xiaohu; Di, Zengfeng; Liu, Xuanyong; Wang, Xi

    2014-01-01

    Graphene has attracted increasing attention for potential applications in biotechnology due to its excellent electronic property and biocompatibility. Here we use both Gram-positive Staphylococcus aureus (S. aureus) and Gram-negative Escherichia coli (E. coli) to investigate the antibacterial actions of large-area monolayer graphene film on conductor Cu, semiconductor Ge and insulator SiO2. The results show that the graphene films on Cu and Ge can surprisingly inhibit the growth of both bacteria, especially the former. However, the proliferation of both bacteria cannot be significantly restricted by the graphene film on SiO2. The morphology of S. aureus and E. coli on graphene films further confirms that the direct contact of both bacteria with graphene on Cu and Ge can cause membrane damage and destroy membrane integrity, while no evident membrane destruction is induced by graphene on SiO2. From the viewpoint of charge transfer, a plausible mechanism is proposed here to explain this phenomenon. This study may provide new insights for the better understanding of antibacterial actions of graphene film and for the better designing of graphene-based antibiotics or other biomedical applications. PMID:24619247

  14. Structural transformation and charge transfer induced ferroelectricity and magnetism in annealed YMnO3

    Directory of Open Access Journals (Sweden)

    Sheng-Hsu Liu

    2011-09-01

    Full Text Available Multiferroic materials such as YMnO3, which uniquely exhibit ferroelectricity and magnetism simultaneously, have been extensively studied for spintronic device applications. However, the origin of multiferroicity remains poorly understood. In this study, the structural phases of YMnO3 ceramics and their lattice distortions after careful annealing were investigated to explain the origins of their multiferroicity. A structural transition from the orthorhombic to the hexagonal phase was observed when the annealing temperature reached around 1100 °C. This structural transformation also results in a magnetic transition from 3D Mn-O-Mn to 2D Mn-O-Mn superexchange coupling. The ferroelectricity was enhanced by escalation of the structural distortion caused by the rising annealing temperature. The annealing effect also results in the re-hybridization of the electronic structure of YMnO3. X-ray absorption near-edge spectra suggest that there is charge transfer from the Y-OT (apical oxygen bonds of Y 4d-O 2p hybridized states to the OT-Mn bonds of Mn 3d-O 2p hybridized states, which is responsible for the enhanced ferroelectricity. This approach could be used to probe the origin of the ferroelectricity and multiferroic properties in rare-earth manganites.

  15. METROLOGICAL ANALYSIS OF CHARGE - TRANSFER CAPACITIVE TRANSDUCER IN THE PRESENCE OF RESISTANCE

    Directory of Open Access Journals (Sweden)

    Plamen NIKOVSKI

    2013-01-01

    Full Text Available One of the major tasks in the design of measuring transducers is improving their accuracy in real conditions. Above all, this problem makes it necessary to evaluate the impact that various non-idealities have on the work of the measuring device. This study points that the presence of active resistance in the input of capacitive transducers, realizing the charge-transfer method, influences the measured result. With a configuration, composed of four analogue switches, the magnitude of the occurring in this case additional error depends on: the value of resistance in the input; the value of the capacity, which is the object of the measurement; the frequency and the phase offset of the clock signals, controlling the switches. The conditions under which error does not exceed 0,1% have been defined and a simple equation, by which its value can be assessed in the general case, has been validated. Presented results are useful in the design and implementation of industrial capacitive transducers

  16. Charge transfer effects on the chemical reactivity of Pd(x)Cu(1-x) nanoalloys.

    Science.gov (United States)

    Castegnaro, M V; Gorgeski, A; Balke, B; Alves, M C M; Morais, J

    2016-01-07

    This work reports on the synthesis and characterization of PdxCu1-x (x = 0.7, 0.5 and 0.3) nanoalloys obtained via an eco-friendly chemical reduction method based on ascorbic acid and trisodium citrate. The average size of the quasi-spherical nanoparticles (NPs) obtained by this method was about 4 nm, as observed by TEM. The colloids containing different NPs were then supported on carbon in order to produce powder samples (PdxCu1-x/C) whose electronic and structural properties were probed by different techniques. XRD analysis indicated the formation of crystalline PdCu alloys with a nanoscaled crystallite size. Core-level XPS results provided a fingerprint of a charge transfer process between Pd and Cu and its dependency on the nanoalloy composition. Additionally, it was verified that alloying was able to change the NP's reactivity towards oxidation and reduction. Indeed, the higher the amount of Pd in the nanoalloy, less oxidized are both the Pd and the Cu atoms in the as-prepared samples. Also, in situ XANES experiments during thermal treatment under a reducing atmosphere showed that the temperature required for a complete reduction of the nanoalloys depends on their composition. These results envisage the control at the atomic level of novel catalytic properties of such nanoalloys.

  17. Charge Transfer in Ultrafine LDH Nanosheets/Graphene Interface with Superior Capacitive Energy Storage Performance.

    Science.gov (United States)

    Jiang, Yingchang; Song, Yun; Li, Yanmei; Tian, Wenchao; Pan, Zhichang; Yang, Peiyu; Li, Yuesheng; Gu, Qinfen; Hu, Linfeng

    2017-11-01

    Two-dimensional LDH nanosheets recently have generated considerable interest in various promising applications because of their intriguing properties. Herein, we report a facile in situ nucleation strategy toward in situ decorating monodispersed Ni-Fe LDH ultrafine nanosheets (UNs) on graphene oxide template based on the precise control and manipulation of LDH UNs anchored, nucleated, grown, and crystallized. Anion-exchange behavior was observed in this Ni-Fe LDH UNs@rGO composite. The Ni-Fe LDH UNs@rGO electrodes displayed a significantly enhanced specific capacitance (2715F g(-1) at 3 A g(-1)) and energy density (82.3 Wh kg(-1) at 661 W kg(-1)), which exceeds the energy densities of most previously reported nickel iron oxide/hydroxides. Moreover, the asymmetric supercapacitor, with the Ni-Fe LDH UNs @rGO composite as the positive electrode material and reduced graphene oxide (rGO) as the negative electrode material, exhibited a high energy density (120 Wh kg (-1)) at an average power density of 1.3 kW kg (-1). A charge transfer from LDH layer to graphene layer, which means a built in electric field directed from LDH to graphene can be established by DFT calculations, which can significantly accelerate reaction kinetics and effectively optimize the capacitive energy storage performance.

  18. Dynamics of charge-transfer excited states relevant to photochemical energy conversion

    Energy Technology Data Exchange (ETDEWEB)

    Lim, E.C.

    1991-11-01

    The primary objective of the research program is to gain a fundamental understanding of the factors governing the efficiency of excited-state charge transfer CT interactions between two chromophores that are brought together in close proximity, either by a very short covalent linkage or by ground-state complex formation. CT and van der Walls (vdW), interactions in covalently bonded bichromophoric compounds in condensed phase, as well as those in vdW complexes in supersonic jets, are being investigated using laser-based techniques under a variety of experimental conditions. This progress report is divided into three parts, according to the class of molecular systems and the phase (liquid vs. gas) in which the excited-state interactions are probed. The first is concerned with the excited states of bridged diaryl compounds in the condensed phase. The second involves the excited states of vdW complexes in supersonic jets. Finally, the third, is concerned with the excited states of electron donor-acceptor (EDA) systems in both the condensed phase and supersonic jets. In each of these studies, we are concerned with the interchromophore interactions ranging from weak vdW forces to strong CT forces, and the factors determining whether the interaction forces are weak or strong in related molecules.

  19. Hydrogen bonded charge transfer molecular salt (4-chloro anilinium-3-nitrophthalate) for photophysical and pharmacological applications

    Science.gov (United States)

    Singaravelan, K.; Chandramohan, A.; Saravanabhavan, M.; Muthu Vijayan Enoch, I. V.; Suganthi, V. S.

    2017-09-01

    Radical scavenging activity against DPPH radical and binding properties of a hydrogen bonded charge transfer molecular salt 4-chloro anilinium-3-nitrophthalate(CANP) with calf thymus DNA has been studied by electronic absorption and emission spectroscopy. The molecular structure and crystallinity of the CANP salt have been established by carried out powder and single crystal X-ray diffraction analysis which indicated that cation and anion are linked through strong N+sbnd H…O- type of hydrogen bond. FTIR spectroscopic study was carried out to know the various functional groups present in the crystal. 1H and 13C NMR spectra were recorded to further confirm the molecular structure of the salt crystal. The thermal stability of the title salt was established by TG/DTA analyses simultaneously on the powdered sample of the title crystal. Further, the CANP salt was examined against various bacteria and fungi strains which showed a remarkable antimicrobial activity compared to that of the standards Ciproflaxin and Clotrimazole. The results showed that the CANP salt could interact with CT-DNA through intercalation. Antioxidant studies of the substrates alone and synthesized CANP salt showed that the latter has been better radical scavenging activity than that of the former against DPPH radical. The third order nonlinear susceptibility of the CANP salt was established by the Z-scan study.

  20. Structural and electronic properties of α -(BEDT-TTF)2I3 , β -(BEDT-TTF)2I3 , and κ -(BEDT-TTF)2X3 (X = I, F, Br, Cl) organic charge transfer salts

    Science.gov (United States)

    Commeau, Benjamin; Geilhufe, R. Matthias; Fernando, Gayanath W.; Balatsky, Alexander V.

    2017-09-01

    (BEDT-TFF ) 2I3 charge transfer salts are reported to show superconductivity and pressure-induced quasi-two-dimensional Dirac cones at the Fermi level. By performing state of the art ab initio calculations in the framework of density functional theory, we investigate the structural and electronic properties of the three structural phases α , β , and κ . We furthermore report about the irreducible representations of the corresponding electronic band structures, symmetry of their crystal structure, and the origin of band crossings. Additionally, we discuss the chemically induced strain in κ -(BEDT-TTF ) 2I3 achieved by replacing the iodine layer with other halogens: fluorine, bromine, and chlorine. In the case of κ -(BEDT-TTF ) 2F3 , we identify topologically protected crossings within the band structure. These crossings are forced to occur due to the nonsymmorphic nature of the crystal. The calculated electronic structures presented here are added to the organic materials database (OMDB).

  1. Resonance Raman examination of the electronic excited states of glycylglycine and other dipeptides: Observation of a carboxylate{yields}amide charge transfer transition

    Energy Technology Data Exchange (ETDEWEB)

    Chen, X.G.; Li, P.; Holtz, J.S.W.; Chi, Z.; Pajcini, V.; Asher, S.A. [Univ. of Pittsburgh, PA (United States); Kelly, L.A. [Brookhaven National Lab., Upton, NY (United States)

    1996-10-09

    We have examined the UV resonance Raman and the VUV absorption spectra of aqueous glycylglycine and other dipeptides. We observe strong resonance Raman enhancement of the amide I, II, and III bands and the amide C{sub {alpha}}H bending mode in a manner similar to that we observed previously with excitation within the {pi}{yields}{pi}{sup *} transition of N-methylacetamide. However, in addition, we observe strong resonance Raman enhancement of the ca. 1400 cm{sup -1} symmetric COO{sup -} stretching vibration, whose 206.5 nm Raman cross section is increased 20-fold compared to that of the carboxylate in sodium acetate, for example. Addition of a methylene spacer between the amide and carboxylate groups causes the resonance Raman enhancement of this symmetric COO{sup -} stretch to disappear. The UV resonance Raman excitation profiles, the Raman depolarization ratio dispersion, and the VUV absorption spectra of glycylglycine and other dipeptides demonstrate the existence of a new 197 nm charge transfer band which involves electron transfer from a nonbonding carboxylate orbital to the amide-like {pi}{sup *} orbital. This transition occurs at the penultimate carboxylate end of all peptides and proteins. 18 refs., 9 figs., 3 tabs.

  2. Ferrocene-donor and 4,5-dicyanoimidazole-acceptor moieties in charge-transfer chromophores with π linkers tailored for second-order nonlinear optics.

    Science.gov (United States)

    Kulhánek, Jiří; Bureš, Filip; Kuznik, Wojciech; Kityk, Iwan V; Mikysek, Tomáš; Růžička, Aleš

    2013-02-01

    A series of new nonlinear optical chromophores (1-15) that were comprised of ferrocene-donor and 4,5-dicyanoimidazole-acceptor moieties and various π linkers of different length were synthesized. Support for the presence of significant DA interactions in these NLO-phores was obtained from the evaluation of the quinoid character of the 1,4-phenylene moieties and their electronic absorption spectra, which featured intense high-energy (HE) bands that were accompanied by less-intense low-energy (LE) bands. The redox behavior of these compounds was investigated by cyclic voltammetry (CV) and by rotating-disc voltammetry (RDV); their electrochemical gaps decreased steadily from 2.64 to 2.09 V. In addition to the experimentally obtained data, DFT calculations of their absorption spectra, HOMO/LUMO levels, and second-order polarizabilities (β) (-2ω,ω,ω) were performed. A structure-property relationship study that was performed by systematically altering the π linker revealed that the intramolecular charge-transfer and nonlinear optical properties of these inorganic-organic hybrid D-π-A systems (1-15) were primarily affected by: 1) The presence of olefinic/acetylenic subunits; 2) the length of the π linker; and 3) the spatial arrangement (planarity) of the π linker. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. First report of charge-transfer induced heat-set hydrogel. Structural insights and remarkable properties

    Science.gov (United States)

    Bhattacharjee, Subham; Maiti, Bappa; Bhattacharya, Santanu

    2016-05-01

    The remarkable ability of a charge-transfer (CT) complex prepared from a pyrene-based donor (Py-D) and a naphthalenediimide-based acceptor (NDI-A) led to the formation of a deep-violet in color, transparent hydrogel at room temperature (RT-gel). Simultaneously, the RT-gel was diluted beyond its critical gelator concentration (CGC) to obtain a transparent sol. Very interestingly, the resultant sol, on heating above 70 °C, transformed into a heat-set gel instantaneously with a hitherto unknown CGC value. Detailed studies revealed the smaller globular aggregates of the RT-gels fuse to form giant globules upon heating, which, in turn, resulted in heat-set gelation through further aggregation. The thermoresponsive property of Py-D alone and 1 : 1 Py-D : NDI-A CT complex was investigated in detail which revealed the hydrophobic collapse of the oxyethylene chains of the CT complex upon heating was mainly responsible for heat-set gelation. Thixotropy, injectability, as well as stimuli responsiveness of the RT-gels were also addressed. In contrast, heat-set gel did not show thixotropic behavior. The X-ray diffraction (XRD) patterns of the xerogel depicted lamellar packing of the CT stacks in the gel phase. Single crystal XRD studies further evidenced the 1 : 1 mixed CT stack formation in the lamellae and also ruled out orthogonal hydrogen bonding possibilities among the hydrazide unit in the CT gel although such interaction was observed in a single crystal of NDI-A alone. In addition, a Ag+-ion triggered metallogelation of NDI-A and nematic liquid-crystalline property of Py-D were also observed.The remarkable ability of a charge-transfer (CT) complex prepared from a pyrene-based donor (Py-D) and a naphthalenediimide-based acceptor (NDI-A) led to the formation of a deep-violet in color, transparent hydrogel at room temperature (RT-gel). Simultaneously, the RT-gel was diluted beyond its critical gelator concentration (CGC) to obtain a transparent sol. Very interestingly, the

  4. Charge transfer effects on the chemical reactivity of PdxCu1-x nanoalloys

    Science.gov (United States)

    Castegnaro, M. V.; Gorgeski, A.; Balke, B.; Alves, M. C. M.; Morais, J.

    2015-12-01

    This work reports on the synthesis and characterization of PdxCu1-x (x = 0.7, 0.5 and 0.3) nanoalloys obtained via an eco-friendly chemical reduction method based on ascorbic acid and trisodium citrate. The average size of the quasi-spherical nanoparticles (NPs) obtained by this method was about 4 nm, as observed by TEM. The colloids containing different NPs were then supported on carbon in order to produce powder samples (PdxCu1-x/C) whose electronic and structural properties were probed by different techniques. XRD analysis indicated the formation of crystalline PdCu alloys with a nanoscaled crystallite size. Core-level XPS results provided a fingerprint of a charge transfer process between Pd and Cu and its dependency on the nanoalloy composition. Additionally, it was verified that alloying was able to change the NP's reactivity towards oxidation and reduction. Indeed, the higher the amount of Pd in the nanoalloy, less oxidized are both the Pd and the Cu atoms in the as-prepared samples. Also, in situ XANES experiments during thermal treatment under a reducing atmosphere showed that the temperature required for a complete reduction of the nanoalloys depends on their composition. These results envisage the control at the atomic level of novel catalytic properties of such nanoalloys.This work reports on the synthesis and characterization of PdxCu1-x (x = 0.7, 0.5 and 0.3) nanoalloys obtained via an eco-friendly chemical reduction method based on ascorbic acid and trisodium citrate. The average size of the quasi-spherical nanoparticles (NPs) obtained by this method was about 4 nm, as observed by TEM. The colloids containing different NPs were then supported on carbon in order to produce powder samples (PdxCu1-x/C) whose electronic and structural properties were probed by different techniques. XRD analysis indicated the formation of crystalline PdCu alloys with a nanoscaled crystallite size. Core-level XPS results provided a fingerprint of a charge transfer process

  5. Looking at Photoinduced Charge Transfer Processes in the IR: Answers to Several Long-Standing Questions.

    Science.gov (United States)

    Dereka, Bogdan; Koch, Marius; Vauthey, Eric

    2017-02-21

    Because of its crucial role in many areas of science and technology, photoinduced electron transfer is the most investigated photochemical reaction. Despite this, several important questions remain open. We present recent efforts to answer some of them, which concern both inter- and intramolecular processes. The decisive factor that allowed these issues to be successfully addressed was the use of time-resolved infrared (TRIR) spectroscopy. Many different transient species, such as tight and loose ion pairs (TIPs and LIPs) and exciplexes, have been invoked to explain the dynamics of intermolecular photoinduced charge separation reactions (i.e., electron transfer between two neutral species) and the production of free ions. However, their structures are essentially unknown, and their exact roles in the reaction mechanism are unclear. Indeed, the commonly used transient electronic absorption spectroscopy does not give much structural insight and cannot clearly distinguish ion pairs from free ions, at least in the visible region. Unambiguous spectral signatures of TIPs, LIPs, and exciplexes could be observed in the IR using electron donor/acceptor (D/A) pairs with adequate vibrational marker modes. The ability to spectrally distinguish these intermediates allowed their dynamics to be disentangled and their roles to be determined. Structural information could be obtained using polarization-resolved TRIR spectroscopy. Our investigations reveal that moderately to highly exergonic reactions result in the formation of both TIPs and LIPs. TIPs are not only generated upon direct charge-transfer excitation of DA complexes, as usually assumed, but are also formed upon static quenching with reactant pairs at distances and orientations enabling charge separation without diffusion. On the other hand, dynamic quenching produces primarily LIPs. In the case of highly exergonic reactions, strong indirect evidence for the generation of ion pairs in an electronic excited state was found

  6. IR spectroscopic investigation of charge transfer at interfaces of organic semiconductors (Conference Presentation)

    Science.gov (United States)

    Beck, Sebastian; Hillebrandt, Sabina; Pucci, Annemarie

    2016-09-01

    In organic electronics, the interactions at interfaces between different organic and inorganic layers play a decisive role for device functionality and performance. Therefore, more detailed, quantitative studies of charge transfer (CT) at such interfaces are needed to improve the understanding of the underlying mechanisms. In this study we show that in-situ infrared spectroscopy can be used to investigate CT effects at organic/organic as well as inorganic/organic interfaces quantitatively. For different combinations of commonly used organic semiconductors such as 4,4´-bis(N-carbazolyl)-1,1´-biphenyl (CBP) or fluorinated zinc phthalocyanine (F4ZnPc) and inorganic contact materials such as molybdenum oxide (MoO3) or indium tin oxide (ITO) the CT at the interface was investigated using in-situ IR spectroscopy. The measurements were carried out under UHV conditions during film growth what enables a careful study of the influence of different parameters such as substrate temperature and layer thickness in a controlled way even on a nanometer scale. When the organic molecules are deposited onto the underlying layer charged and non-charged species form which can be identified and quantitatively analyzed in the IR spectra. It was also found that the deposition sequence can strongly influence the interface properties what might have strong implications on the layer stack design. For example, when MoO3 is deposited onto CBP, the CBP layer is strongly doped, due to diffusion of the deposited transition metal oxide clusters into the organic layer. Financial support by BMBF (project INTERPHASE) is gratefully acknowledged.

  7. Validated spectrophotometric methods for determination of sodium valproate based on charge transfer complexation reactions.

    Science.gov (United States)

    Belal, Tarek S; El-Kafrawy, Dina S; Mahrous, Mohamed S; Abdel-Khalek, Magdi M; Abo-Gharam, Amira H

    2016-02-15

    This work presents the development, validation and application of four simple and direct spectrophotometric methods for determination of sodium valproate (VP) through charge transfer complexation reactions. The first method is based on the reaction of the drug with p-chloranilic acid (p-CA) in acetone to give a purple colored product with maximum absorbance at 524nm. The second method depends on the reaction of VP with dichlone (DC) in dimethylformamide forming a reddish orange product measured at 490nm. The third method is based upon the interaction of VP and picric acid (PA) in chloroform resulting in the formation of a yellow complex measured at 415nm. The fourth method involves the formation of a yellow complex peaking at 361nm upon the reaction of the drug with iodine in chloroform. Experimental conditions affecting the color development were studied and optimized. Stoichiometry of the reactions was determined. The proposed spectrophotometric procedures were effectively validated with respect to linearity, ranges, precision, accuracy, specificity, robustness, detection and quantification limits. Calibration curves of the formed color products with p-CA, DC, PA and iodine showed good linear relationships over the concentration ranges 24-144, 40-200, 2-20 and 1-8μg/mL respectively. The proposed methods were successfully applied to the assay of sodium valproate in tablets and oral solution dosage forms with good accuracy and precision. Assay results were statistically compared to a reference pharmacopoeial HPLC method where no significant differences were observed between the proposed methods and reference method. Copyright © 2015 Elsevier B.V. All rights reserved.

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

    Science.gov (United States)

    Kim, Jeong Soo; Kim, Byung-Man; Kim, Un-Young; Shin, HyeonOh; Nam, Jung Seung; Roh, Deok-Ho; Park, Jun-Hyeok; Kwon, Tae-Hyuk

    2017-10-11

    We developed three types of dithieno[3,2-b;2',3'-d]thiophene (DTT)-based organic sensitizers for high-performance thin photoactive TiO2 films and investigated the simple but powerful molecular engineering of different types of bonding between the triarylamine electron donor and the conjugated DTT π-bridge by the introduction of single, double, and triple bonds. As a result, with only 1.3 μm transparent and 2.5-μm TiO2 scattering layers, the triple-bond sensitizer (T-DAHTDTT) shows the highest power conversion efficiency (η = 8.4%; VOC = 0.73 V, JSC = 15.4 mA·cm(-2), and FF = 0.75) in an iodine electrolyte system under one solar illumination (AM 1.5, 1000 W·m(-2)), followed by the single-bond sensitizer (S-DAHTDTT) (η = 7.6%) and the double-bond sensitizer (D-DAHTDTT) (η = 6.4%). We suggest that the superior performance of T-DAHTDTT comes from enhanced intramolecular charge transfer (ICT) induced by the triple bond. Consequently, T-DAHTDTT exhibits the most active photoelectron injection and charge transport on a TiO2 film during operation, which leads to the highest photocurrent density among the systems studied. We analyzed these correlations mainly in terms of charge injection efficiency, level of photocharge storage, and charge-transport kinetics. This study suggests that the molecular engineering of a triple bond between the electron donor and the π-bridge of a sensitizer increases the performance of dye-sensitized solar cell (DSC) with a thin photoactive film by enhancing not only JSC through improved ICT but also VOC through the evenly distributed sensitizer surface coverage.

  9. Analytical Study for the Charge-Transfer Complexes of Rosuvastatin Calcium with π-Acceptors

    Directory of Open Access Journals (Sweden)

    Nourah Z. Alzoman

    2013-07-01

    Full Text Available Studies were carried out to investigate the charge-transfer (CT reaction of ROS-Ca, as a n-electron donor with various p-acceptors: tetracyanoethylene, p-chloranilic acid, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, 2,3,5,6-tetrabromo-1,4-benzoquinone, 1,3,5-trinitrobenzene, 2,3,5,6-tetrachloro-1,4-benzoquinone, 7,7,8,8-tetracyano-quinodimethane, and 2,4,7-trinitro-9-fluorenone. Different colored CT complexes were obtained. The reaction mechanism and site of interaction were determined by ultraviolet-visible spectrophotometric techniques and computational molecular modeling. The formation of the colored complexes was utilized in the development of simple, rapid and accurate spectrophotometric methods for the determination of ROS-Ca. Under the optimum reaction conditions, linear relationships with good correlation coefficients (0.9984–0.9995 were found between the absorbances and the concentrations of ROS-Ca in the range of 2–200 mg mL−1. The limits of detection ranged from 0.41 to 12.24 mg mL−1. No interference could be observed from the additives commonly present in the tablets or from the drugs that are co-formulated with ROS-Ca in its combined formulations. The methods were successfully applied to the analysis of tablets with good accuracy and precision; the recovery percentages ranged from 99.54–100.46 ± 1.58–1.82%. The results were compared favorably with the reported method. The proposed methods are practical and valuable for routine application in quality control laboratories for determination of ROS-Ca in its bulk form and tablets.

  10. Direct in Situ Measurement of Charge Transfer Processes During Photoelectrochemical Water Oxidation on Catalyzed Hematite.

    Science.gov (United States)

    Qiu, Jingjing; Hajibabaei, Hamed; Nellist, Michael R; Laskowski, Forrest A L; Hamann, Thomas W; Boettcher, Shannon W

    2017-09-27

    Electrocatalysts improve the efficiency of light-absorbing semiconductor photoanodes driving the oxygen evolution reaction, but the precise function(s) of the electrocatalysts remains unclear. We directly measure, for the first time, the interface carrier transport properties of a prototypical visible-light-absorbing semiconductor, α-Fe2O3, in contact with one of the fastest known water oxidation catalysts, Ni0.8Fe0.2O x , by directly measuring/controlling the current and/or voltage at the Ni0.8Fe0.2O x catalyst layer using a second working electrode. The measurements demonstrate that the majority of photogenerated holes in α-Fe2O3 directly transfer to the catalyst film over a wide range of conditions and that the Ni0.8Fe0.2O x is oxidized by photoholes to an operating potential sufficient to drive water oxidation at rates that match the photocurrent generated by the α-Fe2O3. The Ni0.8Fe0.2O x therefore acts as both a hole-collecting contact and a catalyst for the photoelectrochemical water oxidation process. Separate measurements show that the illuminated junction photovoltage across the α-Fe2O3|Ni0.8Fe0.2O x interface is significantly decreased by the oxidation of Ni(2+) to Ni(3+) and the associated increase in the Ni0.8Fe0.2O x electrical conductivity. In sum, the results illustrate the underlying operative charge-transfer and photovoltage generation mechanisms of catalyzed photoelectrodes, thus guiding their continued improvement.

  11. Low-temperature fabrication of alkali metal-organic charge transfer complexes on cotton textile for optoelectronics and gas sensing.

    Science.gov (United States)

    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.

  12. DNA Films Containing the Artificial Nucleobase Imidazole Mediate Charge Transfer in a Silver(I)-Responsive Way.

    Science.gov (United States)

    Léon, J Christian; She, Zhe; Kamal, Ajar; Shamsi, Mohtashim Hassan; Müller, Jens; Kraatz, Heinz-Bernhard

    2017-05-22

    The first sequence-dependent study of DNA films containing metal-mediated base pairs was performed to investigate the charge transfer resistance (RCT ) of metal-modified DNA. The imidazole (Im) deoxyribonucleoside was chosen as a highly Ag(I) -specific ligandoside for the formation of Im-Ag(I) -Im complexes within the duplexes. This new class of site-specifically metal-modified DNA films was characterized by UV, circular dichroism (CD), and X-ray photoelectron spectroscopy (XPS). The electrochemical properties of these systems were investigated by means of electron impedance spectroscopy and scanning electrochemical microscopy. Taken together, these experiments indicated that the incorporation of Ag(I) ions into the DNA films leads to reduced electron transfer through the DNA films. A simple device was proposed that can be switched reversibly between two distinct states with different charge transfer resistance. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Orientation and charge transfer upon adsorption of ethanethiol on Cu(1 1 1) surface at 85 K

    CERN Document Server

    Sardar, S A; Ikenaga, E; Yagi, S; Sekitani, T; Wada, S; Taniguchi, M; Tanaka, K

    2003-01-01

    Orientation and charge transfer upon adsorption of ethanethiol on Cu(1 1 1) surface at 85 K has been investigated by S K-edge near edge X-ray absorption fine structure (NEXAFS) and X-ray photoelectron spectroscopy (XPS) techniques. Exposure-dependent S K-edge NEXAFS identified the monolayer saturation at approx 0.8 L exposure. Polarization-dependent NEXAFS spectra of submonolayer ethanethiol shows that S-C bond is tilted 37+-7 deg. from the surface. Temperature-dependent NEXAFS spectra shows that ethyl thiolate starts breaking at 300-350 K and atomic sulfur creates. A significant amount of charge transfer (1.4 electrons) from copper to ethanethiol molecules has measured by S 1s XPS technique.

  14. The Robin Hood method A novel numerical method for electrostatic problems based on a non-local charge transfer

    Science.gov (United States)

    Lazić, Predrag; Štefančić, Hrvoje; Abraham, Hrvoje

    2006-03-01

    We introduce a novel numerical method, named the Robin Hood method, of solving electrostatic problems. The approach of the method is closest to the boundary element methods, although significant conceptual differences exist with respect to this class of methods. The method achieves equipotentiality of conducting surfaces by iterative non-local charge transfer. For each of the conducting surfaces, non-local charge transfers are performed between surface elements, which differ the most from the targeted equipotentiality of the surface. The method is tested against analytical solutions and its wide range of application is demonstrated. The method has appealing technical characteristics. For the problem with N surface elements, the computational complexity of the method essentially scales with Nα, where α Robin Hood method could prove useful in other classical or even quantum problems. Some future development ideas for possible applications outside electrostatics are addressed.

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

    Directory of Open Access Journals (Sweden)

    Fotini Petraki

    2014-04-01

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

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

    Science.gov (United States)

    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.

  17. Evaluation of bactericidal action of 2-vinylpiridine copolymers containing quaternary ammonium groups and their charge transfer complexes

    Directory of Open Access Journals (Sweden)

    Aline S. S. Valle

    2013-01-01

    Full Text Available We report the development of copolymers based on 2-vinylpyridine with different porosity degrees. The copolymers were quaternized with methyl iodide and acrylonitrile to introduce quaternary ammonium groups on pyridine units. To prepare charge transfer complexes, the unmodified copolymers and their derivatives quaternized were impregnated with iodine. The antibacterial properties of all the polymers were evaluated ranging from of the Escherichia coli strain. The unmodified copolymers did not have antibacterial activity against E.Coli suspensions. The quaternization with methyl iodine and acrylonitrile increased the biocidal performance of these copolymers, but only the copolymer with the lowest porosity modified with methyl iodine showed significant bactericidal action for all E. Coli concentrations. The 2-vinylpiridine copolymers quaternized and impregnated with iodine had higher antibacterial activity than the impregnated ones. The charge transfer complexes derived from the copolymer with the lowest porosity and highest swelling capacity in water had the best bactericidal performance.

  18. Luminescence from the ligand to metal charge transfer state of the neptunyl (V) ion and its complexes in solution

    Science.gov (United States)

    Bradshaw, Rebecca; Sykes, Daniel; Natrajan, Louise S.; Taylor, Robin J.; Livens, Francis R.; Faulkner, Stephen

    2010-03-01

    The photophysical properties of the neptunyl (V) ion in aqueous solution have been studied using time-resolved luminescence spectroscopy. While any f-f transitions in emission are too weak to detect using available technology, the ligand to metal charge transfer state is emissive in the visible part of the spectrum. Both the aquo ion and its complexes with bidentate ligands exhibit biexponential decay kinetics, which can be rationalised by slow exchange on the timescale of the experiment.

  19. Long-range corrected DFT calculations of charge-transfer integrals in model metal-free phthalocyanine complexes

    Czech Academy of Sciences Publication Activity Database

    Mikolajczyk, M. M.; Zalesny, R.; Czyznikowska, Z.; Toman, Petr; Leszczynski, J.; Bartkowiak, W.

    2011-01-01

    Roč. 17, č. 9 (2011), s. 2143-2149 ISSN 1610-2940 R&D Projects: GA ČR(CZ) GAP205/10/2280; GA MŠk MEB051010 Institutional research plan: CEZ:AV0Z40500505 Keywords : charge-transfer integral * density functional theory * long-range corrected functionals Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.797, year: 2011

  20. A how-to approach for a 3D simulation of charge transfer characteristics in a gas electron multiplier (GEM)

    CERN Document Server

    Sharma, A

    1999-01-01

    In this paper a detailed description of how to simulate charge transfer processes in a gaseous device is presented, taking the gas electron multiplier (GEM) as an example. A 3-dimensional simulation of the electric field and avalanche is performed. Results on charge transport are compared to experiment and agree within experimental errors; the avalanche mechanism and positive ion feedback are studied. The procedures used in the simulation are described in detail, and program scripts are appended. (15 refs).

  1. 2-Aminopurine: A Probe of Structural Dynamics and Charge Transfer in DNA and DNA:RNA Hybrids

    OpenAIRE

    O'Neill, Melanie A.; Barton, Jacqueline K.

    2002-01-01

    Spectroscopic techniques are employed to probe relationships between structural dynamics and charge transfer (CT) efficiency in DNA duplexes and DNA:RNA hybrids containing photoexcited 2-aminopurine (Ap*). To better understand the variety of interactions and reactions, including CT, between Ap* and DNA, the fluorescence behavior of Ap* is investigated in a full series of redox-inactive as well as redox-active assemblies. Thus, Ap* is developed as a dual reporter of structural dynamics and bas...

  2. Evidence of charge-transfer ferromagnetism in transparent diluted magnetic oxide nanocrystals: switching the mechanism of magnetic interactions.

    Science.gov (United States)

    Farvid, Shokouh S; Sabergharesou, Tahereh; Hutfluss, Lisa N; Hegde, Manu; Prouzet, Eric; Radovanovic, Pavle V

    2014-05-28

    We report the experimental evidence of a new form of room-temperature ferromagnetism in high surface area nanocrystalline manganese-doped In2O3, prepared from colloidal nanocrystals as building blocks. The nanocrystal structure (bixbyite or corundum) and assembly were controlled by their size, and the type and concentration of dopant precursors. The existence of substitutional paramagnetic Mn dopant ions in mixed valence states (Mn(2+) and Mn(3+)) was confirmed and quantified by different spectroscopic methods, including X-ray absorption and magnetic circular dichroism. The presence of different oxidation states is the basis of ferromagnetism induced by Stoner splitting of the local density of states associated with extended structural defects, due to charge transfer from the Mn dopants. The extent of this charge transfer can be controlled by the relationship between the electronic structures of the nanocrystal host lattice and dopant ions, rendering a higher magnetic moment in bixbyite relative to corundum Mn-doped In2O3. Charge-transfer ferromagnetism assumes no essential role of dopant as a carrier of the magnetic moment, which was directly confirmed by X-ray magnetic circular dichroism, as an element-specific probe of the origin of ferromagnetism. At doping concentrations approaching the percolation limit, charge-transfer ferromagnetism can switch to a double exchange mechanism, given the mixed oxidation states of Mn dopants. The results of this work enable the investigations of the new mechanisms of magnetic ordering in solid state and contribute to the design of new unconventional magnetic and multifunctional materials.

  3. Experimental verification of orbital engineering at the atomic scale: Charge transfer and symmetry breaking in nickelate heterostructures

    Science.gov (United States)

    Phillips, Patrick J.; Rui, Xue; Georgescu, Alexandru B.; Disa, Ankit S.; Longo, Paolo; Okunishi, Eiji; Walker, Fred; Ahn, Charles H.; Ismail-Beigi, Sohrab; Klie, Robert F.

    2017-05-01

    Epitaxial strain, layer confinement, and inversion symmetry breaking have emerged as powerful new approaches to control the electronic and atomic-scale structural properties of complex metal oxides. Trivalent rare-earth (RE) nickelate R E NiO3 heterostructures have been shown to be exemplars since the orbital occupancy, degeneracy, and, consequently, electronic/magnetic properties can be altered as a function of epitaxial strain, layer thickness, and superlattice structure. One recent example is the tricomponent LaTiO3-LaNiO3-LaAlO3 superlattice which exhibits charge transfer and orbital polarization as the result of its interfacial dipole electric field. A crucial step towards control of these parameters for future electronic and magnetic device applications is to develop an understanding of both the magnitude and range of the octahedral network's response towards interfacial strain and electric fields. An approach that provides atomic-scale resolution and sensitivity towards the local octahedral distortions and orbital occupancy is therefore required. Here, we employ atomic-resolution imaging coupled with electron spectroscopies and first-principles theory to examine the role of interfacial charge transfer and symmetry breaking in a tricomponent nickelate superlattice system. We find that nearly complete charge transfer occurs between the LaTiO3 and LaNiO3 layers, resulting in a mixed Ni2 +/Ni3 + valence state. We further demonstrate that this charge transfer is highly localized with a range of about 1 unit cell within the LaNiO3 layers. We also show how Wannier-function-based electron counting provides a simple physical picture of the electron distribution that connects directly with formal valence charges. The results presented here provide important feedback to synthesis efforts aimed at stabilizing new electronic phases that are not accessible by conventional bulk or epitaxial film approaches.

  4. A new type of charge-transfer salts based on tetrathiafulvalene-tetracarboxylate coordination polymers and methyl viologen.

    Science.gov (United States)

    Huang, Yu-De; Huo, Peng; Shao, Ming-Yan; Yin, Jing-Xue; Shen, Wei-Chun; Zhu, Qin-Yu; Dai, Jie

    2014-04-07

    Although charge-transfer compounds based on tetrathiafulvalene (TTF) derivatives have been intensively studied, {[cation](n+)·[TTFs](n-)} ion pair charge-transfer (IPCT) salts have not been reported. The aim of this research is to introduce functional organic cations, such as photoactive methyl viologen (MV(2+)), into the negatively charged TTF-metal coordination framework to obtain this new type of IPCT complex. X-ray structural analysis of the four compounds (MV)2[Li4(L)2(H2O)6] (1), {(MV)(L)[Na2(H2O)8]·4H2O}n (2), {(MV)[Mn(L)(H2O)2]·2H2O}n (3), and {(MV)[Mn(L)(H2O)2]}n (4), reveals that the electron donor (D) TTF moiety and the electron acceptor (A) MV(2+) form a regular mixed-stack arrangement in alternating DADA fashion. The TTF moiety and the MV(2+) cation are essentially parallel stacked to form the column structures. The strong electrostatic interaction is a main force to shorten the distance between the cation and anion planes. Optical diffuse-reflection spectra indicate that charge transfer occurs in these complexes. The ESR and magnetic measurements confirm that there is strong charge-transfer-induced partial electron transfer. Compounds 2, 3, and 4 show an effective and repeatable photocurrent response. The current intensities of 3 and 4 are higher than that of 2, which reflects that the coordination center of the Mn(II) ion has a great effect on the increasing photocurrent response.

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

    Directory of Open Access Journals (Sweden)

    Parul Chawla

    2014-08-01

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

  6. High-Surface-Area Architectures for Improved Charge Transfer Kinetics at the Dark Electrode in Dye-Sensitized Solar Cells

    Energy Technology Data Exchange (ETDEWEB)

    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.

  7. Probing charge transfer between shells of double-walled carbon nanotubes sorted by outer-wall electronic type.

    Science.gov (United States)

    Kalbac, Martin; Green, Alexander A; Hersam, Mark C; Kavan, Ladislav

    2011-08-22

    Double-walled carbon nanotubes (DWCNTs) with outer metallic (M) or semiconducting (S) shells were sorted by density-gradient ultracentrifugation and examined by Raman spectroscopy and in situ Raman spectroelectrochemistry. The combination of sorting and the selection of appropriate laser excitation energies allowed the disentanglement of the effects of different variations of the electronic type (M or S) of the inner and outer tubes in DWCNTs on the doping behavior and charge transfer between the inner and outer walls. Charge transfer from the outer tube to the inner tube occurs only if the electronic states of the outer tube are filled with electrons or holes, and if these filled states are higher in energy than those of the inner tube. Therefore, each combination of inner and outer tube (i.e., inner@outer: M@M, M@S, S@M, and S@S) exhibits a distinct behavior. The potential needed to observe the effects of charge transfer between the inner and outer tubes is found to increase in the following order: M@M < S@M < M@S < S@S. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Science.gov (United States)

    Baumeier, Björn; Andrienko, Denis; Rohlfing, Michael

    2012-08-14

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

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

    Science.gov (United States)

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

    2014-01-01

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

  10. Photophysical properties of trans-3-(4-monomethylamino-phenyl)-acrylonitrile: Evidence of twisted intramolecular charge transfer (TICT) process

    Science.gov (United States)

    Chakraborty, Amrita; Kar, Samiran; Guchhait, Nikhil

    2006-05-01

    A donor acceptor substituted aromatic system trans-3-(4-monomethylamino-phenyl)-acrylonitrile (MMAPA) has been synthesized and its photophysical behavior has been investigated in the solvent of different polarity by steady state absorption and emission, time-resolved emission and quantum chemical calculations. The observed dual fluorescence of MMAPA in polar aprotic solvents has been assigned to emission from the locally excited and twisted intramolecular charge transfer states. The low-energy emission in protic solvent is attributed to the hydrogen-bonded complex. Potential energy surfaces for the ground and excited states along the donor (-NHMe group) and acceptor (acrylonitrile group) twist coordinates have been calculated by time-dependent density functional theory (TDDFT) and time-dependent density functional theory-polarized continuum model (TDDFT-PCM) in the gas phase and in acetonitrile solvent, respectively. Calculations predict that the stabilized excited state along the twist coordinate is responsible for the solvent dependent red shifted charge transfer emission. It is found that the twisting along the donor site is energetically favorable compared to that of the acceptor site. The canonical crossing of the excited states for the twisting of the donor group and localized nitrogen lone pair orbital of -NHMe group at the perpendicular configuration with respect to p-orbitals of benzene ring support TICT model for photo-induced charge transfer reaction in MMAPA molecule.

  11. Spectroscopic and theoretical evidence for the photoinduced twisted intramolecular charge transfer state formation in N,N-dimethylaminonaphthyl-(acrylo)-nitrile

    Energy Technology Data Exchange (ETDEWEB)

    Singh, Rupashree Balia; Mahanta, Subrata; Kar, Samiran [Department of Chemistry, University of Calcutta, 92, A. P. C. Road, Kolkata 700009 (India); Guchhait, Nikhil [Department of Chemistry, University of Calcutta, 92, A. P. C. Road, Kolkata 700009 (India)], E-mail: nikhil.guchhait@rediffmail.com

    2008-09-15

    The phenomenon of excited state twisted intramolecular charge transfer (TICT) process in N,N-dimethylaminonaphthyl-(acrylo)-nitrile (DMANAN) has been reported on the basis of steady-state absorption and fluorescence spectroscopy in combination with quantum chemical calculations. The absorption and fluorescence characteristics of DMANAN in solvents of different polarity reveal the presence of a single species in the ground state which forms the intramolecular charge transfer state upon photoexcitation. The observed dual fluorescence is assigned to a high-energy emission from the locally excited or the Franck-Condon state and the red-shifted emission from the charge transfer (CT) state. In polar protic solvents, hydrogen-bonding interaction on CT emission has been established from the linear dependency of the position of the low-energy emission maxima on hydrogen-bonding parameter ({alpha}). The experimental findings have been correlated with the theoretical results based on TICT model obtained at density functional theory (DFT) level. The theoretical potential energy surface for the first excited state along both the donor and acceptor twist coordinates in the gas phase obtained by time dependent density functional theory (TDDFT) method and in polar solvent by time dependent density functional theory-polarized continuum model (TDDFT-PCM) method predicts well the experimental spectral properties.

  12. A charge transfer ionic-embedded atom method potential for the O-Al-Ni-Co-Fe system

    Energy Technology Data Exchange (ETDEWEB)

    Zhou Xiaowang; Wadley, Haydn N G [Department of Materials Science and Engineering, 116 Engineer' s Way, University of Virginia, Charlottesville, VA 22904-4745 (United States)

    2005-06-15

    Magnetic tunnel junctions (MTJs) require the growth of a thin ({approx}20 A) dielectric metal oxide layer, such as Al{sub 2}O{sub 3}, on a ferromagnetic metal layer, such as Co, CoFe, or CoNiFe. The atomic assembly mechanisms that combine to form a uniformly thin metal oxide layer on these metal surfaces are not well understood. The application of molecular dynamics simulations to the growth of metal and metal oxide multilayers that involve more than one metal element has not been possible using the conventional interatomic potentials. A recently proposed modified charge transfer ionic-embedded atom method potential appears to correctly enable the charge transfer between oxygen and numerous metal elements to be modelled in a format amenable for molecular dynamics studies. Here we parametrize this charge transfer ionic-embedded atom method potential for the quinternary O-Al-Ni-Co-Fe system so that a direct molecular dynamics simulation of the growth of the tunnelling magnetoresistive multilayers can be realized.

  13. Robust Stability Analysis of Fractional-Order Hopfield Neural Networks with Parameter Uncertainties

    Directory of Open Access Journals (Sweden)

    Shuo Zhang

    2014-01-01

    Full Text Available The issue of robust stability for fractional-order Hopfield neural networks with parameter uncertainties is investigated in this paper. For such neural system, its existence, uniqueness, and global Mittag-Leffler stability of the equilibrium point are analyzed by employing suitable Lyapunov functionals. Based on the fractional-order Lyapunov direct method, the sufficient conditions are proposed for the robust stability of the studied networks. Moreover, robust synchronization and quasi-synchronization between the class of neural networks are discussed. Furthermore, some numerical examples are given to show the effectiveness of our obtained theoretical results.

  14. On the interfacial charge transfer between solid and liquid Li(+) electrolytes.

    Science.gov (United States)

    Schleutker, Marco; Bahner, Jochen; Tsai, Chih-Long; Stolten, Detlef; Korte, Carsten

    2017-10-11

    The Li(+) ion transfer between a solid and a liquid Li(+) electrolyte has been investigated by DC polarisation techniques. The current density i is measured as a function of the electrochemical potential drop Δ[small mu, Greek, tilde]Li(+) at the interface, using a liquid electrolyte with different Li(+) concentrations. The subject of this experimental study is the interface between the solid electrolyte Ta-substituted lithium lanthanum zirconate (Li6.6La3Zr1.6Ta0.4O12) and a liquid electrolyte consisting of LiPF6 dissolved in ethylene carbonate/dimethyl carbonate (1 : 1). The functional course of i vs. Δ[small mu, Greek, tilde]Li(+) can be described by a serial connection between a constant ohmic resistance Rslei and a current dependent thermally activated ion transfer process. For the present solid-liquid electrolyte interface the areal resistance Rslei of the surface layer is independent of the Li(+) concentration in the liquid electrolyte. At room temperature a value of about 300 Ω cm(2) is found. The constant ohmic resistance Rslei can be attributed to a surface layer on the solid electrolyte with a (relatively) low conductivity (solid-liquid electrolyte interphase). The low conducting surface layer is formed by degradation reactions with the liquid electrolyte. Rslei is considerably increased if a small amount (ppm) of water is added to the liquid electrolyte. The thermally activated ionic transfer process obeys a Butler-Volmer like behaviour, resulting in an exchange current density i0 depending on the Li(+) concentration in the liquid electrolyte by a power-law. At a Li(+) concentration of 1 mol l(-1) a value of 53.1 μA cm(-2) is found. A charge transfer coefficient α of ∼0.44 is measured. The finding of a superposed constant ohmic resistance due to a solid-liquid electrolyte interphase and a current dependent thermally activated ion transfer process is confirmed by the results of two former experimental studies from the literature, performing AC

  15. Axially Bound Ruthenium Phthalocyanine Monolayers on Indium Tin Oxide: Structure, Energetics, and Charge Transfer Properties.

    Science.gov (United States)

    Ehamparam, Ramanan; Oquendo, Luis E; Liao, Michael W; Brynnel, Ambjorn K; Ou, Kai-Lin; Armstrong, Neal R; McGrath, Dominic V; Saavedra, S Scott

    2017-08-30

    The efficiency of charge collection at the organic/transparent conducting oxide (TCO) interface in organic photovoltaic (OPV) devices affects overall device efficiency. Modifying the TCO with an electrochemically active molecule may enhance OPV efficiency by providing a charge-transfer pathway between the electrode and the organic active layer, and may also mitigate surface recombination. The synthesis and characterization of phosphonic acid-ruthenium phthalocyanine (RuPcPA) monolayer films on indium tin oxide (ITO), designed to facilitate charge harvesting at ITO electrodes, is presented in this work. The PA group was installed axially relative to the Pc plane so that upon deposition, RuPcPA molecules were preferentially aligned with the ITO surface plane. The tilt angle of 22° between the normal axes to the Pc plane and the ITO surface plane, measured by attenuated total reflectance (ATR) spectroscopy, is consistent with a predominately in-plane orientation. The effect of surface roughness on RuPcPA orientation was modeled, and a correlation was obtained between experimental and theoretical mean tilt angles. Based on electrochemical and spectroelectrochemical studies, RuPcPA monolayers are composed predominately of monomers. Electrochemical impedance spectroscopy (EIS) and potential modulated-ATR (PM-ATR) spectroscopy were used to characterize the electron-transfer (ET) kinetics of these monolayers. A rate constant of 4.0 × 10 3 s -1 was measured using EIS, consistent with a short tunneling distance between the chromophore and the electrode surface. Using PM-ATR, k s,opt values of 2.2 × 10 3 and 2.4 × 10 3 s -1 were measured using TE and TM polarized light, respectively; the similarity of these values is consistent with a narrow molecular orientation distribution and narrow range of tunneling distances. The ionization potential of RuPcPA-modified ITO was measured using ultraviolet photoelectron spectroscopy and the results indicate favorable energetics for

  16. Hydrogen bond strengthening induces fluorescence quenching of PRODAN derivative by turning on twisted intramolecular charge transfer

    Science.gov (United States)

    Yang, Yonggang; Li, Donglin; Li, Chaozheng; Liu, YuFang; Jiang, Kai

    2017-12-01

    Researchers have proposed different effective mechanisms of hydrogen bonding (HB) on the fluorescence of 6-propionyl-2-dimethylaminonaphthalene (PRODAN) and its derivatives. Herein, excited state transition and dynamics analysis confirm that the fluorescence of PD (a derivative of PRODAN with ethyl replaced by 3-hydroxy-2,2-dimethylpropan) emits from the planar intramolecular charge transfer (PICT) state rather than twist ICT (TICT) state, because the fluorescence emission and surface hopping from the TICT state to the twist ground (T-S0) state is energy forbidden. Nevertheless, the strengthening of intramolecular-HB (intra-HB) and intermolecular-HB (inter-HB) of PD-(methanol)2 smooth the pathway of surface hopping from TICT to T-S0 state and the external conversion going to planar ground state by decreasing the energy difference of the two states. This smoothing changes the fluorescence state of PD-(methanol)2 to the TICT state in which fluorescence emission does not occur but surface hopping, leading to the partial fluorescence quenching of PD in methanol solvent. This conclusion is different from previous related reports. Moreover, the inter-HB strengthening of PD-methanol in PICT state induces the cleavage of intra-HB and a fluorescence red-shift of 54 nm compared to PD. This red-shift increases to 66 nm for PD-(methanol)2 for the strengthening of the one intra-HB and two inter-HBs. The dipole moments of PD-methanol and PD-(methanol)2 respectively increase about 10.3D and 8.1D in PICT state compared to PD. The synergistic effect of intra-HB and inter-HB induces partial quenching of PD in methanol solvent by turning on the TICT state and fluorescence red-shift. This work gives a reasonable description on the fluorescence red-shift and partial quenching of PD in methanol solvent, which will bring insight into the study of spectroscopic properties of molecules owning better spectral characteristics.

  17. Spectrophotometric study of the charge transfer complexation of some amino acid derivative drugs as electron donors with 7,7,8,8-tetracyanoquinodimethane

    Directory of Open Access Journals (Sweden)

    Sheng Yun Li

    2010-04-01

    Full Text Available Charge transfer (CT complexes of some drugs of amino acid derivatives, such as carbocysteine, aminobutyric acid, and levodopa, as electron donors with 7,7,8,8-tetracyanoquinodimethane (TCNQ as electron acceptor have been studied. The spectra obtained for carbocysteine/TCNQ, aminobutyric acid/TCNQ, and levodopa/TCNQ systems show the maximum absorption bands at wavelengths of 422, 415, and 417 nm, respectively. The formation of such complexes was also confirmed by infrared measurements. The stoichiometry of the complexes was found to be 1:1 between the donor and the acceptor. The possible reaction mechanisms were explored. The thermodynamic standard reaction quantities of the complexes between donors and acceptor were estimated. Different variables affecting the reaction were carefully studied and optimized. At the optimum reaction conditions, Beer’s law was obeyed in a concentration limit of 1–30, 1–10, and 2–50 μg mL−1 for carbocysteine, aminobutyric acid, and levodopa, respectively. The limits of detection ranged from 0.3 to 0.8 μg mL−1. The developed methods could be applied successfully for the determination of the studied compounds in their pharmaceutical dosage forms with a good precision and accuracy compared to official and reported methods as revealed by t- and F-tests.

  18. Mass and charge transfer on various relevant scales in polymer electrolyte fuel cells[Dissertation 16991

    Energy Technology Data Exchange (ETDEWEB)

    Freunberger, S. A.

    2007-07-01

    This dissertation is concerned with the development, experimental diagnostics and mathematical modelling and simulation of polymer electrolyte fuel cells (PEFC). The central themes throughout this thesis are the closely interlinked phenomena of mass and charge transfer. In the face of developing a PEFC system for vehicle propulsion these phenomena are scrutinized on a broad range of relevant scales. Starting from the material related level of the membrane and the gas diffusion layer (GDL) we turn to length scales, where structural features of the cell additionally come into play. These are the scale of flow channels and ribs, the single cell and the cell stack followed by the cell, stack, and system development for an automotive power train. In Chapter 3 selected fundamental material models and properties, respectively, are explored that are crucial for the mathematical modelling and simulation of PEFC, as needed in some succeeding parts of this work. First, established mathematical models for mass and charge transfer in the membrane are compared within the framework of the membrane electrode assembly (MEA), which represents the electrochemical unit. Second, reliable values for effective diffusivities in the GDLs which are vital for the simulation of gaseous mass transport are measured. Therefore, a method is developed that allows measuring this quantity both as a function of compression and direction as this is a prerequisite of sophisticated more-dimensional numerical PEFC-models. Besides the cross section of the catalyst layer (CL) mass transfer under channels and ribs is considered as a major source of losses in particular under high load operation. As up to now there have been solely non-validated theoretical investigations, in Chapter 4 an experimental method is developed that is for the first time capable of resolving the current density distribution on the this scale. For this, the electron conductors in the cell are considered as 2-dimensional shunt

  19. A Lagrange multiplier and Hopfield-type barrier function method for the traveling salesman problem.

    Science.gov (United States)

    Dang, Chuangyin; Xu, Lei

    2002-02-01

    A Lagrange multiplier and Hopfield-type barrier function method is proposed for approximating a solution of the traveling salesman problem. The method is derived from applications of Lagrange multipliers and a Hopfield-type barrier function and attempts to produce a solution of high quality by generating a minimum point of a barrier problem for a sequence of descending values of the barrier parameter. For any given value of the barrier parameter, the method searches for a minimum point of the barrier problem in a feasible descent direction, which has a desired property that lower and upper bounds on variables are always satisfied automatically if the step length is a number between zero and one. At each iteration, the feasible descent direction is found by updating Lagrange multipliers with a globally convergent iterative procedure. For any given value of the barrier parameter, the method converges to a stationary point of the barrier problem without any condition on the objective function. Theoretical and numerical results show that the method seems more effective and efficient than the softassign algorithm.

  20. Spectrophotometric, FTIR and theoretical studies of the charge-transfer complexes between isoniazid (pyridine-4-carboxylic acid hydrazide) and the acceptors (p-chloranil, chloranilic acid and tetracyanoethylene) in acetonitrile, their association constants, thermodynamic properties and other related properties.

    Science.gov (United States)

    Bagchi Chattaraj, Seema; Sharma, Kakali; Chakrabortty, Ashutosh; Lahiri, Sujit Chandra

    2012-09-01

    Spectrophotometric, FTIR and theoretical studies of the charge-transfer complexes between Isoniazid (pyridine-4-carboxylic acid hydrazide) and the acceptors (p-chloranil, chloranilic acid and tetracyanoethylene) in acetonitrile, their association constants, thermodynamic properties and other related properties were studied. Isoniazid (INH), a widely used anti tubercular agent was found to form beautifully colored charge-transfer complexes with p-chloranil, chloranilic acid and tetracyanoethylene in acetonitrile. The absorption maxima of the complexes were 484, 519 and 479 nm, respectively (isoniazid had no absorption, but the acceptors had absorption in these regions). The composition of the complexes were determined to be 1:1 from Job's method of continuous variations depending on the time period of experiments as the stability of some of the complexes (p-chloranil and tetracyanoethylene complexes) was time dependent. Solid complexes formed between isoniazid and the acceptors were isolated but p-chloranil was found to form two different complexes. FTIR spectra of the complexes and the acceptors were measured. FTIR spectra of the complexes showed considerable shift in absorption peaks, changes in intensities of the peaks and formation of the new band (probably due to hydrogen bonding) on complexation. The thermodynamic association constants and other thermodynamic parameters of the complexes were determined spectrophotometrically taking D and A in varying ratios (2:8-8:2) and also in equimolar ratios. The complex formation was found to be spontaneous and associated with negative changes of ΔG(0), ΔH(0) and ΔS(0). The energies hν(CT) of the charge-transfer complexes were compared with the theoretical values of hν(CT) of the complexes obtained from HOMO and LUMO of the donor and the acceptors. Density function theory utilizing different basis sets was used for calculation. hν(CT) (experimental) values of the transition energies of the complexes in acetonitrile

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

    Science.gov (United States)

    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.

  2. Symmetry-Breaking Charge Transfer in a Zinc Chlorodipyrrin Acceptor for High Open Circuit Voltage Organic Photovoltaics

    KAUST Repository

    Bartynski, Andrew N.

    2015-04-29

    © 2015 American Chemical Society. Low open-circuit voltages significantly limit the power conversion efficiency of organic photovoltaic devices. Typical strategies to enhance the open-circuit voltage involve tuning the HOMO and LUMO positions of the donor (D) and acceptor (A), respectively, to increase the interfacial energy gap or to tailor the donor or acceptor structure at the D/A interface. Here, we present an alternative approach to improve the open-circuit voltage through the use of a zinc chlorodipyrrin, ZCl [bis(dodecachloro-5-mesityldipyrrinato)zinc], as an acceptor, which undergoes symmetry-breaking charge transfer (CT) at the donor/acceptor interface. DBP/ZCl cells exhibit open-circuit voltages of 1.33 V compared to 0.88 V for analogous tetraphenyldibenzoperyflanthrene (DBP)/C60-based devices. Charge transfer state energies measured by Fourier-transform photocurrent spectroscopy and electroluminescence show that C60 forms a CT state of 1.45 ± 0.05 eV in a DBP/C60-based organic photovoltaic device, while ZCl as acceptor gives a CT state energy of 1.70 ± 0.05 eV in the corresponding device structure. In the ZCl device this results in an energetic loss between ECT and qVOC of 0.37 eV, substantially less than the 0.6 eV typically observed for organic systems and equal to the recombination losses seen in high-efficiency Si and GaAs devices. The substantial increase in open-circuit voltage and reduction in recombination losses for devices utilizing ZCl demonstrate the great promise of symmetry-breaking charge transfer in organic photovoltaic devices.

  3. Synergizing Noncovalent Bonding Interactions in the Self-Assembly of Organic Charge-Transfer Ferroelectrics and Metal-Organic Frameworks

    Science.gov (United States)

    Cao, Dennis

    Contemporary supramolecular chemistry---chemistry beyond the molecule---seeks to leverage noncovalent bonding interactions to generate emergent properties and complexity. These aims extend beyond the solution phase and into the solid state, where crystalline organic materials have attracted much attention for their ability to imitate the physical properties of inorganic crystals. This Thesis outlines my efforts to understand the properties of the solid-state materials that are self-assembled with noncovalent bonding motifs which I have helped to realize. In the first five Chapters, I chronicle the development of the lock-arm supramolecular ordering (LASO) paradigm, which is a general molecular design strategy for amplifying the crystallization of charge transfer complexes that revolves around the synergistic action of hydrogen bonding and charge transfer interactions. In an effort to expand upon the LASO paradigm, I identify a two-point halogen-bonding motif which appears to operate orthogonally from the hydrogen bonding and charge transfer interactions. Since some of these single crystalline materials are ferroelectric at room temperature, I discuss the implications of these experimental observations and reconcile them with the centrosymmetric space groups assigned after X-ray crystallographic refinements. I conclude in the final two Chapters by recording my endeavors to control the assembly of metal-organic frameworks (MOFs) with noncovalent bonding interactions between [2]catenane-bearing struts. First of all, I describe the formation of syndiotactic pi-stacked 2D MOF layers before highlighting a two-component MOF that assembles with a magic number ratio of components that is independent of the molar proportions present in the crystallization medium.

  4. Cooperative coupling of the Li cation and groups to amplify the charge transfer between C60 and corannulene

    Science.gov (United States)

    Sun, Gang; Xu, Jing; Chen, Zhi-Yuan; Lei, E.; Liu, Xiang-Shuai; Liu, Chun-Guang

    2017-02-01

    In present work, four complexes have been designed to investigate the effect of Li+ cation and substituent on the geometric structures and a series of electronic properties using density functional theory. The calculated results indicate that the charge decomposition (CDA) analysis and extend charge decomposition analysis (ECDA) of four complexes have the same sequence. The average d values defined the distances between C60 and corannulene display the inverse sequence. Consequently, the cooperative coupling of the Li+ cation and appropriate substituent is predicted to be an effective way to enhance the charge transfer between the C60 and corannulene derivatives.

  5. Terahertz-pulse driven modulation of electronic spectra: Modeling electron-phonon coupling in charge-transfer crystals

    Science.gov (United States)

    Di Maiolo, Francesco; Masino, Matteo; Painelli, Anna

    2017-08-01

    We calculate the optical spectra of a charge-transfer crystal modulated by a terahertz pulse, accounting for electron-vibration coupling. The model Hamiltonian is parametrized against first principle calculations and adiabatic results are validated against a fully non-adiabatic calculation where relaxation phenomena are introduced via the coupling of the quantum system to a dissipative bath of classic anharmonic oscillators. The experiment is well reproduced by the proposed model with no need to introduce any ad hoc assumption on the temporal dependence of model parameters, but just accounting for the quadratic dependence of the Hubbard U on non-totally symmetric molecular coordinates.

  6. Ultrafast broadband laser spectroscopy reveals energy and charge transfer in novel donor-acceptor triads for photovoltaic applications

    Energy Technology Data Exchange (ETDEWEB)

    Roland, T; Ramirez, G Hernandez; Leonard, J; Mery, S; Haacke, S, E-mail: stefan.haacke@ipcms.u-strasbg.fr [Institut de Physique et Chimie des Materiaux de Strasbourg, Strasbourg University - CNRS UMR 7504, F-67034 Strasbourg (France)

    2011-02-01

    Triggered by the quest for new organic materials and micro-structures for photovoltaic applications, a novel class of donor-acceptor-donor (DAD) triads extended with siloxane chains has been synthesized in our labs. Because of the siloxane chains, the molecules self-organize into a smectic liquid crystal phase, resulting in a stacking of the DAD cores.We report here a preliminary study of the ultrafast dynamics of energy and charge transfer studied by femtosecond broadband transient absorption experiments on isolated triads in chloroform.

  7. Twisted intra-molecular charge transfer investigations of semiorganic triglycine phosphate single crystal for non linear optical applications

    Science.gov (United States)

    Meera, M. R.; Joselin Beaula, T.; Rayar, S. L.; Bena Jothy, V.

    2017-09-01

    NLO materials are gaining importance in technologies such as optical communication, optical computing and dynamic image processing. Many NLO crystals grown by mixing amino acids with various organic and inorganic acids have been reported in the literature. Hence, glycine mixed semi-organic material will be of special interest as a fundamental building block to develop many complex crystals with improved NLO properties. A semi organic Single crystal of Triglycine Phosphate (TGP) which was grown and spectral analysis have been using FTIR and Raman spectral analysis. Natural Bond Orbital Analysis and the atomic natural charges are also predicted. HOMO LUMO energy gap value suggests the possibility of charge transfer within the molecule.

  8. Charge-Transfer Dynamics in the Lowest Excited State of a Pentacene–Fullerene Complex: Implications for Organic Solar Cells

    KAUST Repository

    Joseph, Saju

    2017-10-02

    We characterize the dynamic nature of the lowest excited state in a pentacene/C60 complex on the femtosecond time scale, via a combination of ab initio molecular dynamics and time-dependent density functional theory. We analyze the correlations between the molecular vibrations of the complex and the oscillations in the electron-transfer character of its lowest excited state, which point to vibration-induced coherences between the (pentacene-based) local-excitation (LE) state and the complex charge-transfer (CT) state. We discuss the implications of our results on this model system for the exciton-dissociation process in organic solar cells.

  9. Use of the Charge Transfer Reactions for the Spectrophotometric Determination of Risperidone in Pure and in Dosage Forms

    Directory of Open Access Journals (Sweden)

    Hemavathi Nagaraju Deepakumari

    2013-01-01

    Full Text Available The aim of study was to develop and validate two simple, sensitive, and extraction-free spectrophotometric methods for the estimation of risperidone in both pure and pharmaceutical preparations. They are based on the charge transfer complexation reactions between risperidone (RSP as n-electron donor and p-chloranilic acid (p-CA in method A and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ in method B as π-acceptors. In method A, RSP reacts with p-CA in methanol to produce a bright pink-colored chromogen measured at 530 nm whereas, in method B, RSP reacts with DDQ in dichloromethane to form orange-colored complex with a maximum absorption at 460 nm. Beer's law was obeyed in the concentration range of 0–25 and 0–50 μg/mL with molar absorptivity of and L/moL/cm for RSP in methods A and B, respectively. The effects of variables such as reagents, time, and stability of the charge transfer complexes were investigated to optimize the procedures. The proposed methods have been successfully applied to the determination of RSP in pharmaceutical formulations. Results indicate that the methods are accurate, precise, and reproducible (relative standard deviation %.

  10. Synthesis, characterization and pharmacological investigation of a new charge-transfer complex of 3-aminopyridinum-p-toluenesulfonate

    Science.gov (United States)

    Murugesan, Venkatesan; Saravanabhavan, Munusamy; Sekar, Marimuthu

    2015-03-01

    The hydrogen-bonded charge-transfer complex, 3-aminopyridinum-p-toluenesulfonate was formed by the reaction between 3-aminopyridine and p-toluenesulfonic acid. On the basis of various spectroscopic results, the molecular structure has been confirmed. The crystal structure was deduced by single crystal X-ray diffraction analysis which indicated that cation and anion are linked through strong N+sbnd H--O- type of hydrogen bond. The hydrogen bonded charge transfer crystal was screened for its pharmacology, such as microbial, DNA binding/cleavage and antioxidant activity. The antibacterial and antifungal activities of the synthesized complex were examined against various bacteria and fungi strains, which showed a poor antibacterial and antifungal activity compared with standard antibacterial and fungal species. The DNA binding results indicated that the complex could interact with DNA through intercalation. The cleavage of the complex with CT-DNA inferred that the effects of cleavage are dose dependent. Antioxidant studies of the complex showed the significant antioxidant activity against DPPH, OH and ABTS radicals.

  11. Utility of Charge Transfer and Ion-Pair Complexation for Spectrophotometric Determination of Eletriptan Hydrobromide in Pure and Dosage Forms

    Directory of Open Access Journals (Sweden)

    Ayman A. Gouda

    2013-01-01

    Full Text Available Three simple, sensitive, and accurate spectrophotometric methods have been developed for the determination of eletriptan hydrobromide (ELT in pure and dosage forms. The first two methods are based on charge transfer complex formation between ELT and chromogenic reagents quinalizarin (Quinz and alizarin red S (ARS producing charge transfer complexes which showed an absorption maximum at 569 and 533 nm for Quinz and ARS, respectively. The third method is based on the formation of ion-pair complex between ELT with molybdenum(V-thiocyanate inorganic complex in hydrochloric acid medium followed by extraction of the colored ion-pair with dichloromethane and measured at 470 nm. Different variables affecting the reactions were studied and optimized. Beer's law is obeyed in the concentration ranges 2.0–18, 1.0–8.0, and 2.0–32 μg mL−1 for Quinz, ARS, and Mo(V-thiocyanate, respectively. The molar absorptivity, Sandell sensitivity, detection, and quantification limits are also calculated. The correlation coefficients were ≥0.9994 with a relative standard deviation (R.S.D%. of ≤0.925. The proposed methods were successfully applied for simultaneous determination of ELT in tablets with good accuracy and precision and without interferences from common additives, and the validity is assessed by applying the standard addition technique, which is compared with those obtained using the reported method.

  12. Enhanced Bulk and Interfacial Charge Transfer Dynamics for Efficient Photoelectrochemical Water Splitting: The Case of Hematite Nanorod Arrays.

    Science.gov (United States)

    Wang, Jian; Feng, Bo; Su, Jinzhan; Guo, Liejin

    2016-09-07

    Charge transport in the bulk and across the semiconductor/electrolyte interface is one of the major issues that limits photoelectrochemical (PEC) performance in hematite photoelectrodes. Efficient charge transport in the entire hematite is of great importance to obtaining high photoelectrochemical properties. Herein, to reach this goal, we employed both TiO2 underlayer and overlayer deposition on hematite nanorod films, followed by a fast annealing treatment. The TiO2 underlayer and overlayer not only serve as dopant sources for carrier density increase but also reduce charge recombination at the fluorine-doped tin oxide (FTO)/hematite interface and accelerate charge transfer across the hematite/electrolyte interface. This synergistic doping and interface modifying effects give rise to an enhanced photoelectrochemical water oxidation performance of hematite nanorod arrays, generating an impressive photocurrent density of 1.49 mA cm(-2) at 1.23 V vs RHE. This is the first report on using both underlayer and overlayer modification with the same material to improve charge transport through the entire electron transport path in hematite, which provides a novel way to manipulate charge transfer across the semiconductor interface for a high-performance photoelectrode.

  13. Spectrophotometric study on the charge transfer complex between sumatriptan succinate and some π-acceptors and alizarin derivatives

    Directory of Open Access Journals (Sweden)

    El Sheikh Ragaa

    2013-01-01

    Full Text Available A facile, accurate, sensitive and validated spectrophotometric methods for the determination of sumatriptan succinate (SMT in pure and in dosage forms are described. The methods are based on the formation of charge transfer products between SMT and chromogenic reagents 2,3-dichloro-5,6 dicyano-p-benzoquinone (DDQ, 7,7,8,8-tetracyanoquinodimethane(TCNQ, quinalizarin (Quiz and alizarin red S (ARS producing charge transfer complexes which showed an absorption maximum at 461, 841, 567 and 529 nm for DDQ, TCNQ, Quiz and ARS, respectively. The optimization of the reaction conditions such as the type of solvent, reagent concentration and reaction time were investigated. Beer’s law is obeyed in the concentration ranges 1.0-80 mg mL-1. The molar absorptivity, Sandell sensitivity, detection and quantification limits are also calculated. The correlation coefficient was ≥0.9994 with a relative standard deviation (R.S.D. of ≤ 1.08. The proposed methods were successfully applied for determination of sumatriptan in tablets with good accuracy and precision and without interferences from common additives by applying the standard addition technique. Developed methods have been validated statistically for their accuracy, precision, sensitivity, selectivity, robustness and ruggedness as per ICH guidelines and the results compared favourably with those obtained using the reported method.

  14. Spectroscopic and theoretical studies of charge-transfer interaction of 1-(2-pyridylazo)-2-napthol with nitroaromatics.

    Science.gov (United States)

    Karmakar, Animesh; Singh, Bula

    2017-05-15

    1-(2-Pyridylazo)-2-napthol (hereafter 1Q) is widely used as a chelating ligand applied in chelatometric, spectrophotometric analysis of metal ions. It appeared from the literature survey that no inclusion complex of 1Q was reported with nitroaromatics. The formation of charge-transfer complex gives an opportunity to improve the physico-chemical properties of different donors. So the complex of 1Q with 4-nitrophenol (4-NP), 2,4-dinitrophenol (2,4-DNP), picric acid (PA), and 3,5-dinitrosalicylic acid (3,5-DNSA) was described in this work in methanol medium. The ground and excited state binding constants and other spectroscopic data have been determined using UV-vis and fluorescence spectroscopic studies. All the complexes have been synthesized and characterized using FT-IR, 1H NMR, and elemental analysis. Spectroscopic data reveal that 1Q joins by a N+HO- type hydrogen bond with nitroaromatics. Job's plot of the continuous variation of absorbance indicates that stoichiometry of CT-complex was 1:1. Thermal stability of the synthesized complex has determined by TGA-DTA analysis. Energy-minimization DFT calculation further supported the formation of the H-bonded charge-transfer adduct. Copyright © 2017 Elsevier B.V. All rights reserved.

  15. Dynamical Behavior of Delayed Reaction-Diffusion Hopfield Neural Networks Driven by Infinite Dimensional Wiener Processes.

    Science.gov (United States)

    Liang, Xiao; Wang, Linshan; Wang, Yangfan; Wang, Ruili

    2016-09-01

    In this paper, we focus on the long time behavior of the mild solution to delayed reaction-diffusion Hopfield neural networks (DRDHNNs) driven by infinite dimensional Wiener processes. We analyze the existence, uniqueness, and stability of this system under the local Lipschitz function by constructing an appropriate Lyapunov-Krasovskii function and utilizing the semigroup theory. Some easy-to-test criteria affecting the well-posedness and stability of the networks, such as infinite dimensional noise and diffusion effect, are obtained. The criteria can be used as theoretic guidance to stabilize DRDHNNs in practical applications when infinite dimensional noise is taken into consideration. Meanwhile, considering the fact that the standard Brownian motion is a special case of infinite dimensional Wiener process, we undertake an analysis of the local Lipschitz condition, which has a wider range than the global Lipschitz condition. Two samples are given to examine the availability of the results in this paper. Simulations are also given using the MATLAB.

  16. Models of Hopfield-type quaternion neural networks and their energy functions.

    Science.gov (United States)

    Yoshida, Mitsuo; Kuroe, Yasuaki; Mori, Takehiro

    2005-01-01

    Recently models of neural networks that can directly deal with complex numbers, complex-valued neural networks, have been proposed and several studies on their abilities of information processing have been done. Furthermore models of neural networks that can deal with quaternion numbers, which is the extension of complex numbers, have also been proposed. However they are all multilayer quaternion neural networks. This paper proposes models of fully connected recurrent quaternion neural networks, Hopfield-type quaternion neural networks. Since quaternion numbers are non-commutative on multiplication, some different models can be considered. We investigate dynamics of these proposed models from the point of view of the existence of an energy function and derive their conditions for existence.

  17. Adaptive Near-Optimal Multiuser Detection Using a Stochastic and Hysteretic Hopfield Net Receiver

    Directory of Open Access Journals (Sweden)

    Gábor Jeney

    2003-01-01

    Full Text Available This paper proposes a novel adaptive MUD algorithm for a wide variety (practically any kind of interference limited systems, for example, code division multiple access (CDMA. The algorithm is based on recently developed neural network techniques and can perform near optimal detection in the case of unknown channel characteristics. The proposed algorithm consists of two main blocks; one estimates the symbols sent by the transmitters, the other identifies each channel of the corresponding communication links. The estimation of symbols is carried out either by a stochastic Hopfield net (SHN or by a hysteretic neural network (HyNN or both. The channel identification is based on either the self-organizing feature map (SOM or the learning vector quantization (LVQ. The combination of these two blocks yields a powerful real-time detector with near optimal performance. The performance is analyzed by extensive simulations.

  18. Facile, quick and selective visible-light sensing of phenol-containing drug molecules acetaminophen and biosol by use of interfacial charge-transfer transitions with TiO2 nanoparticles

    Science.gov (United States)

    Fujisawa, Jun-ichi; Eda, Takumi; Hanaya, Minoru

    2017-09-01

    Interfacial charge-transfer (ICT) transitions between inorganic semiconductors and organic compounds provide a method for facile and quick visible-light sensing of colorless organic molecules such as biologically important molecules. Here, we demonstrate facile, quick, and selective visible-light sensing of phenol-containing drug molecules 4-acetamidophenol called acetaminophen and 4-isopropyl-3-methylphenol called biosol by use of ICT transitions. The chemical adsorption of these phenol-containing drug molecules on TiO2 nanoparticles via the hydroxy group induces organic-to-TiO2 ICT transitions in the visible region. The ICT band is shifted depending on the substituents in the phenyl derivatives, allow the selective visible-light sensing of them.

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

    Science.gov (United States)

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

    2014-09-18

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

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

    Science.gov (United States)

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

    2015-08-11

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

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

    Science.gov (United States)

    Shukla, P. K.; Mishra, P. C.; Suhai, S.

    Density functional theory (DFT) at the B3LYP/6-31+G* and B3LYP/AUG-cc-pVDZ levels was employed to study O6-methylation of guanine due to its reactions with methyl chloride and methyl bromide and to obtain explanation as to why the methyl halides cause genotoxicity and possess mutagenic and carcinogenic properties. Geometries of the various isolated species involved in the reactions, reactant complexes (RCs), and product complexes (PCs) were optimized in gas phase. Transition states connecting the reactant complexes with the product complexes were also optimized in gas phase at the same levels of theory. The reactant complexes, product complexes, and transition states were solvated in aqueous media using the polarizable continuum model (PCM) of the self-consistent reaction field theory. Zero-point energy (ZPE) correction to total energy and the corresponding thermal energy correction to enthalpy were made in each case. The reactant complexes of the keto form of guanine with methyl chloride and methyl bromide in water are appreciably more stable than the corresponding complexes involving the enol form of guanine. The nature of binding in the product complexes was found to be of the charge transfer type (O6mG+ · X-, X dbond Cl, Br). Binding of HCl, HBr, and H2O molecules to the PCs obtained with the keto form of guanine did not alter the positions of the halide anions in the PCs, and the charge transfer character of the PCs was also not modified due to this binding. Further, the complexes obtained due to the binding of HCl, HBr, and H2O molecules to the PCs had greater stability than the isolated PCs. The reaction barriers involved in the formation of PCs were found to be quite high (?50 kcal/mol). Mechanisms of genotoxicity, mutagenesis and carcinogenesis caused by the methyl halides appear to involve charge transfer-type complex formation. Thus the mechanisms of these processes involving the methyl halides appear to be quite different from those that involve the

  2. Charge transfer and surface defect healing within ZnO nanoparticle decorated graphene hybrid materials

    Science.gov (United States)

    Pham, Chuyen V.; Repp, Sergej; Thomann, Ralf; Krueger, Michael; Weber, Stefan; Erdem, Emre

    2016-05-01

    To harness the unique properties of graphene and ZnO nanoparticles (NPs) for novel applications, the development of graphene-ZnO nanoparticle hybrid materials has attracted great attention and is the subject of ongoing research. For this contribution, graphene-oxide-ZnO (GO-ZnO) and thiol-functionalized reduced graphene oxide-ZnO (TrGO-ZnO) nanohybrid materials were prepared by novel self-assembly processes. Based on electron paramagnetic resonance (EPR) and photoluminescence (PL) investigations on bare ZnO NPs, GO-ZnO and TrGO-ZnO hybrid materials, we found that several physical phenomena were occurring when ZnO NPs were hybridized with GO and TrGO. The electrons trapped in Zn vacancy defects (VZn-) within the core of ZnO NPs vanished by transfer to GO and TrGO in the hybrid materials, thus leading to the disappearance of the core signals in the EPR spectra of ZnO NPs. The thiol groups of TrGO and sulfur can effectively ``heal'' the oxygen vacancy (VO+) related surface defects of ZnO NPs while oxygen-containing functionalities have low healing ability at a synthesis temperature of 100 °C. Photoexcited electron transfer from the conduction band of ZnO NPs to graphene leads to photoluminescence (PL) quenching of near band gap emission (NBE) of both GO-ZnO and TrGO-ZnO. Simultaneously, electron transfer from graphene to defect states of ZnO NPs is the origin of enhanced green defect emission from GO-ZnO. This observation is consistent with the energy level diagram model of hybrid materials.To harness the unique properties of graphene and ZnO nanoparticles (NPs) for novel applications, the development of graphene-ZnO nanoparticle hybrid materials has attracted great attention and is the subject of ongoing research. For this contribution, graphene-oxide-ZnO (GO-ZnO) and thiol-functionalized reduced graphene oxide-ZnO (TrGO-ZnO) nanohybrid materials were prepared by novel self-assembly processes. Based on electron paramagnetic resonance (EPR) and photoluminescence (PL

  3. A collection of fullerenes for synthetic access toward oriented charge-transfer cascades in triple-channel photosystems.

    Science.gov (United States)

    Bolag, Altan; López-Andarias, Javier; Lascano, Santiago; Soleimanpour, Saeideh; Atienza, Carmen; Sakai, Naomi; Martín, Nazario; Matile, Stefan

    2014-05-05

    The development of synthetic methods to build complex functional systems is a central and current challenge in organic chemistry. This goal is important because supramolecular architectures of highest sophistication account for function in nature, and synthetic organic chemistry, contrary to high standards with small molecules, fails to deliver functional systems of similar complexity. In this report, we introduce a collection of fullerenes that is compatible with the construction of multicomponent charge-transfer cascades and can be placed in triple-channel architectures next to stacks of oligothiophenes and naphthalenediimides. For the creation of this collection, modern fullerene chemistry-methanofullerenes and 1,4-diarylfullerenes-is combined with classical Nierengarten-Diederich-Bingel approaches. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Charge Transfer at the Qo-Site of the Cytochrome bc1 Complex Leads to Superoxide Production.

    Science.gov (United States)

    Salo, Adrian Bøgh; Husen, Peter; Solov'yov, Ilia A

    2017-03-02

    The cytochrome bc1 complex is the third protein complex in the electron transport chain of mitochondria or photosynthetic bacteria, and it serves to create an electrochemical gradient across a cellular membrane, which is used to drive ATP synthesis. The purpose of this study is to investigate interactions involving an occasionally trapped oxygen molecule (O2) at the so-called Qo site of the bc1 complex, which is one of the central active sites of the protein complex, where redox reactions are expected to occur. The investigation focuses on revealing the possibility of the oxygen molecule to influence the normal operation of the bc1 complex and acquire an extra electron, thus becoming superoxide, a biologically toxic free radical. The process is modeled by applying quantum chemical calculations to previously performed classical molecular dynamics simulations. Investigations reveal several spontaneous charge transfer modes from amino acid residues and cofactors at the Qo-site to the trapped O2 molecule.

  5. Semiconduction properties of some polyene-iodine charge-transfer complexes and their application in solid-state batteries

    Energy Technology Data Exchange (ETDEWEB)

    Sen, S.; Pal, P.; Misra, T.N. (Indian Association for the Cultivation of Science, Calcutta (India). Dept. of Spectroscopy)

    1993-03-01

    The conjugated polyenes [beta]-carotene, lutein, retinoic acid and [beta]-apo-8'-carotenal are shown to form charge-transfer (CT) complexes with the electron acceptor iodine. The conductivity increases by several orders of magnitude and the activation energy decreases on CT complex formation. Using these complexes as cathodic material, batteries with the configuration Mg/(polyene-iodine CT complex)/graphite are developed. Different battery parameters are evaluated. The effects of ambient temperature and humidity on battery performance are also studied. Results show that a [beta]-apo-8'-carotenal-1[sub 2] based battery has the maximum power density and longest self-life and is suitable for use as a micro-electronic gadget energizer. (author)

  6. Hydrogen-Bond Strength of CC and GG Pairs Determined by Steric Repulsion: Electrostatics and Charge Transfer Overruled.

    Science.gov (United States)

    van der Lubbe, Stephanie C C; Fonseca Guerra, Célia

    2017-08-01

    Theoretical and experimental studies have elucidated the bonding mechanism in hydrogen bonds as an electrostatic interaction, which also exhibits considerable stabilization by charge transfer, polarization, and dispersion interactions. Therefore, these components have been used to rationalize the differences in strength of hydrogen-bonded systems. A completely new viewpoint is presented, in which the Pauli (steric) repulsion controls the mechanism of hydrogen bonding. Quantum chemical computations on the mismatched DNA base pairs CC and GG (C=cytosine, G=guanine) show that the enhanced stabilization and shorter distance of GG is determined entirely by the difference in the Pauli repulsion, which is significantly less repulsive for GG than for CC. This is the first time that evidence is presented for the Pauli repulsion as decisive factor in relative hydrogen-bond strengths and lengths. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Nuclear magnetic resonance study of charge transfer complex formation between Silver Nitrate and Benzylcyanide in Solvent Ethylene Glycol

    CERN Document Server

    Modarress, H

    2003-01-01

    The formation constant for charge transfer complexes between electron acceptor (AgNo sub 3) and electron donor benzylcyanide (C sub 6 H sub 5 -CH sub 2 -C ident to N) in solvent ethyleneglycol [(CH sub 2 OH) sub 2] has been evaluated by using the nuclear magnetic resonance chemical shifts of aromatic group of benzylcyanide measured against external references, tetramethylsilane, hexamethyldisilane and cyclohexane at 20 sup d ig sup C. The external referencing procedure eliminated the interference of internal reference in the course of complexation. The necessary bulk magnetic susceptibility corrections on the measured chemical shifts have been made. The solution nationalised and their effects on the formation constant have been considered and a new equation has been suggested to obtain the main ionic activity coefficient of AgNO sub 3 from nuclear magnetic resonance results. The mean ionic activity coefficient has been taken into account in the formation constant calculations. The results indicated that the a...

  8. Successive Charge Transitions of Unusually High-Valence Fe3.5+ : Charge Disproportionation and Intermetallic Charge Transfer.

    Science.gov (United States)

    Hosaka, Yoshiteru; Denis Romero, Fabio; Ichikawa, Noriya; Saito, Takashi; Shimakawa, Yuichi

    2017-04-03

    A perovskite-structure oxide containing unusually high-valence Fe3.5+ was obtained by high-pressure synthesis. Instability of the Fe3.5+ in Ca0.5 Bi0.5 FeO3 is relieved first by charge disproportionation at 250 K and then by intermetallic charge transfer between A-site Bi and B-site Fe at 200 K. These previously unobserved successive charge transitions are due to competing intermetallic and disproportionation charge instabilities. Both transitions change magnetic and structural properties significantly, indicating strong coupling of charge, spin, and lattice in the present system. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Hanbury Brown-Twiss correlations and noise in the charge transfer statistics through a multiterminal Kondo dot.

    Science.gov (United States)

    Schmidt, T L; Komnik, A; Gogolin, A O

    2007-02-02

    We analyze the charge transfer statistics through a quantum dot in the Kondo regime, when coupled to an arbitrary number of terminals N. Special attention is paid to current cross correlations between concurring transport channels, which show distinct Hanbury Brown-Twiss antibunching for N>2 reflecting the fermionic nature of charge carriers. While this effect weakens as one moves away from the Kondo fixed point, a new type of correlations between nonconcurring channels emerges which are due entirely to the virtual polarization of the Kondo singlet. As these are not obscured by the background from fixed-point correlations they provide a promising means for extracting information on the parameters of the underlying Fermi-liquid model from the experimental data.

  10. Direct correlation of charge transfer absorption with molecular donor:acceptor interfacial area via photothermal deflection spectroscopy

    KAUST Repository

    Domingo, Ester

    2015-04-09

    We show that the Charge Transfer (CT) absorption signal in bulk-heterojunction (BHJ) solar cell blends, measured by photothermal deflection spectroscopy (PDS), is directly proportional to the density of molecular donor/acceptor interfaces. Since the optical transitions from ground state to the interfacial CT state are weakly allowed at photon energies below the optical gap of both donor and acceptor, we can exploit the use of this sensitive linear absorption spectroscopy for such quantification. Moreover, we determine the absolute molar extinction coefficient of the CT transition for an archetypical polymer-fullerene interface. The latter is ~100 times lower than the extinction coefficient of the donor chromophore involved, allowing us to experimentally estimate the transition dipole moment (0.3 D) and the electronic coupling between ground state and CT state to be on the order of 30 meV.

  11. Dynamics of charge-transfer excited states relevant to photochemical energy conversion. Technical report, June 1, 1992--March 30, 1993

    Energy Technology Data Exchange (ETDEWEB)

    Lim, E.C.

    1993-06-01

    A systematic study of intramolecular photoassociation and photoinduced charge transfer (CT) was initiated in bichromophoric systems of M-X-M, where two identical aromatic hydrocarbons M are joined by X=CH{sub 2}, O, NH, etc. Dinaphthylamines, dinaphthylethers, and dinaphthylmethanes in nonpolar solvents form triplet excimers, following inter system crossing of singlets to the triplet manifold; in polar solvents, the molecule forms an intramolecular CT state. The interchromophore interaction study was extended to N-phenyl-2-naphthylamine. The lowest excited singlet states of the dinaphthylamines were studied by semiempirical quantum chemical methods. Exciplex formation was studied in excited states of jet-cooled van der Waals complexes, such as fluorene/substituted benzenes and 1-cyanonaphthalene-aliphatic amines.

  12. Double, Rydberg and charge transfer excitations from pairing matrix fluctuation and particle-particle random phase approximation

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Yang [Department of Chemistry, Duke University, Durham, North Carolina 27708 (United States); Aggelen, Helen van [Department of Chemistry, Duke University, Durham, North Carolina 27708 (United States); Department of Inorganic and Physical Chemistry, Ghent University, 9000 Ghent (Belgium); Yang, Weitao, E-mail: weitao.yang@duke.edu [Department of Chemistry and Department of Physics, Duke University, Durham, North Carolina 27708 (United States)

    2013-12-14

    Double, Rydberg, and charge transfer (CT) excitations have been great challenges for time-dependent density functional theory (TDDFT). Starting from an (N ± 2)-electron single-determinant reference, we investigate excitations for the N-electron system through the pairing matrix fluctuation, which contains information on two-electron addition/removal processes. We adopt the particle-particle random phase approximation (pp-RPA) and the particle-particle Tamm-Dancoff approximation (pp-TDA) to approximate the pairing matrix fluctuation and then determine excitation energies by the differences of two-electron addition/removal energies. This approach captures all types of interesting excitations: single and double excitations are described accurately, Rydberg excitations are in good agreement with experimental data and CT excitations display correct 1/R dependence. Furthermore, the pp-RPA and the pp-TDA have a computational cost similar to TDDFT and consequently are promising for practical calculations.

  13. Size dependence of Eu-O charge transfer process on luminescence characteristics of YBO3:Eu3+ nanocrystals.

    Science.gov (United States)

    Sharma, Prashant K; Dutta, Ranu K; Pandey, Avinash C

    2010-07-15

    Well-crystallized pure hexagonal phase YBO(3):Eu(3+) nanoparticles are prepared by the reverse micelles method. Vacuum ultraviolet photoluminescence (VUVPL) spectroscopy showed size-dependent nonlinear luminescence enhancement with remarkably improved chromaticity (0.62, 0.34), as compared to the commercial bulk YBO(3):Eu(3+) phosphor (0.56, 0.39). The quenching concentration of Eu(3+) doping and the ratio of red ((5)D(0)-->(7)F(2)) to orange ((5)D(0)-->(7)F(1)) emission was found significantly enhanced with the decrease in particle size, making it an ideal VUV phosphor for plasma display panels. The possible explanation for size dependence of the Eu-O charge transfer process via lowering of the structural symmetry is proposed in detail.

  14. Cooperative effects of o- and m-methyl groups on the intramolecular charge-transfer emission properties of dibenzoylmethanatoboron difluorides.

    Science.gov (United States)

    Tanaka, Mirai; Muraoka, Shunsuke; Matsui, Yasunori; Ohta, Eisuke; Ogaki, Takuya; Mizuno, Kazuhiko; Ikeda, Hiroshi

    2017-06-14

    The photophysical properties of o-tolyl-, m-tolyl-, and p-xylyl-substituted asymmetric diaroylmethanatoboron difluorides in a mixture of CH2Cl2 and c-C6H12, and in the crystalline state were determined. In solution, the fluorescence (FL) properties of these substances are controlled by the position and number of methyl groups on the phenyl rings. An especially interesting finding is that FL from the p-xylyl derivative occurs from an excited state which possesses intramolecular charge-transfer character caused by the o- and m-methyl groups cooperatively. The results of X-ray crystallographic analysis reveal that these asymmetric diaroylmethanatoboron difluorides form dyads through orbital overlap of neighboring molecules. This phenomenon governs the unique FL properties of these substances in the solid state.

  15. 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

    Science.gov (United States)

    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.

  16. Strongly coupled cyclometalated ruthenium-triarylamine hybrids: tuning electrochemical properties, intervalence charge transfer, and spin distribution by substituent effects.

    Science.gov (United States)

    Yao, Chang-Jiang; Nie, Hai-Jing; Yang, Wen-Wen; Shao, Jiang-Yang; Yao, Jiannian; Zhong, Yu-Wu

    2014-12-22

    Nine cyclometalated ruthenium complexes with a redox-active diphenylamine unit in the para position to the RuC bond were prepared. MeO, Me, and Cl substituents on the diphenylamine unit and three types of auxiliary ligands-bis(N-methylbenzimidazolyl)pyridine (Mebip), 2,2':6',2''-terpyridine (tpy), and trimethyl-4,4',4''-tricarboxylate-2,2':6',2''-terpyridine (Me3 tctpy)--were used to vary the electronic properties of these complexes. The derivative with an MeO-substituted amine unit and Me3 tctpy ligand was studied by single-crystal X-ray analysis. All complexes display two well-separated redox waves in the potential region of +0.1 to +1.0 V versus Ag/AgCl, and the potential splitting ranges from 360 to 510 mV. Spectroelectrochemical measurements show that these complexes display electrochromism at low potentials and intense near-infrared (NIR) absorptions. In the one-electron oxidized form, the complex with the Cl-substituted amine unit and Mebip ligand shows a moderate ligand-to-metal charge transfer at 800 nm. The other eight complexes show asymmetric, narrow, and intense intervalence charge-transfer transitions in the NIR region, which are independent of the polarity of the solvent. The Mebip-containing complexes display rhombic or broad isotropic EPR signals, whereas the other seven complexes show relatively narrow isotropic EPR signals. In addition, DFT and time-dependent DFT studies were performed to gain insights into the spin distributions and NIR absorptions. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Spectrophotometric determination of quetiapine fumarate in pharmaceuticals and human urine by two charge-transfer complexation reactions

    Directory of Open Access Journals (Sweden)

    Vinay K.B.

    2012-01-01

    Full Text Available Two simple, rapid and accurate spectrophotometric procedures are proposed for the determination of quetiapine fumarate (QTF in pharmaceuticals and in spiked human urine. The methods are based on charge transfer complexation reactions of free base form of the drug (quetiapine, QTP, as n-electron donor (D, with either p-chloranilic acid (p-CAA (method A or 2,3-dichloro-5,6-dicyanoquinone (DDQ (method B as π-acceptors (A. The coloured charge transfer complexes produced exhibit absorption maxima at 520 and 540 nm, in method A and method B, respectively. The experimental conditions such as reagent concentration, reaction solvent and time have been carefully optimized to achieve the maximum sensitivity. Beer’s law is obeyed over the concentration ranges of 8.0 - 160 and 4.0 - 80.0 μg ml-1, for method A and method B, respectively. The calculated molar absorptivity values are 1.77 × 103 and 4.59 × 103 l mol-1cm-1, respectively, for method A and method B. The Sandell sensitivity values, limits of detection (LOD and quantification (LOQ have also been reported. The stoichiometry of the reaction in both cases was accomplished adopting the limiting logarithmic method and was found to be 1: 2 (D: A. The accuracy and precision of the methods were evaluated on intra-day and inter-day basis. The proposed methods were successfully applied for the determination of QTF in pharmaceutical formulations and spiked human urine.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-12-01

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

  19. Controlled Assembly of Heterobinuclear Sites on Mesoporous Silica: Visible Light Charge-Transfer Units with Selectable Redox Properties

    Energy Technology Data Exchange (ETDEWEB)

    Frei, Heinz; Han, Hongxian; Frei, Heinz

    2008-06-04

    Mild synthetic methods are demonstrated for the selective assembly of oxo-bridged heterobinuclear units of the type TiOCrIII, TiOCoII, and TiOCeIII on mesoporous silica support MCM-41. One method takes advantage of the higher acidity and, hence, higher reactivity of titanol compared to silanol OH groups towards CeIII or CoII precursor. The procedure avoids the customary use of strong base. The controlled assembly of the TiOCr system exploits the selective redox reactivity of one metal towards another (TiIII precursor reacting with anchored CrVI centers). The observed selectivity for linking a metal precursor to an already anchored partner versus formation of isolated centers ranges from a factor of six (TiOCe) to complete (TiOCr, TiOCo). Evidence for oxo bridges and determination of the coordination environment of each metal centers is based on K-edge EXAFS (TiOCr), L-edge absorption spectroscopy (Ce), and XANES measurements (Co, Cr). EPR, optical, FT-Raman and FT-IR spectroscopy furnish additional details on oxidation state and coordination environment of donor and acceptor metal centers. In the case of TiOCr, the integrity of the anchored group upon calcination (350 oC) and cycling of the Cr oxidation state is demonstrated. The binuclear units possess metal-to-metal charge-transfer transitions that absorb deep in the visible region. The flexible synthetic method for assembling the units opens up the use of visible light charge transfer pumps featuring donor or acceptor metals with selectable redox potential.

  20. Spectrophotometric determination and thermodynamic studies of the charge transfer complexation of emedastine difumarate with some π-acceptors

    Directory of Open Access Journals (Sweden)

    Abdel-Raeq A. Sawsan

    2017-05-01

    Full Text Available Spectrophotometric procedures were presented for the determination of antihistaminic drug, emedastine difumarate. The methods are based on the charge transfer complexation reaction of the drug with π-acceptors; 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ, chloranilic acid (CA and 7,7,8,8-tetracyanoquinodimethane (TCNQ. Different charge-transfer complexes and colored radical anions were obtained. The formations of the colored complexes were utilized in the development of simple, rapid and accurate spectrophotometric methods for the analysis of emedastine in drug substance and products. Under the optimum reaction conditions, linear relationships with good correlation coefficients (0.9996–0.9999 were found between the absorbance at the relevant maxima and the concentrations of emedastine in the range of 0.8–200 μg mL−1. The limits of detection ranged from 0.06 to 0.76 μg mL−1. The molar absorptivities and association constants for the colored complexes were evaluated using the Benesi–Hildebrand equation. The free energy change (ΔG° and the enthalpy of formation (ΔH° as well as the entropy (ΔS° were also determined. The methods were successfully applied to analyze the drug formulation with mean recovery percentages ± RSD% of 100.04 ± 0.59–100.22 ± 0.72. The results were compared favorably with the official and reported methods.

  1. Differential and total cross sections for charge transfer and transfer-excitation in ion-helium collisions

    Science.gov (United States)

    Halder, S.; Mondal, A.; Samaddar, S.; Mandal, C. R.; Purkait, M.

    2017-09-01

    Total cross sections for single charge transfer in collisions of multicharged bare ions with ground-state helium atoms at incident energy ranging from 40 to 5000 keV/amu have been calculated in the framework of a four-body model of final channel distorted-wave (FC-DW-4B) approximation. In this formalism, distortion in the final channel related to the Coulomb continuum of the target and the Coulomb interaction between the passive electron in the target with the projectile are included. In all cases, total single electron-capture cross sections have been calculated by summing over all contributions up to n =3 shells and subshells. It has been observed that the contribution of the capture cross sections into excited states have insignificant contributions for symmetric collisions. Comprehensive comparisons are made between the four body model of boundary corrected continuum intermediate-state approximations [Phys. Rev. A 83, 032706 (2011), 10.1103/PhysRevA.83.032706] and the present FC-DW-4B model. The main purpose of the present study is to investigate the relative importance of dynamic electron correlation and the role of passive electron in the target at intermediate and high impact energies. In addition, projectile angular differential cross sections (DCS) for charge transfer and transfer-excitation in p -He collisions are calculated at different impact energies. At low projectile energies, the present DCS data exhibits the typical steeply decreasing dependence on the projectile scattering angles, whereas at high impact energies, the double-scattering region centered on the Thomas angle is obtained. Detailed comparisons with the available experimental data and other theories are reported with the purpose of further assessing the relevance of the present model at different impact energies. Overall, the calculated cross sections show good agreement with the available experimental findings.

  2. Spectrophotometric determination of fenoprofen calcium drug in pure and pharmaceutical preparations. Spectroscopic characterization of the charge transfer solid complexes

    Science.gov (United States)

    Mohamed, Marwa E.; Frag, Eman Y. Z.; Hathoot, Abla A.; Shalaby, Essam A.

    2018-01-01

    Simple, accurate and robust spectrophotometric method was developed for determination of fenoprofen calcium drug (FPC). The proposed method was based on the charge transfer (CT) reaction of FPC drug (as n-electron donor) with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), 2,4,6-trinitrophenol (picric acid, PA) or 1,2,5,8-tetrahydroxyanthraquinone (Quinalizarin, QZ) (as π-acceptors) to give highly colored charge transfer complexes. Different variables affecting the reaction such as reagent concentration, temperature and time have been carefully optimized to achieve the highest sensitivity. Beer's law was obeyed over the concentration ranges of 2-60, 0.6-90 and 4-30 μg mL- 1 using DDQ, PA and QZ CT reagents, respectively, with correlation coefficients of 0.9986, 0.9989 and 0.997 and detection limits of 1.78, 0.48 and 2.6 μg mL- 1 for the CT reagents in the same order. Elucidation of the chemical structure of the solid CT complexes formed via reaction between the drug under study and π-acceptors was done using elemental, thermal analyses, IR, 1H NMR and mass spectrometry. X-ray diffraction was used to estimate the crystallinity of the CT complexes. Their biological activities were screened against different bacterial and fungal organisms. The method was applied successfully with satisfactory results for the determination of FPC drug in fenoprofen capsules. The method was validated with respect to linearity, limit of detection and quantification, inter- and intra-days precision and accuracy. The proposed method gave comparable results with the official method.

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

    KAUST Repository

    Jiang, Junlin

    2017-05-25

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

  4. Evidence for coherent mixing of excited and charge-transfer states in the major plant light-harvesting antenna, LHCII.

    Science.gov (United States)

    Ramanan, Charusheela; Ferretti, Marco; van Roon, Henny; Novoderezhkin, Vladimir I; van Grondelle, Rienk

    2017-08-30

    LHCII, the major light harvesting antenna from plants, plays a dual role in photosynthesis. In low light it is a light-harvester, while in high light it is a quencher that protects the organism from photodamage. The switching mechanism between these two orthogonal conditions is mediated by protein dynamic disorder and photoprotective energy dissipation. The latter in particular is thought to occur in part via spectroscopically 'dark' states. We searched for such states in LHCII trimers from spinach, at both room temperature and at 77 K. Using 2D electronic spectroscopy, we explored coherent interactions between chlorophylls absorbing on the low-energy side of LHCII, which is the region that is responsible for both light-harvesting and photoprotection. 2D beating frequency maps allow us to identify four frequencies with strong excitonic character. In particular, our results show the presence of a low-lying state that is coupled to a low-energy excitonic state. We assign this to a mixed excitonic-charge transfer state involving the state with charge separation within the Chl a603-b609 heterodimer, borrowing some dipole strength from the Chl a602-a603 excited states. Such a state may play a role in photoprotection, in conjunction with specific and environmentally controlled realizations of protein dynamic disorder. Our identification and assignment of the coherences observed in the 2D frequency maps suggests that the structure of exciton states as well as a mixing of the excited and charge-transfer states is affected by coupling of these states to resonant vibrations in LHCII.

  5. Charge transferred doping of single layer graphene by mono-dispersed manganese-oxide nanoparticles adsorption

    Science.gov (United States)

    Phan, Thanh Luan; Kang, Myunggoo; Choi, Soo Ho; Kim, You Joong; Jung, Hyun; Yoon, Im Taek; Yang, Woochul

    2017-10-01

    We report an efficient and controllable method to introduce p-type doping in graphene by decoration with Mn3O4 nanoparticles (NPs) on mechanically exfoliated single layer graphene. A monolayer of Mn3O4 NPs, with a diameter in the range of 5-10 nm, was decorated on a graphene film using an ex-situ method, whereas by controlling the coverage of the NPs on the graphene surface, the carrier concentration could be continually adjusted. The p-type of the NP-decorated single layer graphene was confirmed by the Raman G-band. It was found that the carrier concentration could be gradually adjusted up to 26.09 × 1012 cm-2, with 90% coverage of Mn3O4 NPs. The Dirac point of the pristine graphene at the gate bias of 27 V shifted to 150 V for Mn3O4 NP decorated graphene. The p-type graphene doped with Mn3O4 NPs demonstrated significant high air-stability, even under an oxygen atmosphere for 60 days. This approach allows for the opportunity for simple, scalable, and highly stable doping of graphene for future high-performance electronic device applications.

  6. A new molecular design based on hybridized local and charge transfer fluorescence for highly efficient (>6%) deep-blue organic light emitting diodes.

    Science.gov (United States)

    Kumar Konidena, Rajendra; Justin Thomas, K R; Kumar Dubey, Deepak; Sahoo, Snehasis; Jou, Jwo-Huei

    2017-08-22

    A deep-blue emitter was developed by modifying carbazole nuclear positions C2 & C7 with a triphenylamine donor and C3 & C6 with a cyano acceptor. The molecular design features cross-conjugated localized and charge transfer chromophores which results in a hybridized local charge transfer (HLCT) excited state. An organic light emitting diode (OLED) using this material exhibited high external quantum efficiency (6.5%) with excellent color saturation (CIEy ∼ 0.06) and small full-width at half maximum (48 nm).

  7. A study of charge transfer kinetics in dye-sensitized surface conductivity solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Friedrich, Dennis

    2011-05-15

    concentration of the redox species in the electrolyte film, having the fastest decay at the lowest concentration of the redox couple. This was due to the regeneration of the oxidized dye by iodide, screening the positive charge from recombination with injected electrons. The adsorption of cations such as Li{sup +} led to a relatively weak increase of the electron lifetime, although in combination with a redox couple these effects were less clear. The replacement of the iodide/iodine redox couple by the kinetically fast ferrocene/ ferrocenium system caused a dramatic increase of the decay rates of photogenerated charge carriers in subset devices. Thus, showing the importance of the kinetically slow reduction rates of the oxidized redox couple iodide/iodine, leading to an increase of the electron lifetime by the reduction of the dye cation. The analysis of charge carrier kinetics in TiO{sub 2} powders and films displayed a decrease of the decay rate upon dye-sensitization after band-to-band excitation with laser pulses at 355 nm. In the case of ZnO films, the presence of the dye induced a significantly accelerated decay after excitation at 355 nm. In contrast to the ZnO films, ZnO nanorods displayed no such destructive influence of the dye adsorption. Furthermore, after exciting the sample at 355 nm, the decay was found to be independent of the dye and mainly depending on the recombination of electron-hole pairs and electrons with the dye cation at 355 nm and 532 nm, respectively. (orig.)

  8. Photonics at the frontiers. Generation of few-cycle light pulses via NOPCPA and real-time probing of charge transfer in hybrid photovoltaics

    Energy Technology Data Exchange (ETDEWEB)

    Herrmann, Daniel

    2011-11-11

    this thesis for the first time succeeded to resolve the photoinduced charge-transfer in the conjugate polymer polythiophene and in hybrid polythiophene/silicon solar cells in real time. Thereby a controverse debate about the nature of the primary photoexcitation in organic semiconductors is resolved: Excitons dissociate with 140 fs time constant to polarons (charge carriers). Deciding parameters (for instance structural order, charge-carrier mobility) for the efficiency of the generation and extraction of free charge carriers can be determined. Further ultrashort-time experiments at novel organic solar cells have here been begun and indicated.

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

    Science.gov (United States)

    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.

  10. Two Closely Related Organic Charge-Transfer Complexes Based on Tetrathiafulvalene and 9H-fluorenone Derivatives. Competition between Hydrogen Bonding and Stacking Interactions

    Directory of Open Access Journals (Sweden)

    Amparo Salmerón-Valverde

    2015-06-01

    Full Text Available Two 1:1 charge-transfer organic complexes were formed using tetrathiafulvalene as a donor and a 9H-fluorenone derivative as acceptor: 4,5,7-trinitro-9H-fluoren-9-one-2-carboxylic acid (complex 1 or 4,5,7-trinitro-9H-fluoren-9-one-2-carboxylic acid methyl ester (complex 2. Both systems crystallize with alternated donor and acceptor stacks. However, the crystal structure of 1 is influenced by classical hydrogen bonds involving carboxylic acid groups, which force to arrange acceptors as centrosymmetric dimers in the crystal, via R2 2(8 ring motifs, while such a restriction is no longer present in the case of 2, affording thus a different crystal structure. This main difference is reflected in stacking interactions, and, in turn, in the degree of charge transfer observed in the complexes. The degree of charge transfer, estimated using Raman spectroscopy, is δ1 = 0.07 for 1 and δ2 = 0.14 for 2. It thus seems that, at least for the studied complexes, hydrogen bonding is an unfavorable factor for charge transfer.

  11. Efficient two-step photogeneration of long-lived charges in ground-state charge-transfer complexes of conjugated polymer doped with fullerene

    NARCIS (Netherlands)

    Bakulin, Artem A.; Zapunidy, Sergey A.; Pshenichnikov, Maxim S.; van Loosdrecht, Paul H. M.; Paraschuk, Dmitry Yu.

    2009-01-01

    Polarization-sensitive time-resolved visible-infrared pump-probe experiments demonstrate that one can efficiently generate long-lived charges in donor-acceptor charge transfer complex (CTC) of conjugated polymer doped with fullerene, MEH-PPV/dinitroanthraquinone/C(60). In particular, a strong

  12. Isotope effects on the charge transfer into the n=1, 2, and 3 shells of He2+ in collisions with H, D, and T

    NARCIS (Netherlands)

    Stolterfoht, N.; Cabrera-Trujillo, R.; Krstic, P. S.; Hoekstra, R.; Oehrn, Y.; Deumens, E.; Sabin, J. R.

    Processes for charge transfer into He2+ colliding with the atomic isotopes hydrogen (H), deuterium (D), and tritium (T) are theoretically studied at collision energies as low as 30 eV/amu. Probabilities and cross sections for electron capture into different shells of the projectile are calculated

  13. Coexisting Behaviors of Asymmetric Attractors in Hyperbolic-Type Memristor based Hopfield Neural Network

    Directory of Open Access Journals (Sweden)

    Bocheng Bao

    2017-08-01

    Full Text Available A new hyperbolic-type memristor emulator is presented and its frequency-dependent pinched hysteresis loops are analyzed by numerical simulations and confirmed by hardware experiments. Based on the emulator, a novel hyperbolic-type memristor based 3-neuron Hopfield neural network (HNN is proposed, which is achieved through substituting one coupling-connection weight with a memristive synaptic weight. It is numerically shown that the memristive HNN has a dynamical transition from chaotic, to periodic, and further to stable point behaviors with the variations of the memristor inner parameter, implying the stabilization effect of the hyperbolic-type memristor on the chaotic HNN. Of particular interest, it should be highly stressed that for different memristor inner parameters, different coexisting behaviors of asymmetric attractors are emerged under different initial conditions, leading to the existence of multistable oscillation states in the memristive HNN. Furthermore, by using commercial discrete components, a nonlinear circuit is designed and PSPICE circuit simulations and hardware experiments are performed. The results simulated and captured from the realization circuit are consistent with numerical simulations, which well verify the facticity of coexisting asymmetric attractors' behaviors.

  14. On macroscopic quantum phenomena in biomolecules and cells: from Levinthal to Hopfield.

    Science.gov (United States)

    Raković, Dejan; Dugić, Miroljub; Jeknić-Dugić, Jasmina; Plavšić, Milenko; Jaćimovski, Stevo; Setrajčić, Jovan

    2014-01-01

    In the context of the macroscopic quantum phenomena of the second kind, we hereby seek for a solution-in-principle of the long standing problem of the polymer folding, which was considered by Levinthal as (semi)classically intractable. To illuminate it, we applied quantum-chemical and quantum decoherence approaches to conformational transitions. Our analyses imply the existence of novel macroscopic quantum biomolecular phenomena, with biomolecular chain folding in an open environment considered as a subtle interplay between energy and conformation eigenstates of this biomolecule, governed by quantum-chemical and quantum decoherence laws. On the other hand, within an open biological cell, a system of all identical (noninteracting and dynamically noncoupled) biomolecular proteins might be considered as corresponding spatial quantum ensemble of these identical biomolecular processors, providing spatially distributed quantum solution to a single corresponding biomolecular chain folding, whose density of conformational states might be represented as Hopfield-like quantum-holographic associative neural network too (providing an equivalent global quantum-informational alternative to standard molecular-biology local biochemical approach in biomolecules and cells and higher hierarchical levels of organism, as well).

  15. Modelling microtubules in the brain as n-qudit quantum Hopfield network and beyond

    Science.gov (United States)

    Pyari Srivastava, Dayal; Sahni, Vishal; Saran Satsangi, Prem

    2016-01-01

    The scientific approach to understand the nature of consciousness revolves around the study of the human brain. Neurobiological studies that compare the nervous system of different species have accorded the highest place to humans on account of various factors that include a highly developed cortical area comprising of approximately 100 billion neurons, that are intrinsically connected to form a highly complex network. Quantum theories of consciousness are based on mathematical abstraction and the Penrose-Hameroff Orch-OR theory is one of the most promising ones. Inspired by the Penrose-Hameroff Orch-OR theory, Behrman et al. have simulated a quantum Hopfield neural network with the structure of a microtubule. They have used an extremely simplified model of the tubulin dimers with each dimer represented simply as a qubit, a single quantum two-state system. The extension of this model to n-dimensional quantum states or n-qudits presented in this work holds considerable promise for even higher mathematical abstraction in modelling consciousness systems.

  16. Theoretical investigations into the charge transfer properties of thiophene α-substituted naphthodithiophene diimides: excellent n-channel and ambipolar organic semiconductors.

    Science.gov (United States)

    Ji, Li-Fei; Fan, Jian-Xun; Zhang, Shou-Feng; Ren, Ai-Min

    2017-05-31

    A theoretical study was carried out to investigate the electronic structures and the charge transport properties of a series of naphthodithiophene diimide (NDTI) thiophene α-substituted derivatives NDTI-X using density functional theory and classical Marcus charge transfer theory. This study deeply revealed the structure-property relationships by analyzing the intermolecular interactions in crystal structures of C8-NDTI and C8-NDTI-Cl thoroughly by using the Hirshfeld surface, QTAIM theories and symmetry-adapted perturbation theory (SAPT). Our results suggested that a 2-D brick-like π-stacking structure makes C8-NDTI-Cl a more excellent n-type semiconducting material with μmax-e of 2.554 cm(2) V(-1) s(-1) than C8-NDTI with a herringbone-like slipped π-stacking motif. In addition, the calculated results showed that by modifying the thiophene α-positions of NDTI with electron-withdrawing substituents, -F, -Cl and -CN, low-lying LUMO energy levels and a high adiabatic electron affinity EA(a) can be obtained; while introducing electron-donating groups, benzene (-B), thiophene (-T), benzo[b]thiophene (-BT) and naphtha[2,3-b]thiophene (-NT), expanded the molecular π-conjugated backbone, and narrow band gaps, high EA(a) and small reorganization energies can be obtained. Theoretical simulations predict that NDTI-CN is an excellent air-stable n-type organic semiconducting material with an average electron mobility μe of up to 1.743 cm(2) V(-1) s(-1). Owing to their high EA(a), moderate adiabatic ionization potential IP(a) as well as small hole and electron reorganization energies, NDTI-BT and NDTI-NT are two well-balanced air-stable ambipolar semiconducting materials. The theoretical average hole/electron mobilities are as high as 2.708/3.739 cm(2) V(-1) s(-1) for C8-NDTI-NT and 1.597/2.350 cm(2) V(-1) s(-1) for C8-NDTI-BT, respectively.

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

    Science.gov (United States)

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

    2012-11-14

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

  18. Assessing Carbon-Based Anodes for Lithium-Ion Batteries: A Universal Description of Charge-Transfer Binding

    Science.gov (United States)

    Liu, Yuanyue; Wang, Y. Morris; Yakobson, Boris I.; Wood, Brandon C.

    2014-07-01

    Many key performance characteristics of carbon-based lithium-ion battery anodes are largely determined by the strength of binding between lithium (Li) and sp2 carbon (C), which can vary significantly with subtle changes in substrate structure, chemistry, and morphology. Here, we use density functional theory calculations to investigate the interactions of Li with a wide variety of sp2 C substrates, including pristine, defective, and strained graphene, planar C clusters, nanotubes, C edges, and multilayer stacks. In almost all cases, we find a universal linear relation between the Li-C binding energy and the work required to fill previously unoccupied electronic states within the substrate. This suggests that Li capacity is predominantly determined by two key factors—namely, intrinsic quantum capacitance limitations and the absolute placement of the Fermi level. This simple descriptor allows for straightforward prediction of the Li-C binding energy and related battery characteristics in candidate C materials based solely on the substrate electronic structure. It further suggests specific guidelines for designing more effective C-based anodes. The method should be broadly applicable to charge-transfer adsorption on planar substrates, and provides a phenomenological connection to established principles in supercapacitor and catalyst design.

  19. Quantum Confinement of Hybrid Charge Transfer Excitons in GaN/InGaN/Organic Semiconductor Quantum Wells.

    Science.gov (United States)

    Panda, Anurag; Forrest, Stephen R

    2017-12-13

    We investigate hybrid charge transfer exciton (HCTE) confinement in organic-inorganic (OI) quantum wells (QWs) comprising a thin InGaN layer bound on one side by GaN and on the other by the organic semiconductors, tetraphenyldibenzoperiflanthene (DBP) or 4,4'-bis(N-carbazolyl)-1,1'-biphenyl (CBP). A binding energy of 10 meV is calculated for the Coulombically bound free HCTE state between a delocalized electron in GaN and a hole localized in DBP. The binding energy of the HCTE increases to 165 meV when the electron is confined to a 1.5 nm In0.21Ga0.79N QW (HCTEQW). The existence of the HCTEQW is confirmed by measuring the voltage-dependent DBP exciton dissociation yield at the OI heterojunction in the QW devices that decrease with increasing In concentration and decreasing electric field, matching the trends predicted by Poole-Frenkel emission. Combining spectroscopic measurements with optical models, we find that 14 ± 3% of the excitons that reach the GaN/DBP heterojunction form HCTEs and dissociate into free charges, while the remainder recombine. A high nonradiative recombination rate through defect states at the heterointerface account for the lack of observation of HCTEQW photoluminescence from GaN/InGaN/CBP QWs at temperatures as low as 10 K.

  20. Ground state isomerism in betacarboline hydrogen bond complexes: The charge transfer nature of its large Stokes shifted emission

    Science.gov (United States)

    Sánchez-Coronilla, Antonio; Balón, Manuel; Muñoz, María A.; Hidalgo, José; Carmona, Carmen

    2008-07-01

    The hydrogen bonding and excited state proton transfer reactions between betacarboline, 9 H-pyrido[3,4- b]indole, BC, and 1,1,1,3,3,3-hexafluoropropan-2-ol, HFIP, have been studied in the aprotic solvents cyclohexane and toluene by absorption, steady state and time resolved fluorescence measurements. On the basis of these results and those of previous works (Refs. [A. Sánchez-Coronilla, C. Carmona, M.A. Muñoz, M. Balón, Chem. Phys., 327 (2006) 70] and [A. Sánchez-Coronilla, M. Balón, M.A. Muñoz, C. Carmona, Chem. Phys. 344 (2008) 72]) two main fundamental conclusions can be drawn on the photophysical behaviour of BC. Thus, it is shown, for the first time, that the non-cyclic double hydrogen bond complexes formed through both nitrogen atoms of BC, DHB, can suffer, in their ground state, an isomerisation process. These adducts acquire a quinoid structure in cyclohexane, but maintain a dipolar zwitterionic structure in toluene. Moreover, it is concluded that the observed large Stokes shifted emission, around 520 nm, is not due, as it has been so far generally accepted, to the emission of a BC zwitterionic phototautomer, but to the intramolecular charge transfer, ICT, excited state emissions of the DHB hydrogen bond adducts.

  1. Ferroelectric BaTiO3 dipole induced charge transfer enhancement in dye-sensitized solar cells

    Science.gov (United States)

    Feng, Keyuan; Liu, Xiaoyan; Si, Donghui; Tang, Xiao; Xing, An; Osada, Minoru; Xiao, Peng

    2017-05-01

    BaTiO3/TiO2 nanocomposite films with varied amount of BaTiO3 are fabricated and applied as photoanodes for dye-sensitized solar cells (DSCs) and demonstrated enhanced power conversion efficiency. Ferroelectricity of BaTiO3 in the film after subjected to a annealing process up to 450 °C is examined by Switching Spectroscopy Piezoresponse Force Microscopy (SSPFM). The highest performance is achieved in 1.0 wt% BaTiO3 addition as a result of increased photocurrent density (Jsc) and fill factor (FF), regardless of reduction of dye-loading. Electrochemical impedance spectroscopy (EIS) measurements at different bias voltages (≦Voc) in dark suggest that ferroelectric dipole induced electric field has positive effects on enhancing electron mobility and suppressing charge recombination. Although more detailed experiments are needed in designing of the nanocomposite films for compensating characteristics of dye-loading and electron mobility, introduction of ferroelectric dipole induced electric field into the photoanode would be a good strategy in achieving further improvement of power conversion efficiency of DSCs through improved charge transfer properties.

  2. A Validated High-Throughput Fluorometric Method for Determination of Omeprazole in Quality Control Laboratory via Charge Transfer Sensitized Fluorescence.

    Science.gov (United States)

    Mahmoud, Ashraf M; Ahmed, Sameh A

    2016-03-01

    A high-throughput 96-microwell plate fluorometric method was developed and validated to determine omeprazole (OMZ) in its dosage forms. The method was based on the charge-transfer (CT) sensitized fluorescence reaction of OMZ with 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone (DDQ). This fluorescence reaction provided a new approach for simple, sensitive and selective determinations of OMZ in pharmaceutical preparations. In the present method, the fluorescence reaction was carried out in 96-microwell plates as reaction vessels in order to increase the automation of the methodology and the efficiency of its use in quality control laboratories. All factors affecting the fluorescence reaction were carefully studied and the conditions were optimized. The stoichiometry of the fluorescence reaction between OMZ and DDQ was determined and the reaction mechanism was suggested. Under the optimum conditions, the linear range was 100-6000 ng/ml with the lowest LOD of 33 ng/ml. Analytical performance of the proposed assay, in terms of accuracy and precision, was statistically validated and the results were satisfactory; RSD was <2.6 % and the accuracy was 98.6-101.6 %. The method was successfully applied to the analysis of OMZ in its dosage forms; the recovery values were 98.26-99.60 ± 0.95-2.22 %. The developed methodology may provide a safer, automated and economic tool for the analysis of OMZ in quality control laboratories.

  3. Spectrophotometric study of the charge-transfer and ion-pair complexation of methamphetamine with some acceptors

    Science.gov (United States)

    Shahdousti, Parvin; Aghamohammadi, Mohammad; Alizadeh, Naader

    2008-04-01

    The charge-transfer (CT) complexes of methamphetamine (MPA) as a n-donor with several acceptors including bromocresolgreen (BCG), bromocresolpurple (BCP), chlorophenolred (CPR), picric acid (PIC), and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) have been studied spectrophotometrically in chloroform solutions in order to obtain some information about their stoichiometry and stability of complexation. The oscillator strengths, transition dipole moments and resonance energy of the complex in the ground state for all complexes have been calculated. Vertical ionization potential of MPA and electron affinity of acceptors were determined by ab initio calculation. The acceptors were also used to utilize a simple and sensitive extraction-spectrophotometric method for the determination of MPA. The method is based on the formation of 1:1 ion-pair association complexes of MPA with BCG, BCP and PIC in chloroform medium. Beer's plots were obeyed in a general concentration range of 0.24-22 μg ml -1 for the investigated drug with different acceptors. The proposed methods were applied successfully for the determination of MAP in pure and abuse drug with good accuracy and precision.

  4. A hermetic self-sustained microbial solar cell based on Chlorella vulgaris and a versatile charge transfer chain

    Science.gov (United States)

    Pan, Keliang; Zhou, Peijiang

    2015-10-01

    A hermetic noble-metal-free membrane-less microbial solar cell (MSC) is established. The substances decomposition and regeneration in this MSC are carried out only by Chlorella vulgaris simultaneously. The conversion of metabolism types of C. vulgaris is controlled only by illumination. By using a pleiotropic redox mediator and a cupric hexacyanoferrate modified cathode, a two-phase three-stage charge transfer chain is formed. Through this pathway, the one microorganism self-sustained system gets a long-term power output up to 0.04773 mW/cm2 at 0.423 V without any material exchange with external, which is 50 times higher than that obtained from the original system. Benefiting from this electron buffer system, the battery will achieve an electricity generation in both light and dark conditions. There is almost no consumption of any substrates throughout the stabilized process, and no more additions are required. This maintenance-free and extremely inexpensive reactor with a simple structure and a long service life demonstrates the possibility of combining the microbial, chemical and photo cells.

  5. In/Ga-free, inkjet-printed charge transfer doping for solution-processed ZnO.

    Science.gov (United States)

    Yu, Seong Hun; Kim, Beom Joon; Kang, Moon Sung; Kim, Se Hyun; Han, Jong Hun; Lee, Jun Young; Cho, Jeong Ho

    2013-10-09

    An In/Ga-free doping method of zinc oxide (ZnO) is demonstrated utilizing a printable charge transfer doping layer (CTDL) based on (3-aminopropyl)triethoxysilane (APS) molecules. The self-assembled APS molecules placed on top of ZnO thin films lead to n-type doping of ZnO and filling shallow electron traps, due to the strong electron-donating characteristics of the amine group in APS molecules. The CTDL doping can tune the threshold voltage and the mobility of the ZnO thin-film transistors (TFTs) as one varies the grafting density of the APS molecules and the thickness of the underneath ZnO thin films. From an optimized condition, high-performance ZnO TFTs can be achieved that exhibit an electron mobility of 4.2 cm(2)/(V s), a threshold voltage of 10.5 V, and an on/off current ratio larger than 10(7). More importantly, the method is applicable to simple inkjet processes, which lead to produce high-performance depletion load ZnO inverters through selective deposition of CTDL on ZnO thin films.

  6. The origin of the antiferromagnetic behaviour of the charge-transfer compound (HMTTF)[Ni(mnt)2].

    Science.gov (United States)

    Vela, Sergi; Fumanal, Maria; Deumal, Mercè

    2015-01-14

    The charge-transfer (HMTTF)[Ni(mnt)2] material (1) was the first mixed-stack compound reported to present ferromagnetic (FM) interactions between the donor (D) and acceptor (A) units within each mixed-stack. Despite the presence of a dominant FM interaction, its magnetic susceptibility curve, χ(T), corresponded to that of an antiferromagnetic (AFM) compound at low temperatures, a fact that was tentatively explained in terms of a FM-to-AFM magnetic transition. In this work, the First-Principles Bottom-Up procedure has been applied to rationalize the magnetic properties of 1. The results presented herein indicate the presence of up to five sizeable JAB magnetic exchange interactions (26.0, -1.7, 1.9, 0.1, and -99.3 cm(-1)) that create a complex 2D magnetic network. This magnetic topology not only produces a calculated χ(T) curve that is in excellent agreement with the experimental measurements, but also allows us to understand the magnetic behaviour of 1, in the full range of temperatures, solely in terms of the different Boltzmann population of diamagnetic and paramagnetic spin states as the temperature changes. Our data thus provide a plausible explanation for the AFM behaviour of 1 at low temperatures that does not involve a phase transition.

  7. Control of the dipole layer of polar organic molecules adsorbed on metal surfaces via different charge-transfer channels

    Science.gov (United States)

    Lin, Meng-Kai; Nakayama, Yasuo; Zhuang, Ying-Jie; Su, Kai-Jun; Wang, Chin-Yung; Pi, Tun-Wen; Metz, Sebastian; Papadopoulos, Theodoros A.; Chiang, T.-C.; Ishii, Hisao; Tang, S.-J.

    2017-02-01

    Organic molecules with a permanent electric dipole moment have been widely used as a template for further growth of molecular layers in device structures. Key properties of the resulting organic films such as energy level alignment (ELA), work function, and injection/collection barrier are linked to the magnitude and direction of the dipole moment at the interface. Using angle-resolved photoemission spectroscopy (ARPES), we have systematically investigated the coverage-dependent work function and spectral line shapes of occupied molecular energy states (MESs) of chloroaluminium-phthalocyanine (ClAlPc) grown on Ag(111). We demonstrate that the dipole orientation of the first ClAlPc layer can be controlled by adjusting the deposition rate and postannealing conditions, and we find that the ELA at the interface differs by ˜0.4 eV between the Cl up and down configurations of the adsorbed ClAlPc molecules. These observations are rationalized by density functional theory (DFT) calculations based on a realistic model of the ClAlPc/Ag(111) interface, which reveal that the different orientations of the ClAlPc dipole layer lead to different charge-transfer channels between the adsorbed ClAlPc and Ag(111) substrate. Our findings provide a useful framework toward method development for ELA tuning.

  8. Theoretical evidence of charge transfer interaction between SO₂ and deep eutectic solvents formed by choline chloride and glycerol.

    Science.gov (United States)

    Li, Hongping; Chang, Yonghui; Zhu, Wenshuai; Wang, Changwei; Wang, Chao; Yin, Sheng; Zhang, Ming; Li, Huaming

    2015-11-21

    The nature of the interaction between deep eutectic solvents (DESs), formed by ChCl and glycerol, and SO2 has been systematically investigated using the M06-2X density functional combined with cluster models. Block-localized wave function energy decomposition (BLW-ED) analysis shows that the interaction between SO2 and DESs is dominated by a charge transfer interaction. After this interaction, the SO2 molecule becomes negatively charged, whereas the ChCl-glycerol molecule is positively charged, which is the result of Lewis acid-base interaction. The current result affords a theoretical proof that it is highly useful and efficient to manipulate the Lewis acidity of absorbents for SO2 capture. Moreover, hydrogen bonding as well as electrostatic interactions may also contribute to the stability of the complex. Structure analysis shows that solvent molecules will adjust their geometries to interact with SO2. In addition, the structure of SO2 is barely changed after interaction. The interaction energy between different cluster models and SO2 ranges from -6.8 to -14.4 kcal mol(-1). It is found that the interaction energy is very sensitive to the solvent structure. The moderate interaction between ChCl-glycerol and SO2 is consistent with the concept that highly efficient solvents for SO2 absorption should not only be solvable but also regenerable.

  9. Visible Light Absorption of Binuclear TiOCoII Charge-Transfer UnitAssembled in Mesoporous Silica

    Energy Technology Data Exchange (ETDEWEB)

    Han, Hongxian; Frei, Heinz

    2007-01-30

    Grafting of CoII(NCCH3)2Cl2 onto mesoporous Ti-MCM-41 silicain acetonitrile solution affords binuclear Ti-O-CoII sites on the poresurface under complete replacement of the precursor ligands byinteractions with anchored Ti centers and the silica surface. The CoIIligand field spectrum signals that the Co centers are anchored on thepore surface in tetrahedral coordination. FT-infrared action spectroscopyusing ammonia gas adsorption reveals Co-O-Si bond modes at 831 and 762cm-1. No Co oxide clusters are observed in the as-synthesized material.The bimetallic moieties feature an absorption extending from the UV intothe visible to about 600 nm which is attributed to the TiIV-O-CoII?3TiIII-O-CoIII metal-to-metal charge-transfer (MMCT) transition. Thechromophore is absent in MCM-41 containing Ti and Co centers isolatedfrom each other; this material was synthesized by grafting CoII onto aTi-MCM-41 sample with the Ti centers protected by a cyclopentadienylligand. The result indicates that the appearance of the charge-transferabsorption requires that the metal centers are linked by an oxo bridge,which is additionally supported by XANES spectroscopy. The MMCTchromophore of Ti-O-CoII units has sufficient oxidation power to serve asvisible light electron pump for driving multi-electron transfer catalystsof demanding uphill reactions such as water oxidation.

  10. A multidimensional design of charge transfer interfaces via D-A-D linking fashion for electrophysiological sensing of neurotransmitters.

    Science.gov (United States)

    Liu, He; Liu, Chaoyi; Gu, Yue; Li, Cong; Yan, Xiaoyi; Zhang, Tingting; Lu, Nannan; Zheng, Bo; Li, Yaru; Zhang, Zhiquan; Yang, Ming

    2018-01-15

    Donor-Acceptor (D-A) structure like host-guest pair serves as an organic charge-transfer (C-T) material with pregnant electrochemical and photochemical properties. Phenothiazine, a conjugated nitrogen-sulfur heterocyclic compound with broad pharmaceutical profile, is a strong electron donating system and applied in the synthesis of various classic antipsychotic drugs. In this proposal, a novel D-A molecule, 2,3-bis(4-(10H-phenothiazin-10-yl)phenyl)fumaronitrile (PTBFN), containig a diphenylfumaronitrile as the electrophilic central core and two phenothiazines as the peripheral electron donor functional groups is first designed and synthesized. Subsequently, the C-T layer based on the PTBFN polymer, poly(PTBFN), is obtained via a straightforward electrochemical method and used as an efficient electrocatalyst for dopamine (DA) detection. The logarithm of oxidation peak currents present an outstanding linear response to that of the DA concentration varying from 0.005 to 350μM with a detection limit down to 0.70nM, wherein the interferences of uric acid (UA) and ascorbic acid (AA) could be eliminated effectively. Moreover, the biosensor displays decent stability, excellent selectivity for different interfering compounds and applicability in real samples analysis. The favorable sensing performance suggests that the nontrivial D-A architecture is one of the promising bioaffinity catalysts for electrocatalysis and expected to provide wider application potential for biosensing construction and medical diagnostics. Copyright © 2017 Elsevier B.V. All rights reserved.

  11. Room temperature deintercalation of alkali metal atoms from epitaxial graphene by formation of charge-transfer complexes

    Energy Technology Data Exchange (ETDEWEB)

    Shin, H.-C.; Ahn, S. J.; Kim, H. W.; Moon, Y.; Rai, K. B. [Department of Physics, Sungkyunkwan University, Suwon 440-746 (Korea, Republic of); Woo, S. H. [College of Pharmacy, Chungnam National University, Daejeon 305–764 (Korea, Republic of); Ahn, J. R., E-mail: jrahn@skku.edu [Department of Physics, Sungkyunkwan University, Suwon 440-746 (Korea, Republic of); SAINT, Sungkyunkwan University, Suwon 440-746 (Korea, Republic of)

    2016-08-22

    Atom (or molecule) intercalations and deintercalations have been used to control the electronic properties of graphene. In general, finite energies above room temperature (RT) thermal energy are required for the intercalations and deintercalations. Here, we demonstrate that alkali metal atoms can be deintercalated from epitaxial graphene on a SiC substrate at RT, resulting in the reduction in density of states at the Fermi level. The change in density of states at the Fermi level at RT can be applied to a highly sensitive graphene sensor operating at RT. Na atoms, which were intercalated at a temperature of 80 °C, were deintercalated at a high temperature above 1000 °C when only a thermal treatment was used. In contrast to the thermal treatment, the intercalated Na atoms were deintercalated at RT when tetrafluorotetracyanoquinodimethane (F4-TCNQ) molecules were adsorbed on the surface. The RT deintercalation occurred via the formation of charge-transfer complexes between Na atoms and F4-TCNQ molecules.

  12. Demonstration of Improved Charge Transfer in Graphene/Au Nanorods Plasmonic Hybrids Stabilized by Benzyl Thiol Linkers

    Directory of Open Access Journals (Sweden)

    Giuseppe Valerio Bianco

    2016-01-01

    Full Text Available Hybrids based on graphene decorated with plasmonic gold (Au nanostructures are being investigated as possible materials combination to add to graphene functionalities of tunable plasmon resonance and enhanced absorption at selected wavelength in the visible-near-infrared region of the spectrum. Here, we report a solution drop-casting approach for fabricating stable hybrids based on chemical vapor deposition (CVD graphene and Au nanorods, which are able to activate effective charge transfer from graphene. We demonstrate that CVD graphene functionalization by benzyl thiol (BZT provides the linker to strong anchoring, via S-Au bonds, Au nanorods to graphene. Optical measurements by spectroscopic ellipsometry give evidence of the introduction of plasmon resonances at 1.85 and 2.25 eV in the Au nanorods/BZT/graphene hybrids, which enable surface enhanced Raman scattering (SERS detection. Furthermore, an effective electron transfer from graphene to Au nanorods, resulting in an enhancement of p-type doping of graphene with a consequent decrease of its sheet resistance, is probed by Raman spectroscopy and corroborated by electrical measurements.

  13. Dynamics of charge-transfer excited states relevant to photochemical energy conversion. Progress report, June 1, 1991--November 15, 1991

    Energy Technology Data Exchange (ETDEWEB)

    Lim, E.C.

    1991-11-01

    The primary objective of the research program is to gain a fundamental understanding of the factors governing the efficiency of excited-state charge transfer CT interactions between two chromophores that are brought together in close proximity, either by a very short covalent linkage or by ground-state complex formation. CT and van der Walls (vdW), interactions in covalently bonded bichromophoric compounds in condensed phase, as well as those in vdW complexes in supersonic jets, are being investigated using laser-based techniques under a variety of experimental conditions. This progress report is divided into three parts, according to the class of molecular systems and the phase (liquid vs. gas) in which the excited-state interactions are probed. The first is concerned with the excited states of bridged diaryl compounds in the condensed phase. The second involves the excited states of vdW complexes in supersonic jets. Finally, the third, is concerned with the excited states of electron donor-acceptor (EDA) systems in both the condensed phase and supersonic jets. In each of these studies, we are concerned with the interchromophore interactions ranging from weak vdW forces to strong CT forces, and the factors determining whether the interaction forces are weak or strong in related molecules.

  14. H-shaped oligothiophenes with low band gaps and amphoteric redox properties

    KAUST Repository

    Luo, Jing

    2010-12-17

    H-shaped bridged oligothiophenes HT-1 and HT-2 were synthesized by two different approaches. Different from normal oligothiophenes, HT-1 and HT-2 showed low band gaps and amphoteric redox behaviors due to intramolecular charge transfer, which is further supported by time-dependent DFT calculations. © 2010 American Chemical Society.

  15. Ligand-to-metal charge-transfer dynamics in a blue copper protein plastocyanin: a molecular dynamics study.

    Science.gov (United States)

    Ando, Koji

    2008-01-17

    Equilibrium and nonequilibrium dynamics of a blue copper protein plastocyanin in an oxidized state are studied by molecular dynamics (MD) simulation. Potential energy functions of the lowest seven electronic states, including ligand-to-metal charge-transfer (LMCT) and copper d --> d excited states, were taken from our previous work (Ando, K. J. Phys. Chem. B 2004, 108, 3940), which employed ab initio molecular orbital and density functional calculations on the active-site model. The equilibrium MD simulations in the ground state indicate that ligand motions coupled to transition from the ground state to the LMCT state are mostly represented by stretching and bending vibrations of the Cu-S(Cys) distance, Ndelta(His)-Cu-Ndelta(His) angle, and S(Cys)-Cu-[Ndelta(His)]2 trigonal pyramid structure. The nonequilibrium dynamics on the LMCT potential exhibit rapid decays in which surface crossings to the d --> d and the first excited states occur in 70-80 fs. The crossing dynamics mostly correlate with cleavage of the Cu-S(Cys) bond and the associated response in the Ndelta(His)-Cu-Ndelta(His) moiety. The average dynamics of the vertical energy gap coordinates exhibit an overdamped decay with a recurrence oscillation in 500 fs, which shows clear coherence surviving after the ensemble averaging. This oscillation stems mostly from the recoiling motion of the Ndelta(His)-Cu-Ndelta(His) part. The dynamics of the energy gaps after this coherent oscillation are randomized such that the ensemble average yields flat profiles along time, although each single trajectory exhibits fluctuations with amplitudes large enough to reach surface crossings. These indicate that the relaxation from the LMCT state first occurs via ballistic and coherent potential crossings in 70-80 and 500 fs, followed by thermally activated random transitions.

  16. Rational Design of Charge-Transfer Interactions in Halogen-Bonded Co-crystals toward Versatile Solid-State Optoelectronics.

    Science.gov (United States)

    Zhu, Weigang; Zheng, Renhui; Zhen, Yonggang; Yu, Zhenyi; Dong, Huanli; Fu, Hongbing; Shi, Qiang; Hu, Wenping

    2015-09-02

    Charge-transfer (CT) interactions between donor (D) and acceptor (A) groups, as well as CT exciton dynamics, play important roles in optoelectronic devices, such as organic solar cells, photodetectors, and light-emitting sources, which are not yet well understood. In this contribution, the self-assembly behavior, molecular stacking structure, CT interactions, density functional theory (DFT) calculations, and corresponding physicochemical properties of two similar halogen-bonded co-crystals are comprehensively investigated and compared, to construct an "assembly-structure-CT-property" relationship. Bpe-IFB wire-like crystals (where Bpe = 1,2-bis(4-pyridyl)ethylene and IFB = 1,3,5-trifluoro-2,4,6-triiodobenzene), packed in a segregated stacking form with CT ground and excited states, are measured to be quasi-one-dimensional (1D) semiconductors and show strong violet-blue photoluminescence (PL) from the lowest CT1 excitons (ΦPL = 26.1%), which can be confined and propagate oppositely along the 1D axial direction. In comparison, Bpe-F4DIB block-like crystals (F4DIB = 1,4-diiodotetrafluorobenzene), packed in a mixed stacking form without CT interactions, are determined to be insulators and exhibit unique white light emission and two-dimensional optical waveguide property. Surprisingly, it seems that the intrinsic spectroscopic states of Bpe and F4DIB do not change after co-crystallization, which is also confirmed by theoretical calculations, thus offering a new design principle for white light emitting materials. More importantly, we show that the CT interactions in co-crystals are related to their molecular packing and can be triggered or suppressed by crystal engineering, which eventually leads to distinct optoelectronic properties. These results help us to rationally control the CT interactions in organic D-A systems by tuning the molecular stacking, toward the development of a fantastic "optoelectronic world".

  17. Monopyrrolotetrathiafulvalene-succinamide conjugates and their TCNQ charge transfer complex based supramolecular gels with multiple stimulus responsiveness.

    Science.gov (United States)

    Liu, Yucun; Zheng, Ningjuan; Chen, Tie; Jin, Longyi; Yin, Bingzhu

    2014-09-21

    A series of monopyrrolotetrathiafulvalene-succinamide conjugates and their 7,7,8,8-tetracyano-p-quinodimethane (TCNQ) charge transfer (CT) complexes have been synthesized and investigated as new low-molecular mass organogelators. The gelation capability of these conjugates is highly dependent on the length of the alkyl chain of the terminal amide. Thus, only the short alkyl chain derivatives and could efficiently gelate cyclohexane and methylcyclohexane (MCH). Surprisingly, these gelators react with TCNQ to form stable CT complex gels in both cyclohexane and MCH. The FE-SEM images of the native gels reveal the characteristic gelation morphologies of microporous or fibrous structures, whereas the morphologies of CT complex gels show the fibrillar and globular aggregates in cyclohexane and MCH, respectively. SAXS study of the native gel and the CT complex gel of in cyclohexane suggests that the molecules maintain rectangular and hexagonal columnar molecular packing models in the gel phase, respectively. The native gels undergo a reversible gel-sol phase transition upon exposure to external stimuli, such as temperature and chemical oxidation/reduction. Alternatively, the corresponding CT complex gels exhibit a complicated response to external stimuli. Chemical oxidation by I2 results in the destruction of the gel state. However, neither Fe(3+) nor Cu(2+) can induce the collapse of the gel phase. Interestingly, all the gels show an irreversible gel-sol transition on successively triggering with trifluoroacetic acid and triethylamine. The reformation of the gel from the sol state is achieved just by the addition of water, showing the phase-selective gelation of the solvents from their mixtures with water.

  18. High throughput microwell spectrophotometric assay for olmesartan medoxomil in tablets based on its charge-transfer reaction with DDQ

    Directory of Open Access Journals (Sweden)

    Darwish Ibrahim A.

    2014-03-01

    Full Text Available The study describes the development and validation of a new microwell-based spectrophotometric assay for determination of olmesartan medoxomil (OLM in tablets. The formation of a colored charge-transfer (CT complex between OLM as an n-electron donor and 2,3-dichloro- -5,6-dicyano-1,4-benzoquinone (DDQ as a p-electron acceptor was investigated, and employed as the basis for the development of the new assay. The proposed assay was conducted in 96-microwell plates. The absorbance of the colored-CT complex was measured at 460 nm with a microplate reader. Optimum conditions of the reaction and the analytical procedures of the assay were established. Under the optimum conditions, a linear relationship with a good correlation coefficient was found between the absorbance and the concentration of OLM in the range of 2-200 μg per well. The limits of detection and quantitation were 0.53 and 1.61 μg per well, respectively. No interference was observed from the excipients present in OLM tablets or from hydrochlorothiazide and amlodipine besylate that were co-formulated with OLM in some of its formulations. The assay was successfully applied to the analysis of OLM in tablets with good accuracy and precision. The assay described herein has a great practical value in the routine analysis of OLM in quality control laboratories, since it has a high throughput property and consumes low volumes of organic solvent. It thus offers a reduction in the exposure of analysts to the toxic effects of organic solvents, as well as a reduction in the cost of analysis.

  19. Some Observations on the Development of Superior Photocatalytic Systems for Application to Water Purification by the “Adsorb and Shuttle” or the Interphase Charge Transfer Mechanisms

    Directory of Open Access Journals (Sweden)

    Cooper Langford

    2014-11-01

    Full Text Available Adsorb and shuttle (A/S and interfacial charge transfer are the two major strategies for overcoming recombination in photocatalysis in this era of nanoparticle composites. Their relationships are considered here. A review of key literature is accompanied by a presentation of three new experiments within the overall aim of assessing the relation of these strategies. The cases presented include: A/S by a high silica zeolite/TiO2 composite, charge transfer (CT between phases in a TiO2/WO3 composite and both A/S and CT by composites of TiO2 with powered activated carbon (AC and single-walled carbon nanotubes (SWCNT. The opportunities presented by the two strategies for moving toward photocatalysts that could support applications for the removal of contaminants from drinking water or that lead to a practical adsorbent for organics that could be regenerated photocatalytically link this discussion to ongoing research here.

  20. Charge transfer mechanism for the formation of metallic states at the KTaO3/SrTiO3 interface

    KAUST Repository

    Nazir, Safdar

    2011-03-29

    The electronic and optical properties of the KTaO3/SrTiO3 heterointerface are analyzed by the full-potential linearized augmented plane-wave approach of density functional theory. Optimization of the atomic positions points at subordinate changes in the crystal structure and chemical bonding near the interface, which is due to a minimal lattice mismatch. The creation of metallic interface states thus is not affected by structural relaxation but can be explained by charge transfer between transition metal and oxygen atoms. It is to be expected that a charge transfer is likewise important for related interfaces such as LaAlO3/SrTiO3. The KTaO3/SrTiO3 system is ideal for disentangling the complex behavior of metallic interface states, since almost no structural relaxation takes place.

  1. Charge-Transfer Complexes and Photochemistry of Ozone with Ferrocene and n-Butylferrocene: A UV-vis Matrix-Isolation Study.

    Science.gov (United States)

    Pinelo, Laura F; Kugel, Roger W; Ault, Bruce S

    2015-10-15

    The reactions of ozone with ferrocene (cp2Fe) and with n-butylferrocene (n-butyl cp2Fe) were studied using matrix isolation, UV-vis spectroscopy, and theoretical calculations. The codeposition of cp2Fe with O3 and of n-butyl cp2Fe with O3 into an argon matrix led to the production of 1:1 charge-transfer complexes with absorptions at 765 and 815 nm, respectively. These absorptions contribute to the green matrix color observed upon initial deposition. The charge-transfer complexes underwent photochemical reactions upon irradiation with red light (λ ≥ 600 nm). Theoretical UV-vis spectra of the charge-transfer complexes and photochemical products were calculated using TD-DFT at the B3LYP/6-311G++(d,2p) level of theory. The calculated UV-vis spectra were in good agreement with the experimental results. MO analysis of these long-wavelength transitions showed them to be n→ π* on the ozone subunit in the complex and indicated that the formation of the charge-transfer complex between ozone and cp2Fe or n-butyl cp2Fe affects how readily the π* orbital on O3 is populated when red light (λ ≥ 600 nm) is absorbed. 1:1 complexes of cp2Fe and n-butyl cp2Fe with O2 were also observed experimentally and calculated theoretically. These results support and enhance previous infrared studies of the mechanism of photooxidation of ferrocene by ozone, a reaction that has considerable significance for the formation of iron oxide thin films for a range of applications.

  2. Comparison of the Impact of Zinc Vacancies on Charge Separation and Charge Transfer at ZnO/Sexithienyl and ZnO/Fullerene Interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Li, Hong [School of Chemistry and Biochemistry and Center for Organic Photonics and Electronics, Georgia Institute of Technology, Atlanta GA 30332-0400 USA; Bredas, Jean-Luc [Solar and Photovoltaics Engineering Research Center, Physical Science and Engineering Division, King Abdullah University of Science and Technology-KAUST, Thuwal 23955-6900 Kingdom of Saudi Arabia

    2015-11-09

    The impact of surface zinc vacancies on charge transfer and charge separation at donor/ZnO and acceptor/ZnO interfaces is identified via density functional theory calculations. The results show their effect to be related to the stronger internal electric field present near these vacancies. Thus, such surface defects can have a significant negative impact on the performance of hybrid solar cells using ZnO as electron acceptors.

  3. Challenging Adiabatic Time-dependent Density Functional Theory with a Hubbard Dimer: The Case of Time-Resolved Long-Range Charge Transfer

    CERN Document Server

    Fuks, Johanna I

    2014-01-01

    We explore an asymmetric two-fermion Hubbard dimer to test the accuracy of the adiabatic approximation of time-dependent density functional theory in modelling time-resolved charge transfer. We show that the model shares essential features of a ground state long-range molecule in real-space, and by applying a resonant field we show that the model also reproduces essential traits of the CT dynamics. The simplicity of the model allows us to propagate with an "adiabatically-exact" approximation, i.e. one that uses the exact ground-state exchange-correlation functional, and compare with the exact propagation. This allows us to study the impact of the time-dependent charge-transfer step feature in the exact correlation potential of real molecules on the resulting dynamics. Tuning the parameters of the dimer allows a study both of charge-transfer between open-shell fragments and between closed-shell fragments. We find that the adiabatically-exact functional is unable to properly transfer charge, even in situations ...

  4. Single-molecule conductance of a chemically modified, π-extended tetrathiafulvalene and its charge-transfer complex with F4TCNQ

    Directory of Open Access Journals (Sweden)

    Raúl García

    2015-06-01

    Full Text Available We describe the synthesis and single-molecule electrical transport properties of a molecular wire containing a π-extended tetrathiafulvalene (exTTF group and its charge-transfer complex with F4TCNQ. We form single-molecule junctions using the in situ break junction technique using a homebuilt scanning tunneling microscope with a range of conductance between 10 G0 down to 10−7 G0. Within this range we do not observe a clear conductance signature of the neutral parent molecule, suggesting either that its conductance is too low or that it does not form a stable junction. Conversely, we do find a clear conductance signature in the experiments carried out on the charge-transfer complex. Due to the fact we expected this species to have a higher conductance than the neutral molecule, we believe this supports the idea that the conductance of the neutral molecule is very low, below our measurement sensitivity. This idea is further supported by theoretical calculations. To the best of our knowledge, these are the first reported single-molecule conductance measurements on a molecular charge-transfer species.

  5. Electron-lattice interactions strongly renormalize the charge-transfer energy in the spin-chain cuprate Li2CuO2.

    Science.gov (United States)

    Johnston, Steve; Monney, Claude; Bisogni, Valentina; Zhou, Ke-Jin; Kraus, Roberto; Behr, Günter; Strocov, Vladimir N; Málek, Jiři; Drechsler, Stefan-Ludwig; Geck, Jochen; Schmitt, Thorsten; van den Brink, Jeroen

    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 Li2CuO2, where 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 Li2CuO2.

  6. Enhancement in charge transfer by non-ligand exchange process for colloidal hybrid organic(MEH-PPV):inorganic(CdSe) nanocomposites

    Science.gov (United States)

    Mehta, Aarti; Sharma, Shailesh N.; Singh, V. N.; Srivastva, A. K.; Chand, S.

    2012-10-01

    In this work, we demonstrate the effect of surface modification of as-synthesized oleylamine-capped spherical CdSe QDs of size (5-7 nm). The as-prepared CdSe QDs are highly luminescent, monodispersive and exhibit energy transfer effects upon their dispersion in MEH-PPV polymer matrix. However, repetitive washing of CdSe QDs upon suitable chemical treatment leads to enhancement in charge transfer process as observed in their corresponding MEH-PPV: CdSe nanocomposites. Here, no evidence of agglomeration effects and surface states were found. This enhancement in charge transfer is mainly due to the partial removal of oleylamine capping ligand, which acts as a hindrance in the interaction between polymer and CdSe QDs. The importance of this study is that as-synthesized CdSe QDs show effective energy transfer whereas after chemical treatment, it shows enhanced charge transfer mechanism which makes their corresponding nanocomposites useful for different applications in organic electronic devices such as efficient electroluminescent (OLED) and photovoltaic (OPV) devices respectively.

  7. Increased charge transfer of PVDF-HFP based electrolyte by addition of graphite nanofiber and its application in dye-sensitized solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Xing Guan; Jin, En Mei; Gu, Hal-Bon, E-mail: hbgu@chonnam.ac.kr

    2013-12-15

    The PEO and PVDF-HFP mixtures were used as polymer electrolytes in solid-state dye-sensitized solar cells (DSSCs). Correlation between the ionic conductivity and cell performance by varying the composition of polymer electrolytes was investigated to elucidate the importance of the ionic conductivity in determining the charge transfer and energy conversion efficiency of solid-state DSSCs. In this work, for increasing the ionic conductivity and charge transfer, GNF was added to the polymer electrolyte. The ionic conductivity of polymer electrolyte containing GNF (0.005 g) is 8.67 × 10{sup −4} S cm{sup −1} and pristine polymer electrolyte is 3.81 × 10{sup −4} S cm{sup −1}. The charge transfer of GNF (0.005 g) added DSSCs is faster than the other samples, the electron transport time is 1.53 ms and electron life time is 27.20 ms. The increase of current density with the polymer electrolyte containing GNF (0.005 g) can be possibly attributed to the direct contact between dye/TiO{sub 2} and I{sup −}/I{sub 3}{sup −} that will improve the charge transportation. The highest energy conversion efficiency of 4.60% is obtained for polymer electrolyte containing GNF (0.005 g)

  8. Synthesis of charge transfer complex of chloranilic acid as acceptor with p-nitroaniline as donor: Crystallographic, UV-visible spectrophotometric and antimicrobial studies

    Science.gov (United States)

    Zulkarnain; Khan, Ishaat M.; Ahmad, Afaq; Miyan, Lal; Ahmad, Musheer; Azizc, Nafe

    2017-08-01

    The charge transfer interaction between p-nitroaniline (PNA) and chloranilic (CAA) acid was studied spectrophotometrically in methanol at different temperatures within the range 298-328 K. This experimental work explores the nature of charge-transfer interactions that play a significant role in chemistry and biology. Structure of synthesized charge transfer (CT) complex was investigated by different technique such as X-ray crystallography, FTIR, 1HNMR, UV-visible spectroscopy, XRD and TGA-DTA, which indicates the presence of N+sbnd Hrbd2bd O- bond between donor and acceptor moieties. Spectrophotometric studies of CT complexes were carried out in methanol at different temperatures to estimate thermodynamic parameters such as formation constant (KCT), molar absorptivity (εCT), free energy change (ΔG), enthalpy change (ΔH), resonance energy (RN), oscillator strength (f), transition dipole moment (μEN) and interaction energy (ECT) were also calculated. The effect of temperatures on all the parameters was studied in methanol. 1:1 stoichiometric of CT-complex was ascertained by Benesi-Hildebrand plots giving straight line, which are good agreement with other analysis. Synthesized CT complex was screened for its antimicrobial activity such as antibacterial activity against two gram-positive bacteria, Staphylococcus aureus and bacillus subtilis and two gram negative bacteria Escherichia coli and pseudomonas aeruginosa, and antifungal activity against fungi Fusarium oxysporum, and Aspergillus flavus.

  9. Mathematical improvement of the Hopfield model for feasible solutions to the traveling salesman problem by a synapse dynamical system.

    Science.gov (United States)

    Takahashi, Y

    1998-01-01

    It is well known that the Hopfield Model (HM) for neural networks to solve the Traveling Salesman Problem (TSP) suffers from three major drawbacks. (1) It can converge on nonoptimal locally minimum solutions. (2) It can converge on infeasible solutions. (3) Results are very sensitive to the careful tuning of its parameters. A number of methods have been proposed to overcome (a) well. In contrast, work on (b) and (c) has not been sufficient; techniques have not been generalized to more general optimization problems. Thus this paper mathematically resolves (b) and (c) to such an extent that the resolution can be applied to solving with some general network continuous optimization problems including the Hopfield version of the TSP. It first constructs an Extended HM (E-HM) that overcomes both (b) and (c). Fundamental techniques of the E-HM lie in the addition of a synapse dynamical system cooperated with the current HM unit dynamical system. It is this synapse dynamical system that makes the TSP constraint hold at any final states for whatever choices of the IIM parameters and an initial state. The paper then generalizes the E-HM further to a network that can solve a class of continuous optimization problems with a constraint equation where both of the objective function and the constraint function are nonnegative and continuously differentiable.

  10. On the nature of stabilization in weak, medium, and strong charge-transfer complexes: CCSD(T)/CBS and SAPT calculations.

    Science.gov (United States)

    Karthikeyan, S; Sedlak, Robert; Hobza, Pavel

    2011-09-01

    Weak, medium, and strong charge-transfer (CT) complexes containing various electron donors (C(2)H(4), C(2)H(2), NH(3), NMe(3), HCN, H(2)O) and acceptors (F(2), Cl(2), BH(3), SO(2)) were investigated at the CCSD(T)/complete basis set (CBS) limit. The nature of the stabilization for these CT complexes was evaluated on the basis of perturbative NBO calculations and DFT-SAPT/CBS calculations. The structure of all of the complexes was determined by the counterpoise-corrected gradient optimization performed at the MP2/cc-pVTZ level, and most of complexes possess a linear-like contact structure. The total stabilization energies lie between 1 and 55 kcal/mol and the strongest complexes contain BH(3) as an electron acceptor. When ordering the electron donors and electron acceptors on the basis of these energies, we obtain the same order as that based on the perturbative E2 charge-transfer energies, which provides evidence that the charge-transfer term is the dominant energy contribution. The CCSD(T) correction term, defined as the difference between the CCSD(T) and MP2 interaction energies, is mostly small, which allows the investigation of the CT complexes of this type at the "cheap" MP2/CBS level. In the case of weak and medium CT complexes (with stabilization energy smaller than about 15 kcal/mol), the dominant stabilization originates in the electrostatic term; the dispersion as well as induction and δ(HF) terms covering the CT energy contribution are, however, important as well. For strong CT complexes, induction energy is the second (after electrostatic) most important energy term. The role of the induction and δ(HF) terms is unique and characteristic for CT complexes. For all CT complexes, the CCSD(T)/CBS and DFT-SAPT/CBS stabilization energies are comparable, and surprisingly, it is true even for very strong CT complexes with stabilization energy close to 50 kcal/mol characteristic by substantial charge transfer (more than 0.3 e). It is thus possible to conclude

  11. Multiple Electron Charge Transfer Chemistries for Electrochemical Energy Storage Systems: The Metal Boride and Metal Air Battery

    Science.gov (United States)

    Stuart, Jessica F.

    The primary focus of this work has been to develop high-energy capacity batteries capable of undergoing multiple electron charge transfer redox reactions to address the growing demand for improved electrical energy storage systems that can be applied to a range of applications. As the levels of carbon dioxide (CO2) increase in the Earth's atmosphere, the effects on climate change become increasingly apparent. According to the Energy Information Administration (EIA), the U.S. electric power sector is responsible for the release of 2,039 million metric tons of CO2 annually, equating to 39% of total U.S. energy-related CO2 emissions. Both nationally and abroad, there are numerous issues associated with the generation and use of electricity aside from the overwhelming dependence on fossil fuels and the subsequent carbon emissions, including reliability of the grid and the utilization of renewable energies. Renewable energy makes up a relatively small portion of total energy contributions worldwide, accounting for only 13% of the 3,955 billion kilowatt-hours of electricity produced each year, as reported by the EIA. As the demand to reduce our dependence on fossils fuels and transition to renewable energy sources increases, cost effective large-scale electrical energy storage must be established for renewable energy to become a sustainable option for the future. A high capacity energy storage system capable of leveling the intermittent nature of energy sources such as solar, wind, and water into the electric grid and provide electricity at times of high demand will facilitate this transition. In 2008, the Licht Group presented the highest volumetric energy capacity battery, the vanadium diboride (VB2) air battery, exceedingly proficient in transferring eleven electrons per molecule. This body of work focuses on new developments to this early battery such as fundamentally understanding the net discharge mechanism of the system, evaluation of the properties and

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-11-12

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

  13. Statistical Mechanics of Coherent Ising Machine — The Case of Ferromagnetic and Finite-Loading Hopfield Models —

    Science.gov (United States)

    Aonishi, Toru; Mimura, Kazushi; Utsunomiya, Shoko; Okada, Masato; Yamamoto, Yoshihisa

    2017-10-01

    The coherent Ising machine (CIM) has attracted attention as one of the most effective Ising computing architectures for solving large scale optimization problems because of its scalability and high-speed computational ability. However, it is difficult to implement the Ising computation in the CIM because the theories and techniques of classical thermodynamic equilibrium Ising spin systems cannot be directly applied to the CIM. This means we have to adapt these theories and techniques to the CIM. Here we focus on a ferromagnetic model and a finite loading Hopfield model, which are canonical models sharing a common mathematical structure with almost all other Ising models. We derive macroscopic equations to capture nonequilibrium phase transitions in these models. The statistical mechanical methods developed here constitute a basis for constructing evaluation methods for other Ising computation models.

  14. Modeling and Experimental Demonstration of a Hopfield Network Analog-to-Digital Converter with Hybrid CMOS/Memristor Circuits.

    Science.gov (United States)

    Guo, Xinjie; Merrikh-Bayat, Farnood; Gao, Ligang; Hoskins, Brian D; Alibart, Fabien; Linares-Barranco, Bernabe; Theogarajan, Luke; Teuscher, Christof; Strukov, Dmitri B

    2015-01-01

    The purpose of this work was to demonstrate the feasibility of building recurrent artificial neural networks with hybrid complementary metal oxide semiconductor (CMOS)/memristor circuits. To do so, we modeled a Hopfield network implementing an analog-to-digital converter (ADC) with up to 8 bits of precision. Major shortcomings affecting the ADC's precision, such as the non-ideal behavior of CMOS circuitry and the specific limitations of memristors, were investigated and an effective solution was proposed, capitalizing on the in-field programmability of memristors. The theoretical work was validated experimentally by demonstrating the successful operation of a 4-bit ADC circuit implemented with discrete Pt/TiO2- x /Pt memristors and CMOS integrated circuit components.

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

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-05-28

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

  17. Shape similarity of charge-transfer (CT) excitation energy curves in a series of donor-acceptor complexes and its description with a transferable energy of CT orbital

    Science.gov (United States)

    Gritsenko, O. V.

    2017-08-01

    A simple nature of charge-transfer (CT) in the prototype complexes Dp -F2 (Dp =NH3 , H2O) manifests itself in a very close shape of their CT excitation energy curves ωCT (R) along the donor-acceptor separation R. It affords a simple orbital description in terms of the CT orbitals (CTOs) obtained with a transformation of the virtual orbitals of the standard local density approximation (LDA). The transferable energy of the relevant CTO as a function of R closely approximates the common shape of ωCT (R) , while the height of the individual curve is determined with the ionization potential of Dp .

  18. Combined Inter- and Intramolecular Charge-Transfer Processes for Highly Efficient Fluorescent Organic Light-Emitting Diodes with Reduced Triplet Exciton Quenching.

    Science.gov (United States)

    Moon, Chang-Ki; Suzuki, Katsuaki; Shizu, Katsuyuki; Adachi, Chihaya; Kaji, Hironori; Kim, Jang-Joo

    2017-05-01

    Inter- and intramolecular charge-transfer processes are combined using an exciplex-forming host and a thermally activated delayed fluorescent dopant, for fabricating efficient fluorescent organic light-emitting diodes along with the reduced efficiency roll-off at high current densities. Extra conversion on the host from triplet exciplexes to singlet exciplexes followed by energy transfer to the dopant reduces population of triplet excitons on dopant molecules, thereby reducing the triplet exciton annihilations at high current densities. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Highly efficient ZnO/Au Schottky barrier dye-sensitized solar cells: Role of gold nanoparticles on the charge-transfer process

    OpenAIRE

    Tanujjal Bora; Htet H. Kyaw; Soumik Sarkar; Samir K. Pal; Joydeep Dutta

    2011-01-01

    Zinc oxide (ZnO) nanorods decorated with gold (Au) nanoparticles have been synthesized and used to fabricate dye-sensitized solar cells (DSSC). The picosecond-resolved, time-correlated single-photon-count (TCSPC) spectroscopy technique was used to explore the charge-transfer mechanism in the ZnO/Au-nanocomposite DSSC. Due to the formation of the Schottky barrier at the ZnO/Au interface and the higher optical absorptions of the ZnO/Au photoelectrodes arising from the surface plasmon absorption...

  20. D/sup -/ production by multiple charge-transfer collisions of low-energy D ions and atoms in cesium vapor

    Energy Technology Data Exchange (ETDEWEB)

    Hooper, E.B. Jr.; Willmann, P.A.; Schlachter, A.S.

    1978-01-22

    The production of D/sup -/ by multiple charge-transfer collisions of a D/sup +/ beam in a cesium-vapor target is considered for D/sup +/ energies above 300 eV. The cross sections relevant to D/sup -/ formation are obtained by a least-squares fit of three-charge-state differential equations to experimental yield curves. Implications for production of intense negative-ion beams are discussed, and speculations are made about extrapolation to lower engeries.

  1. Spectroscopic and thermodynamic study of charge transfer complex formation between cloxacillin sodium and riboflavin in aqueous ethanol media of varying composition

    Science.gov (United States)

    Roy, Dalim Kumar; Saha, Avijit; Mukherjee, Asok K.

    2006-03-01

    Cloxacillin sodium has been shown to form a charge transfer complex of 2:1 stoichiometry with riboflavin (Vitamin B 2) in aqueous ethanol medium. The enthalpy and entropy of formation of this complex have been determined by estimating the formation constant spectrophotometrically at five different temperatures in pure water medium. Pronounced effect of dielectric constant of the medium on the magnitude of K has been observed by determining K in aqueous ethanol mixtures of varying composition. This has been rationalized in terms of ionic dissociation of the cloxacillin sodium (D -Na +), hydrolysis of the anion D - and complexation of the free acid, DH with riboflavin.

  2. Organic Metals. Mono- and 2,5-Di-substituted 7,7,8,8-Tetracyano-p-quinodimethanes and Conductivities of their Charge-Transfer Complexes

    DEFF Research Database (Denmark)

    Andersen, Jan Rud; Jørgensen, Ole

    1979-01-01

    procedures utilizing multiple recrystallizations from CH3CN, followed by gradient sublimation, yield high quality materials for the preparation of conducting organic charge-transfer complexes based on these acceptors. Field-ionization mass spectrometry was found to be a convenient means of monitoring......The syntheses of the electron acceptors methyl-7,7,8,8-tetracyano-p-quinodimethane (MTCNQ)(10), 2,5-dimethyl-7,7,8,8-tetracyano-p-quinodimethane (DMTCNQ)(5a), and 2,5-diethyl-7,7,8,8-tetracyano-p-quinodimethane (DETCNQ)(5b) from commercially available starting materials are described. Purification...

  3. Room temperature insulating ferromagnetism induced by charge transfer in ultrathin (110) La0.7Sr0.3MnO3 films

    Science.gov (United States)

    Quan, Zhiyong; Wu, Biao; Zhang, Fei; Zhou, Guowei; Zang, Julu; Xu, Xiaohong

    2017-02-01

    The achievement of high temperature ferromagnetism in perovskite manganites has proved both fundamentally and technologically important for spintronics devices. However, high operating temperatures have not been achieved due to the depression of the Curie temperature and the rapid spin filtering efficiency loss, which are the main obstacles for practical applications. Here, we report unexpected room temperature insulating ferromagnetism in ultrathin (110) oriented La0.7Sr0.3MnO3 (LSMO) films. The relationships between room temperature ferromagnetism, charge transfer, and orbital occupancy are investigated, with X-ray absorption spectroscopy (XAS) and X-ray linear dichroism (XLD) measurements. Our results suggest that the room temperature insulating ferromagnetism is originated from super-exchange interaction between Mn2+ and Mn3+. The formation of Mn2+ ions is related to the charge transfer induced by oxygen vacancies. Moreover, a preferential orbital occupancy of eg(3z2-r2) in Mn3+ ions is crucial to the in-plane super-exchange coupling in ultrathin (110) LSMO films, resulting in insulating ferromagnetic behavior. This work may lead to the development of barrier materials in spin filter tunnel junctions and understanding of ferromagnetic coupling in insulating perovskite films.

  4. Highly efficient ZnO/Au Schottky barrier dye-sensitized solar cells: Role of gold nanoparticles on the charge-transfer process

    Science.gov (United States)

    Bora, Tanujjal; Kyaw, Htet H; Sarkar, Soumik; Pal, Samir K

    2011-01-01

    Summary Zinc oxide (ZnO) nanorods decorated with gold (Au) nanoparticles have been synthesized and used to fabricate dye-sensitized solar cells (DSSC). The picosecond-resolved, time-correlated single-photon-count (TCSPC) spectroscopy technique was used to explore the charge-transfer mechanism in the ZnO/Au-nanocomposite DSSC. Due to the formation of the Schottky barrier at the ZnO/Au interface and the higher optical absorptions of the ZnO/Au photoelectrodes arising from the surface plasmon absorption of the Au nanoparticles, enhanced power-conversion efficiency (PCE) of 6.49% for small-area (0.1 cm2) ZnO/Au-nanocomposite DSSC was achieved compared to the 5.34% efficiency of the bare ZnO nanorod DSSC. The TCSPC studies revealed similar dynamics for the charge transfer from dye molecules to ZnO both in the presence and absence of Au nanoparticles. A slower fluorescence decay associated with the electron recombination process, observed in the presence of Au nanoparticles, confirmed the blocking of the electron transfer from ZnO back to the dye or electrolyte by the Schottky barrier formed at the ZnO/Au interface. For large area DSSC (1 cm2), ~130% enhancement in PCE (from 0.50% to 1.16%) was achieved after incorporation of the Au nanoparticles into the ZnO nanorods. PMID:22043457

  5. Highly efficient ZnO/Au Schottky barrier dye-sensitized solar cells: Role of gold nanoparticles on the charge-transfer process

    Directory of Open Access Journals (Sweden)

    Tanujjal Bora

    2011-10-01

    Full Text Available Zinc oxide (ZnO nanorods decorated with gold (Au nanoparticles have been synthesized and used to fabricate dye-sensitized solar cells (DSSC. The picosecond-resolved, time-correlated single-photon-count (TCSPC spectroscopy technique was used to explore the charge-transfer mechanism in the ZnO/Au-nanocomposite DSSC. Due to the formation of the Schottky barrier at the ZnO/Au interface and the higher optical absorptions of the ZnO/Au photoelectrodes arising from the surface plasmon absorption of the Au nanoparticles, enhanced power-conversion efficiency (PCE of 6.49% for small-area (0.1 cm2 ZnO/Au-nanocomposite DSSC was achieved compared to the 5.34% efficiency of the bare ZnO nanorod DSSC. The TCSPC studies revealed similar dynamics for the charge transfer from dye molecules to ZnO both in the presence and absence of Au nanoparticles. A slower fluorescence decay associated with the electron recombination process, observed in the presence of Au nanoparticles, confirmed the blocking of the electron transfer from ZnO back to the dye or electrolyte by the Schottky barrier formed at the ZnO/Au interface. For large area DSSC (1 cm2, ~130% enhancement in PCE (from 0.50% to 1.16% was achieved after incorporation of the Au nanoparticles into the ZnO nanorods.

  6. Synthesis, spectral behaviour and photophysics of donor-acceptor kind of chalcones: Excited state intramolecular charge transfer and fluorescence quenching studies

    Science.gov (United States)

    Pannipara, Mehboobali; Asiri, Abdullah M.; Alamry, Khalid A.; Arshad, Muhammad N.; El-Daly, Samy A.

    2015-02-01

    The spectral and photophysical properties of two chalcones containing electron donating and accepting groups with intramolecular charge transfer characteristics were synthesized and characterized by 1H NMR, 13C NMR and X-ray crystallography. Both compounds show very strong solvent polarity dependent changes in their photophysical characteristics, namely, remarkable red shift in the emission spectra with increasing solvent polarity, large change in Stokes shift, significant reduction in the fluorescence quantum yield; indicating that the fluorescence states of these compounds are of intramolecular charge transfer (ICT) character. The solvent effect on the photophysical parameters such as singlet absorption, molar absorptivity, oscillator strength, dipole moment, fluorescence spectra, and fluorescence quantum yield of both compounds have been investigated comprehensively. For both dyes, Lippert-Mataga and Reichardt's correlations were used to estimate the difference between the excited and ground state dipole moments (Δμ). The interactions of dyes with colloidal silver nanoparticles (Ag NPs) were also studied in ethanol using steady state fluorescence quenching measurements. The fluorescence quenching data reveal that dynamic quenching and energy transfer play a major role in the fluorescence quenching of dyes by Ag NPs.

  7. Anion-cation charge-transfer properties and spectral studies of [M(phen)3][Cd4(SPh)10] (M = Ru, Fe, and Ni).

    Science.gov (United States)

    Jiang, Jian-Bing; Bian, Guo-Qing; Zhang, Ya-Ping; Luo, Wen; Zhu, Qin-Yu; Dai, Jie

    2011-10-07

    Three anion-cation compounds 1-3 with formula [M(phen)(3)][Cd(4)(SPh)(10)]·Sol (M = Ru(2+), Fe(2+), and Ni(2+), Sol = MeCN and H(2)O) have been synthesized and characterized by single-crystal analysis. Both the cations and anion are well-known ions, but the properties of the co-assembled compounds are interesting. Molecular structures and charge-transfer between the cations and anions in crystal and even in solution are discussed. These compounds are isomorphous and short inter-ion interactions are found in these crystals, such as π···π stacking and C-H···π contacts. Both spectroscopic and theoretical calculated results indicate that there is anion-cation charge-transfer (ACCT) between the Ru-phen complex dye and the Cd-SPh cluster, which plays an important role in their photophysical properties. The intensity of the fluorescent emission of the [Ru(phen)(3)](2+) is enhanced when the cation interacts with the [Cd(4)(SPh)(10)](2-) anion. The mechanism for the enhancement of photoluminescence has been proposed.

  8. A heteroleptic push-pull substituted iron(II) bis(tridentate) complex with low-energy charge-transfer states.

    Science.gov (United States)

    Mengel, Andreas K C; Förster, Christoph; Breivogel, Aaron; Mack, Katharina; Ochsmann, Julian R; Laquai, Frédéric; Ksenofontov, Vadim; Heinze, Katja

    2015-01-07

    A heteroleptic iron(II) complex [Fe(dcpp)(ddpd)](2+) with a strongly electron-withdrawing ligand (dcpp, 2,6-bis(2-carboxypyridyl)pyridine) and a strongly electron-donating tridentate tripyridine ligand (ddpd, N,N'-dimethyl-N,N'-dipyridine-2-yl-pyridine-2,6-diamine) is reported. Both ligands form six-membered chelate rings with the iron center, inducing a strong ligand field. This results in a high-energy, high-spin state ((5) T2 , (t2g )(4) (eg *)(2) ) and a low-spin ground state ((1) A1 , (t2g )(6) (eg *)(0) ). The intermediate triplet spin state ((3) T1 , (t2g )(5) (eg *)(1) ) is suggested to be between these states on the basis of the rapid dynamics after photoexcitation. The low-energy π(*) orbitals of dcpp allow low-energy MLCT absorption plus additional low-energy LL'CT absorptions from ddpd to dcpp. The directional charge-transfer character is probed by electrochemical and optical analyses, Mößbauer spectroscopy, and EPR spectroscopy of the adjacent redox states [Fe(dcpp)(ddpd)](3+) and [Fe(dcpp)(ddpd)](+) , augmented by density functional calculations. The combined effect of push-pull substitution and the strong ligand field paves the way for long-lived charge-transfer states in iron(II) complexes. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Charge Transfer Enhancement in the D-π-A Type Porphyrin Dyes: A Density Functional Theory (DFT and Time-Dependent Density Functional Theory (TD-DFT Study

    Directory of Open Access Journals (Sweden)

    Guo-Jun Kang

    2016-11-01

    Full Text Available The electronic geometries and optical properties of two D-π-A type zinc porphyrin dyes (NCH3-YD2 and TPhe-YD were systematically investigated by density functional theory (DFT and time-dependent density functional theory (TD-DFT to reveal the origin of significantly altered charge transfer enhancement by changing the electron donor of the famous porphyrin-based sensitizer YD2-o-C8. The molecular geometries and photophysical properties of dyes before and after binding to the TiO2 cluster were fully investigated. From the analyses of natural bond orbital (NBO, extended charge decomposition analysis (ECDA, and electron density variations (Δρ between the excited state and ground state, it was found that the introduction of N(CH32 and 1,1,2-triphenylethene groups enhanced the intramolecular charge-transfer (ICT character compared to YD2-o-C8. The absorption wavelength and transition possess character were significantly influenced by N(CH32 and 1,1,2-triphenylethene groups. NCH3-YD2 with N(CH32 groups in the donor part is an effective way to improve the interactions between the dyes and TiO2 surface, light having efficiency (LHE, and free energy change (ΔGinject, which is expected to be an efficient dye for use in dye-sensitized solar cells (DSSCs.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-01-01

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

  11. Charge-transfer excitations in low-gap systems under the influence of solvation and conformational disorder: Exploring range-separation tuning

    Science.gov (United States)

    de Queiroz, Thiago B.; Kümmel, Stephan

    2014-08-01

    Charge transfer excitations play a prominent role in the fields of molecular electronics and light harvesting. At the same time they have developed a reputation for being hard to predict with time-dependent density functional theory, which is the otherwise predominant method for calculating molecular structure and excitations. Recently, it has been demonstrated that range-separated hybrid functionals, in particular with an "optimally tuned" range separation parameter, describe charge-transfer excitations reliably for different molecules. Many of these studies focused on molecules in vacuum. Here we investigate the influence of solvation on the electronic excitations of thiophene oligomers, i.e., paradigm low gap systems. We take into account bulk solvation using a continuum solvation model and geometrical distortions from molecular dynamics. From our study, three main findings emerge. First, geometrical distortions increase absorption energies by about 0.5 eV for the longer thiophene oligomers. Second, combining optimal tuning of the range separation parameter with a continuum solvation method is not straightforward and has to be approached with great care. Third, optimally tuned range-separated hybrids without a short-range exchange component tend to inherit undesirable characteristics of semi-local functionals: with increasing system size the range separation parameter takes a smaller value, leading to a functional of effectively more semi-local nature and thus not accurately capturing, e.g., the saturation of the optical gap with increasing system size.

  12. Synthesis and characterization of Ag doped ZnS quantum dots for enhanced photocatalysis of Strychnine asa poison: Charge transfer behavior study by electrochemical impedance and time-resolved photoluminescence spectroscopy.

    Science.gov (United States)

    Gupta, Vinod Kumar; Fakhri, Ali; Azad, Mona; Agarwal, Shilpi

    2018-01-15

    In this study, the photocatalytic degradation of Strychnine was investigated by ZnS quantum dots and doped with silver in UV systems. ZnS and Ag-ZnS quantum dots were synthesized by chemical method and characterized by powder X-ray diffraction, transmission electron microscopy, UV-vis spectra and photoluminescence. The charge transfer process on the semicon-ductor/electrolyte interface was investigated via electrochemical impedance spectroscopy (EIS) and time-resolved photoluminescence. The average diameters of ZnS and Ag doped ZnS QDs were 3.0-5.0nm and 3.0-5.3nm, respectively. The band gap of ZnS and Ag-ZnS QDs was computed as 3.47 and 3.1eV, respectively. The surface area values of ZnS and Ag-ZnS QDs have been found as 78.25 and 89.54m2/g, respectively. The influences of key operating parameters such as initial pH, catalyst dosage, UV radiation intensity, reaction time as well as the effect of initial Strychnine concentration on mineralization extents were studied. The results of the study showed that the maximum removal efficiency of Strychnine had been achieved by un-doped and Ag-doped ZnS QDs at radiation intensity of 100W/m2, at time of 60min, pH of 3 and initial Strychnine concentration of 20mg/ml. Also the observations clearly showed that the photocatalysis process with Ag doped ZnS QDs are more effective than un-doped ZnS QDs. Copyright © 2017 Elsevier Inc. All rights reserved.

  13. Exploring the pH dependent SERS spectra of 2-mercaptoimidazole molecule adsorbed on silver nanocolloids in the light of Albrecht's "A" term and Herzberg-Teller charge transfer contribution.

    Science.gov (United States)

    Chandra, Subhendu; Chowdhury, Joydeep; Ghosh, Manash; Talapatra, G B

    2013-06-01

    The pH dependent surface-enhanced Raman scattering (SERS) spectra of biologically and industrially significant, 2-mercaptoimidazole (2-MI) molecule at 1.0×10(-10)M concentration have been investigated. The pH dependent SERS spectra are compared with the corresponding normal Raman spectra (NRS) of the molecule. The vibrational analyses of the pH dependent NRS spectra of the molecule reveal that in the acidic pH medium, the cationic form of the molecule is preponderant, while in the neutral pH, the existence of the cationic, normal, ylidic, and anionic forms of the molecule are all prevalent. However, in the alkaline pH medium, the anionic form of the molecule is estimated to be dominant. The SERS spectral analyses suggest the predominant adsorption of the cationic and the normal forms of the molecule on the nanocolloidal silver surface at acidic pH of the medium. However, at neutral pH, the cationic and/or normal, ylidic forms of the molecule take active part in the adsorption process, while considerable interactions of the normal, ylidic and/or anionic forms of the molecule with the nanocolloidal silver surface are presaged at alkaline pH of the medium. The genesis of selective enhancements of the Raman bands in the SERS spectra of the molecule recorded at various pH values of the medium has been unveiled from the view of the Albretcht's "A" and Herzberg-Teller (HT) charge transfer (CT) contribution. Copyright © 2013 Elsevier Inc. All rights reserved.

  14. Simultaneous resonance Raman detection of the heme a3-Fe-CO and CuB-CO species in CO-bound ba3-cytochrome c oxidase from Thermus thermophilus. Evidence for a charge transfer CuB-CO transition.

    Science.gov (United States)

    Pinakoulaki, Eftychia; Ohta, Takehiro; Soulimane, Tewfik; Kitagawa, Teizo; Varotsis, Constantinos

    2004-05-28

    Understanding of the chemical nature of the dioxygen and nitric oxide moiety of ba3-cytochrome c oxidase from Thermus thermophilus is crucial for elucidation of its physiological function. In the present work, direct resonance Raman (RR) observation of the Fe-C-O stretching and bending modes and the C-O stretching mode of the CuB-CO complex unambiguously establishes the vibrational characteristics of the heme-copper moiety in ba3-oxidase. We assigned the bands at 507 and 568 cm(-1) to the Fe-CO stretching and Fe-C-O bending modes, respectively. The frequencies of these modes in conjunction with the C-O mode at 1973 cm(-1) showed, despite the extreme values of the Fe-CO and C-O stretching vibrations, the presence of the alpha-conformation in the catalytic center of the enzyme. These data, distinctly different from those observed for the caa3-oxidase, are discussed in terms of the proposed coupling of the alpha-and beta-conformations that occur in the binuclear center of heme-copper oxidases with enzymatic activity. The CuB-CO complex was identified by its nu(CO) at 2053 cm(-1) and was strongly enhanced with 413.1 nm excitation indicating the presence of a metal-to-ligand charge transfer transition state near 410 nm. These findings provide, for the first time, RR vibrational information on the EPR silent CuB(I) that is located at the O2 delivery channel and has been proposed to play a crucial role in both the catalytic and proton pumping mechanisms of heme-copper oxidases.

  15. Photodissociation of van der Waals complexes of iodine X-I2 (X = I2, C2H4) via charge-transfer state: A velocity map imaging investigation

    Science.gov (United States)

    Bogomolov, Alexandr S.; Goldort, Veniamin G.; Kochubei, Sergei A.; Baklanov, Alexey V.

    2017-12-01

    The photodissociation of van der Waals complexes of iodine X-I2 (X = I2, C2H4) excited via Charge-Transfer (CT) band has been studied with the velocity map imaging technique. Photodissociation of both complexes gives rise to translationally "hot" molecular iodine I2 via channels differing by kinetic energy and angular distribution of the recoil directions. These measured characteristics together with the analysis of the model potential energy surface for these complexes allow us to infer the back-electron-transfer (BET) in the CT state to be a source of observed photodissociation channels and to make conclusions on the location of conical intersections where the BET process takes place. The BET process is concluded to provide an I2 molecule in the electronic ground state with moderate vibrational excitation as well as X molecule in the electronic excited state. In the case of X = I2, the BET process converts anion I2- of the CT state into the neutral I2 in the repulsive excited electronic state which then dissociates promptly giving rise to a pair of I atoms in the fine states 2P1/2. In the case of C2H4-I2, the C2H4 molecules appear in the triplet T1 electronic state. Conical intersection for corresponding BET process becomes energetically accessible after partial twisting of C2H4+ frame in the excited CT state of complex. The C2H4(T)-I2 complex gives rise to triplet ethylene as well as singlet ethylene via the T-S conversion.

  16. Tunable band structures in digital oxides with layered crystal habits

    Science.gov (United States)

    Shin, Yongjin; Rondinelli, James M.

    2017-11-01

    We use density functional calculations to show that heterovalent cation-order sequences enable control over band-gap variations up to several eV and band-gap closure in the bulk band insulator LaSrAlO4. The band-gap control originates from the internal electric fields induced by the digital chemical order, which induces picoscale band bending; the electric-field magnitude is mainly governed by the inequivalent charged monoxide layers afforded by the layered crystal habit. Charge transfer and ionic relaxations across these layers play secondary roles. This understanding is used to construct and validate a descriptor that captures the layer-charge variation and to predict changes in the electronic gap in layered oxides exhibiting antisite defects and in other chemistries.

  17. Comparative study on contribution of charge-transfer collision to excitations of iron ion between argon radio-frequency inductively-coupled plasma and nitrogen microwave induced plasma

    Energy Technology Data Exchange (ETDEWEB)

    Satoh, Kozue; Wagatsuma, Kazuaki, E-mail: wagatuma@imr.tohoku.ac.jp

    2015-06-01

    This paper describes an ionization/excitation phenomenon of singly-ionized iron occurring in an Okamoto-cavity microwave induced plasma (MIP) as well as an argon radio-frequency inductively-coupled plasma (ICP), by comparing the Boltzmann distribution among iron ionic lines (Fe II) having a wide range of the excitation energy from 4.76 to 9.01 eV. It indicated in both the plasmas that plots of Fe II lines having lower excitation energies (4.76 to 5.88 eV) were fitted on each linear relationship, implying that their excitations were caused by a dominant thermal process such as collision with energetic electron. However, Fe II lines having higher excitation energies (more than 7.55 eV) had a different behavior from each other. In the ICP, Boltzmann plots of Fe II lines assigned to the higher excited levels also followed the normal Boltzmann relationship among the low-lying excited levels, even including a deviation from it in particular excited levels having an excitation energy of ca. 7.8 eV. This deviation can be attributed to a charge-transfer collision with argon ion, which results in the overpopulation of these excited levels, but the contribution is small. On the other hand, the distribution of the high-lying excited levels was non-thermal in the Okamoto-cavity MIP, which did not follow the normal Boltzmann relationship among the low-lying excited levels. A probable reason for the non-thermal characteristics in the MIP is that a charge-transfer collision with nitrogen molecule ion having many vibrational/rotational levels could work for populating the 3d{sup 6}4p (3d{sup 5}4s4p) excited levels of iron ion broadly over an energy range of 7.6–9.0 eV, while collisional excitation by energetic electron would occur insufficiently to excite these high-energy levels. - Highlights: • This paper describes the excitation mechanism of iron ion in Okamoto-cavity MIP in comparison with conventional ICP. • Boltzmann distribution is studied among iron ionic lines of

  18. Investigation of the charge-transfer in photo-excited nanoparticles for CO2 reduction in non-aqueous media

    Directory of Open Access Journals (Sweden)

    Dimitrijević Nada M.

    2013-01-01

    Full Text Available Photoinduced charge separation in TiO2 and Cu2O semiconductor nanoparticles was examined using Electron Paramagnetic Resonance spectroscopy in order to get insight into the photocatalytic reduction of CO2 in nonaqueous media. For dissolution/grafting of CO2 we have used carboxy-PEG4-amine, and as a solvent poly(ethylene glycol 200. We have found that, in this system, reduction of CO2 starts at potential of -0.5 V vs Ag/AgCl, which is significantly more positive than the potential for electrochemical reduction of CO2 in most organic solvents and water (-2.0 V vs. Ag/AgCl. The electron transfer from excited nanoparticles to CO2 is governed both by thermodynamic and kinetic parameters, namely by the redox potential of conduction band electrons and adsorption/binding of CO2 on the surface of nanoparticles.

  19. Absorption Spectrum of a Ru(II)-Aquo Complex in Vacuo: Resolving Individual Charge-Transfer Transitions.

    Science.gov (United States)

    Xu, Shuang; Weber, J Mathias

    2015-11-25

    Ruthenium(II) complexes are of great interest as homogeneous catalysts and as photosensitizers; however, their absorption spectra are typically very broad and offer only little insight into their electronic structure. We present the electronic spectrum of the aquo complex [(trpy)(bipy)Ru(II)-OH2](2+) measured by photodissociation spectroscopy of mass-selected ions in vacuo (bipy = 2,2'-bipyridine and trpy = 2,2':6',2″-terpyridine). In the visible and near-UV, [(trpy)(bipy)Ru(II)-OH2](2+) has several electronic bands that are not resolved in absorption spectra of this complex in solution but are partially resolved in vacuo. The experimental results are compared with results from time-dependent density functional theory calculations.

  20. Study of conformational stability, structural, electronic and charge transfer properties of cladrin using vibrational spectroscopy and DFT calculations.

    Science.gov (United States)

    Singh, Swapnil; Singh, Harshita; Srivastava, Anubha; Tandon, Poonam; Sinha, Kirti; Bharti, Purnima; Kumar, Sudhir; Kumar, Padam; Maurya, Rakesh

    2014-11-11

    In the present work, a detailed conformational study of cladrin (3-(3,4-dimethoxy phenyl)-7-hydroxychromen-4-one) has been done by using spectroscopic techniques (FT-IR/FT-Raman/UV-Vis/NMR) and quantum chemical calculations. The optimized geometry, wavenumber and intensity of the vibrational bands of the cladrin in ground state were calculated by density functional theory (DFT) employing 6-311++G(d,p) basis sets. The study has been focused on the two most stable conformers that are selected after the full geometry optimization of the molecule. A detailed assignment of the FT-IR and FT-Raman spectra has been done for both the conformers along with potential energy distribution for each vibrational mode. The observed and scaled wavenumber of most of the bands has been found to be in good agreement. The UV-Vis spectrum has been recorded and compared with calculated spectrum. In addition, 1H and 13C nuclear magnetic resonance spectra have been also recorded and compared with the calculated data that shows the inter or intramolecular hydrogen bonding. The electronic properties such as HOMO-LUMO energies were calculated by using time-dependent density functional theory. Molecular electrostatic potential has been plotted to elucidate the reactive part of the molecule. Natural bond orbital analysis was performed to investigate the molecular stability. Non linear optical property of the molecule have been studied by calculating the electric dipole moment (μ) and the first hyperpolarizability (β) that results in the nonlinearity of the molecule. Copyright © 2014 Elsevier B.V. All rights reserved.

  1. Dynamic changes in charge-transfer resistance at Li metal/Li7La3Zr2O12 interfaces during electrochemical Li dissolution/deposition cycles

    Science.gov (United States)

    Koshikawa, Hiroyuki; Matsuda, Shoichi; Kamiya, Kazuhide; Miyayama, Masaru; Kubo, Yoshimi; Uosaki, Kohei; Hashimoto, Kazuhito; Nakanishi, Shuji

    2018-02-01

    Dynamic changes in the charge-transfer resistance at a Li/Li7La3Zr2O12 (LLZ) interface during lithium (Li) dissolution/deposition cycles are investigated with an alternative current (AC) impedance technique in a three-electrode system. The resistance respectively increases and decreases during electrodissolution and electrodeposition of Li. The resistance does not return to the initial value after one cycle of Li dissolution and deposition, which indicates that the change in resistance during dissolution is larger than that during deposition. Furthermore, the resistance is almost constant when Li deposition proceeds without prior Li dissolution. The respective increase and decrease in the interfacial resistance during Li dissolution and deposition is most likely due to the formation and disappearance of voids at the Li/LLZ interface, and the voids formation during Li dissolution is suggested to be a critical factor that influences the interfacial resistance.

  2. Restoring interlayer Josephson coupling in La1.885Ba0.115CuO4 by charge transfer melting of stripe order

    Science.gov (United States)

    Khanna, V.; Mankowsky, R.; Petrich, M.; Bromberger, H.; Cavill, S. A.; Möhr-Vorobeva, E.; Nicoletti, D.; Laplace, Y.; Gu, G. D.; Hill, J. P.; Först, M.; Cavalleri, A.; Dhesi, S. S.

    2016-06-01

    We show that disruption of charge-density-wave (stripe) order by charge transfer excitation, enhances the superconducting phase rigidity in La1.885Ba0.115CuO4 . Time-resolved resonant soft x-ray diffraction demonstrates that charge order melting is prompt following near-infrared photoexcitation whereas the crystal structure remains intact for moderate fluences. THz time-domain spectroscopy reveals that, for the first 2 ps following photoexcitation, a new Josephson plasma resonance edge, at higher frequency with respect to the equilibrium edge, is induced indicating enhanced superconducting interlayer coupling. The fluence dependence of the charge-order melting and the enhanced superconducting interlayer coupling are correlated with a saturation limit of ˜0.5 mJ /cm2 . Using a combination of x-ray and optical spectroscopies we establish a hierarchy of timescales between enhanced superconductivity, melting of charge order, and rearrangement of the crystal structure.

  3. Intramolecular charge transfer reaction in 3-amino-4-methyl benzoic acid: a study from condensed phase to jet-cooled molecular beam

    Science.gov (United States)

    Ghosh, S.; Paul, B. K.; Chakraborty, A.; Nath, D. N.; Guchhait, N.

    2012-03-01

    The present work reports the spectral signatures of intramolecular charge transfer (ICT) reaction in 3-amino-4-methyl benzoic acid (AMBA). AMBA exhibits large red-shifted emission in various solvents with the emission maxima being highly sensitive to the solvent polarity. Solvatochromic measurements of AMBA on the basis of its steady state absorption and emission properties appears to confirm the operation of photoinduced ICT reaction in it with the ICT state being characterized by a higher excited state dipole moment than that of the ground state. Laser induced fluorescence excitation spectra and dispersed fluorescence spectra of AMBA and its solvated clusters with polar solvent methanol in the cooled jet yield quite distinct evidence for the occurrence of ICT reaction in polar solvent.

  4. Trajectory-dependent energy- and charge-transfer in collisions of Br sup + ( sup 3 P sub 2) with Pt(1 1 1)

    CERN Document Server

    Maazouz, P L; Jacobs, D C

    2003-01-01

    Collisions of hyperthermal energy Br sup + ( sup 3 P sub 2) with Pt(1 1 1) produces scattered Br sup - ( sup 1 S sub 0) with a yield approaching 7%. The energy distribution of the scattered product exhibits an unusual dependence on the collision energy. Specifically, as the incident energy increases from 34 to 54 eV, the peak energy of scattered Br sup - ( sup 1 S sub 0) decreases. Furthermore, the anion yield reaches a sharp maximum when Br sup + ( sup 3 P sub 2) approaches the surface with 26 eV of translational energy. The unusual scattering behavior is attributed to a trajectory dependent collision-induced deformation of the lattice. The corresponding electronic perturbation evolves synchronously with the motion of the departing projectile - leading to an enhanced charge-transfer probability.

  5. Impact of electron delocalization on the nature of the charge-transfer states in model pentacene/C60 Interfaces: A density functional theory study

    KAUST Repository

    Yang, Bing

    2014-12-04

    Electronic delocalization effects have been proposed to play a key role in photocurrent generation in organic photovoltaic devices. Here, we study the role of charge delocalization on the nature of the charge-transfer (CT) states in the case of model complexes consisting of several pentacene molecules and one fullerene (C60) molecule, which are representative of donor/acceptor heterojunctions. The energies of the CT states are examined by means of time-dependent density functional theory (TD-DFT) using the long-range-corrected functional, ωB97X, with an optimized range-separation parameter, ω. We provide a general description of how the nature of the CT states is impacted by molecular packing (i.e., interfacial donor/acceptor orientations), system size, and intermolecular interactions, features of importance in the understanding of the charge-separation mechanism.

  6. Sparfloxacin charge transfer complexes with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone and tetracyanoquinodimethane: Molecular structures, spectral, and DFT studies

    Science.gov (United States)

    Shehab, Ola R.; Mansour, Ahmed M.

    2015-08-01

    A simple, sensitive and rapid method was developed for the quantitative analysis of sparfloxacin in its pharmaceutical formulations through the formation of charge transfer complexes with π-acceptor systems. The Lambert-Beer's law was obeyed in the concentration ranges of 7-70 and 10-50 μg/mL sparfloxacin for 2,3-dichloro-5,6-dicyano-1,4-benzoquinone and tetracyanoquinodimethane. Structural characterization of the isolated solid CT complexes was carried out by IR, 1H NMR, UV-Vis. and MS. The experimental studies were complemented by quantum chemical calculations at DFT level of theory. The electronic structures were investigated by TD-DFT calculations. Natural bond orbital analysis and molecular electrostatic potential maps were helpful in assigning the CT route. The formation constant, molar extinction coefficient, oscillator strength, dipole moment, standard free energy and ionization potential were calculated.

  7. Defect Healing and Charge Transfer-Mediated Valley Polarization in MoS2/MoSe2/MoS2Trilayer van der Waals Heterostructures.

    Science.gov (United States)

    Surrente, Alessandro; Dumcenco, Dumitru; Yang, Zhuo; Kuc, Agnieszka; Jing, Yu; Heine, Thomas; Kung, Yen-Cheng; Maude, Duncan K; Kis, Andras; Plochocka, Paulina

    2017-07-12

    Monolayer transition metal dichalcogenides (TMDCs) grown by chemical vapor deposition (CVD) are plagued by a significantly lower optical quality compared to exfoliated TMDCs. In this work, we show that the optical quality of CVD-grown MoSe 2 is completely recovered if the material is sandwiched in MoS 2 /MoSe 2 /MoS 2 trilayer van der Waals heterostructures. We show by means of density functional theory that this remarkable and unexpected result is due to defect healing: S atoms of the more reactive MoS 2 layers are donated to heal Se vacancy defects in the middle MoSe 2 layer. In addition, the trilayer structure exhibits a considerable charge-transfer mediated valley polarization of MoSe 2 without the need for resonant excitation. Our fabrication approach, relying solely on simple flake transfer technique, paves the way for the scalable production of large-area TMDC materials with excellent optical quality.

  8. Theoretical investigation of the interaction between aromatic sulfur compounds and [BMIM](+)[FeCl4](-) ionic liquid in desulfurization: A novel charge transfer mechanism.

    Science.gov (United States)

    Li, Hongping; Zhu, Wenshuai; Chang, Yonghui; Jiang, Wei; Zhang, Ming; Yin, Sheng; Xia, Jiexiang; Li, Huaming

    2015-06-01

    In this work, interaction nature between a group of aromatic sulfur compounds and [BMIM](+)[FeCl4](-) have been investigated by density functional theory (DFT). A coordination structure is found to be critical to the mechanism of extractive desulfurization. Interaction energy and extractive selectivity follow the order: thiophene (TH)desulfurization is attributed to the charge transfer effect. During extractive desulfurization, electrons on aromatic sulfur compounds transfer into the Lewis part of ionic liquid, namely, [FeCl4](-). Furthermore, it is better to consider the Lewis acidity of Fe-containing ionic liquid by the whole unit (such as [FeCl4](-) and aromatic sulfur compounds (X)) rather than only Fe or S atom. Copyright © 2015 Elsevier Inc. All rights reserved.

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

    CERN Document Server

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

    2002-01-01

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

  10. Determination of nicotine in tobacco with second-order spectra data of charge-transfer complex in ethanol-water binary solvents processed by parallel factor analysis

    Science.gov (United States)

    Gao, Shuqin; Liao, Lifu; Xiao, Xilin; Zhao, Zhiyuan; Du, Nan; Du, Jiangfeng

    2010-05-01

    A new spectrophotometric method for the determination of nicotine in mixtures without pre-separation has been proposed. Nicotine could react with 2,4-dinitrophenol through a charge-transfer reaction to form a colored complex. The second-order data from the visible absorption spectra of the complex in a series of ethanol-water binary solvents with various water volume fractions could be expressed as the combination of two bilinear data matrices. With the bilinear model, the second-order spectra data of mixtures containing nicotine and other interferents could be analysed by using second-order calibration algorithms, and the determination of nicotine in the mixtures could be achieved. The algorithm used here was parallel factor analysis. The method has been successfully used to determine nicotine in tobacco samples with satisfactory results.

  11. Control of interfacial charge-transfer interaction of dye and p-CuI in solid-state dye-sensitized solar cells

    Science.gov (United States)

    Moribe, Shinya; Kato, Naohiko; Higuchi, Kazuo; Mizumoto, Katsuyoshi; Toyoda, Tatsuo

    2017-04-01

    We systematically investigated the photovoltaic and absorption characteristics of solid-state dye-sensitized solar cells with CuI to elucidate the impact of the interaction between the dye and CuI. For the ruthenium complex N719, the incident photon-to-current conversion efficiency (IPCE) on the longer-wavelength side decreased owing to the change of the metal-to-ligand charge transfer (CT) of N719 due to the interaction between the thiocyanate groups of N719 and CuI. In contrast, when D149 — which included rhodanine groups — was used, the interaction with CuI and the resultant CT increased the IPCE. The results provide a new strategy for improving the photovoltaic performance by controlling the interfacial CT between the dye and CuI.

  12. Probing charge transfer in a novel class of luminescent perovskite-based heterostructures composed of quantum dots bound to RE-activated CaTiO3 phosphors

    Science.gov (United States)

    Lewis, Crystal S.; Liu, Haiqing; Han, Jinkyu; Wang, Lei; Yue, Shiyu; Brennan, Nicholas A.; Wong, Stanislaus S.

    2016-01-01

    We report on the synthesis and structural characterization of novel semiconducting heterostructures composed of cadmium selenide (CdSe) quantum dots (QDs) attached onto the surfaces of novel high-surface area, porous rare-earth-ion doped alkaline earth titanate micron-scale spherical motifs, i.e. both Eu-doped and Pr-doped CaTiO3, composed of constituent, component nanoparticles. These unique metal oxide perovskite building blocks were created by a multi-pronged synthetic strategy involving molten salt and hydrothermal protocols. Subsequently, optical characterization of these heterostructures indicated a clear behavioral dependence of charge transfer in these systems upon a number of parameters such as the nature of the dopant, the reaction temperature, and particle size. Specifically, 2.7 nm diameter ligand-functionalized CdSe QDs were anchored onto sub-micron sized CaTiO3-based spherical assemblies, prepared by molten salt protocols. We found that both the Pr- and Eu-doped CaTiO3 displayed pronounced PL emissions, with maximum intensities observed using optimized lanthanide concentrations of 0.2 mol% and 6 mol%, respectively. Analogous experiments were performed on Eu-doped BaTiO3 and SrTiO3 motifs, but CaTiO3 still performed as the most effective host material amongst the three perovskite systems tested. Moreover, the ligand-capped CdSe QD-doped CaTiO3 heterostructures exhibited effective charge transfer between the two individual constituent nanoscale components, an assertion corroborated by the corresponding quenching of their measured PL signals.We report on the synthesis and structural characterization of novel semiconducting heterostructures composed of cadmium selenide (CdSe) quantum dots (QDs) attached onto the surfaces of novel high-surface area, porous rare-earth-ion doped alkaline earth titanate micron-scale spherical motifs, i.e. both Eu-doped and Pr-doped CaTiO3, composed of constituent, component nanoparticles. These unique metal oxide perovskite

  13. Cyanide anion sensing mechanism of 1,3,5,7-tetratolyl aza-BODIPY: Intramolecular charge transfer and partial configuration change

    Science.gov (United States)

    Bhat, Haamid R.; Jha, Prakash C.

    2017-02-01

    The cyanide anion sensing mechanism of 1,3,5,7-tetratolyl aza-BODIPY (1) has been rigorously investigated using density functional theory and time dependent-density functional theory methods. Mulliken charge distribution and Natural Bond Orbital analysis reveals that cyanide addition may occur at both electrophilic centers with equal probability. The molecular orbital analysis reveals that first excited state (S1) of 1 is a local excited state with π-π∗ transition, whereas for 2 (the cyano form of 1), S1 , a charge-separation state, is found to be responsible for the intramolecular charge transfer (ICT) process which in conjunction with partial configuration change induces fluorescence stimulation in 2.

  14. Morphological transition of the host-structure influences solvent-relaxation: A wavelength-selective fluorescence exploration through environment-sensitive intramolecular charge transfer photophysics

    Science.gov (United States)

    Paul, Bijan Kumar; Guchhait, Nikhil

    2011-10-01

    Here, we report the modulation of photo-induced intramolecular charge transfer (ICT) photophysics of N,N-dimethylaminonaphthyl-acrylo-nitrile (DMANAN) associated with sphere-to-rod structural transition of SDS micelles induced by increasing ionic strength of the medium. Emphasis is rendered on the exploration of solvent-relaxation associated with this transition on the basis of wavelength-selective fluorescence technique which includes monitoring of red-edge excitation shift (REES) and excitation/emission anisotropy profiles. Based on micropolarity determination and organization of solvent water around the probe microenvironment we argue that the present results advocate for rod-shaped micelles to be a better mimic for membrane bilayers than spherical micelles.

  15. Utility of positron annihilation lifetime technique for the assessment of spectroscopic data of some charge-transfer complexes derived from N-(1-Naphthyl)ethylenediamine dihydrochloride.

    Science.gov (United States)

    Refat, Moamen S; Adam, Abdel Majid A; Sharshar, T; Saad, Hosam A; Eldaroti, Hala H

    2014-03-25

    In this work, structural, thermal, morphological, pharmacological screening and positron annihilation lifetime measurements were performed on the interactions between a N-(1-Naphthyl)ethylenediamine dihydrochloride (NEDA·2HCl) donor and three types of acceptors to characterize these CT complexes. The three types of acceptors include π-acceptors (quinol and picric acid), σ-acceptors (iodine) and vacant orbital acceptors (tin(IV) tetrachloride and zinc chloride). The positron annihilation lifetime parameters were found to be dependent on the structure, electronic configuration, the power of acceptors and molecular weight of the CT complexes. The positron annihilation lifetime spectroscopy can be used as a probe for the formation of charge-transfer (CT) complexes. Copyright © 2013 Elsevier B.V. All rights reserved.

  16. Evaluating the Performance of DFT Functionals in Assessing the Interaction Energy and Ground-State Charge Transfer of Donor/Acceptor Complexes: Tetrathiafulvalene−Tetracyanoquinodimethane (TTF−TCNQ) as a Model Case

    KAUST Repository

    Sini, Gjergji

    2011-03-08

    We have evaluated the performance of several density functional theory (DFT) functionals for the description of the ground-state electronic structure and charge transfer in donor/acceptor complexes. The tetrathiafulvalene- tetracyanoquinodimethane (TTF-TCNQ) complex has been considered as a model test case. Hybrid functionals have been chosen together with recently proposed long-range corrected functionals (ωB97X, ωB97X-D, LRC-ωPBEh, and LC-ωPBE) in order to assess the sensitivity of the results to the treatment and magnitude of exact exchange. The results show an approximately linear dependence of the ground-state charge transfer with the HOMO TTF-LUMOTCNQ energy gap, which in turn depends linearly on the percentage of exact exchange in the functional. The reliability of ground-state charge transfer values calculated in the framework of a monodeterminantal DFT approach was also examined. © 2011 American Chemical Society.

  17. A novel chalcone-analogue as an optical sensor based on ground and excited states intramolecular charge transfer: A combined experimental and theoretical study

    Energy Technology Data Exchange (ETDEWEB)

    Fayed, Tarek A. [Chemistry Department, Faculty of Science, Tanta University, 31527-Tanta (Egypt)], E-mail: tfayed2003@yahoo.co.uk

    2006-05-31

    Steady-state absorption and emission spectroscopic techniques as well as semiempirical quantum calculations at the AM1 and ZINDO/S levels have been used to investigate the intramolecular charge transfer (ICT) behaviour of a novel chalcone namely; 1-(2-pyridyl)-5-(4-dimethylaminophenyl)-penta-2,4-diene-1-one, DMAC. The ground state DMAC has a significant ICT character and a great sensitivity to the hydrogen bond donating ability of the medium as reflected from the change of the absorption spectra in pure and mixed organic solvents. On the other hand, its excited singlet state exhibits high ICT characters as manifested by the drastic solvatochromic effects. These results are consistent with the data of charge density calculations in both the ground and excited state, which indicates enhancement of the charge transfer from the dimethyl-amino group to the carbonyl oxygen upon excitation. Also, the dipole moment calculations indicates a highly dipolar excited singlet state ({delta}{mu} {sub eg} = 15.5 D). The solvent dependence of the fluorescence quantum yield of DMAC was interpreted on the basis of positive and negative solvatokinetic as well as the hydrogen bonding effects. Incorporation of the 2-pyridyl group in the chemical structure of the present DMAC led to design of a potential optical sensor for probing acidity of the medium and metal cations such as Zn{sup 2+}, Cd{sup 2+} and Hg{sup 2+}. This was concluded from the high acidochromic and metallochromic behaviour of DMAC on adding such cations to its acetonitrile solutions.

  18. Two states are not enough: quantitative evaluation of the valence-bond intramolecular charge-transfer model and its use in predicting bond length alternation effects.

    Science.gov (United States)

    Jarowski, Peter D; Mo, Yirong

    2014-12-15

    The structural weights of the canonical resonance contributors used in the Two-state valence-bond charge-transfer model, neutral (N, R1) and ionic (VB-CT, R2), to the ground states and excited states of a series of linear dipolar intramolecular charge-transfer chromophores containing a buta-1,3-dien-1,4-diyl bridge have been computed by using the block-localized wavefunction (BLW) method at the B3LYP/6-311+G(d) level to provide the first quantitative assessment of this simple model. Ground- and excited-state analysis reveals surprisingly low ground-state structural weights for the VB-CT resonance form using either this Two-state model or an expanded Ten-state model. The VB-CT state is found to be more prominent in the excited state. Individual resonance forms were structurally optimized to understand the origins of the bond length alternation (BLA) of the bridging unit. Using a Wheland energy-based weighting scheme, the weighted average of the optimized bond lengths with the Two-state model was unable to reproduce the BLA features with values 0.04 to 0.02 Å too large compared to the fully delocalized (FD) structure (BLW: ca. -0.13 to -0.07 Å, FD: ca. -0.09 to -0.05 Å). Instead, an expanded Ten-state model fit the BLA values of the FD structure to within only 0.001 Å of FD. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Photoinduced excitation and charge transfer processes of organic dyes with siloxane anchoring groups: a combined spectroscopic and computational study.

    Science.gov (United States)

    Castellucci, Elena; Monini, Marco; Bessi, Matteo; Iagatti, Alessandro; Bussotti, Laura; Sinicropi, Adalgisa; Calamante, Massimo; Zani, Lorenzo; Basosi, Riccardo; Reginato, Gianna; Mordini, Alessandro; Foggi, Paolo; Di Donato, Mariangela

    2017-06-14

    Dye-sensitized solar cells (DSSCs) have attracted significant interest in the last few years as effective low-cost devices for solar energy conversion. We have analyzed the excited state dynamics of several organic dyes bearing both cyanoacrylic acid and siloxane anchoring groups. The spectroscopic properties of the dyes have been studied both in solution and when adsorbed on a TiO2 film using stationary and time-resolved techniques, probing the sub-picosecond to nanosecond time interval. The comparison between the spectra registered in solution and on the solid substrate evidences different pathways for energy and electron relaxation. The transient spectra of the TiO2-adsorbed dyes show the appearance of a long wavelength excited state absorption band, attributed to the cationic dye species, which is absent in the spectra measured in solution. Furthermore, the kinetic traces of the samples adsorbed on the TiO2 film show a long decay component not present in solution which constitutes indirect evidence of electron transfer between the dye and the semiconductor. The interpretation of the experimental results has been supported by theoretical DFT calculations of the excited state energies and by the analysis of molecular orbitals of the analyzed dye molecules.

  20. Photoinduced charge transfer properties and photocatalytic activity in Bi2O3/BaTiO3 composite photocatalyst.

    Science.gov (United States)

    Fan, Haimei; Li, Haiyan; Liu, Bingkun; Lu, Yongchun; Xie, Tengfeng; Wang, Dejun

    2012-09-26

    A series of Bi(2)O(3)/BaTiO(3) composite photocatalysts with different mass ratios of Bi(2)O(3) vs BaTiO(3) were prepared by an impregnating-annealing method. X-ray diffraction (XRD), high-resolution transmission electron microscopic (HRTEM), and UV-vis diffuse reflection spectroscopy (DRS) confirmed that Bi(2)O(3) and BaTiO(3) coexisted in the composites. The results of surface photovoltage (SPV) experiments showed enhancements of photovoltaic response in composites, which indicated a higher separation efficiency of photoinduced charges due to the establishment of an efficient interfacial electric field between Bi(2)O(3) and BaTiO(3) in the composites. The consistency of phtocatalytic activity and photovoltaic response intensity of photocatalysts showed that the efficiency interfacial electric field between Bi(2)O(3) and BaTiO(3) played an important role in improving the degradation efficiency of Rhodamine B (RhB). The 60%-Bi(2)O(3)/BaTiO(3) sample with the best activity was found by optimizing the mass ratios of Bi(2)O(3) vs. BaTiO(3). On the basis of the work function (WF) measurements, a reasonable energy band diagram was proposed for BaTiO(3)/Bi(2)O(3) composite. It would be helpful in designing and constructing high efficiency heterogeneous semiconductor photocatalyst.