Science.gov

Sample records for charge transfer complexes

  1. Charge transfer complexes of certain aromatic polyimides

    NASA Technical Reports Server (NTRS)

    Gordina, T. A.; Kotov, B. V.; Kolninov, O. V.; Pravednikov, A. N.

    1985-01-01

    By electron spectroscopy it was shown that aromatic polyimides containing electron-donor residues of diamines -C6H4-X-C6H-(X=NH, NCH3, NC6H5, O, S, and CH2) form charge transfer complexes with low-molecular-weight electron acceptors. Based on the data obtained, the hypothesis was advanced that the coloration of the polyimides per se is due to the formation of charge transfer complexes between the electron-acceptor imide fragments and the electron-donor residues of the diamines.

  2. Coronene-based charge-transfer complexes

    NASA Astrophysics Data System (ADS)

    Yoshida, Yukihiro; Isomura, Kazuhide; Kumagai, Yoshihide; Maesato, Mitsuhiko; Kishida, Hideo; Mizuno, Motohiro; Saito, Gunzi

    2016-08-01

    Recent developments in the arena of charge-transfer complexes composed of the D 6h-symmetric polycyclic aromatic hydrocarbon, coronene, are highlighted with emphasis on the structural and physical properties of these complexes. Because of the dual electron-donating and -accepting abilities of coronene, this group involves structurally-defined four cation salts and three anion salts. The Jahn-Teller distortions and in-plane motion of coronene molecules in the solids, both of which are closely associated with the high symmetry of coronene molecules, and syntheses of clathrate-type complexes are also presented.

  3. Ytterbocene charge-transfer molecular wire complexes.

    PubMed

    Carlson, Christin N; Kuehl, Christopher J; Da Re, Ryan E; Veauthier, Jacqueline M; Schelter, Eric J; Milligan, Ashley E; Scott, Brian L; Bauer, Eric D; Thompson, J D; Morris, David E; John, Kevin D

    2006-06-07

    A systematic study of the novel charge-transfer [(f)14-(pi)0-(f)14 --> (f)13-(pi)2-(f)13] electronic state found in 2:1 metal-to-ligand adducts of the type [(Cp)2Yb](BL)[Yb(Cp)2] [BL = tetra(2-pyridyl)pyrazine (tppz) (1), 6',6' '-bis(2-pyridyl)-2,2':4',4'':2'',2'''-quaterpyridine (qtp) (2), 1,4-di(terpyridyl)-benzene (dtb) (3), Cp = (C5Me5)] has been conducted with the aim of determining the effects of increased Yb-Yb separation on the magnetic and electronic properties of these materials. The neutral [(f)13-(pi)2-(f)13], cationic [(f)13-(pi)1-(f)13] and dicationic [(f)13-(pi)0-(f)13] states of these complexes were studied by cyclic voltammetry, UV-vis-NIR electronic absorption spectroscopy, NMR, X-ray crystallography, and magnetic susceptibility measurements. The spectroscopic and magnetic data for the neutral bimetallic complexes is consistent with an [(f)13(pi)2(f)13] ground-state electronic configuration in which each ytterbocene fragment donates one electron to give a singlet dianionic bridging ligand with two paramagnetic Yb(III) centers. The voltammetric data demonstrate that the electronic interaction in the neutral molecular wires 1-3, as manifested in the separation between successive metal reduction waves, is large compared to analogous transition metal systems. Electronic spectra for the neutral and monocationic bimetallic species are dominated by pi-pi and pi-pi transitions, masking the f-f bands that are expected to best reflect the electronic metal-metal interactions. However, these metal-localized transitions are observed when the electrons are removed from the bridging ligand via chemical oxidation to yield the dicationic species, and they suggest very little electronic interaction between metal centers in the absence of pi electrons on the bridging ligands. Analysis of the magnetic data reveals that the qtp complex displays antiferromagnetic coupling of the type Yb(alpha)(alphabeta)Yb(beta) at approximately 13 K.

  4. Primary cells utilize halogen-organic charge transfer complex

    NASA Technical Reports Server (NTRS)

    Gutmann, F.; Hermann, A. M.; Rembaum, A.

    1966-01-01

    Electrochemical cells with solid state components employ charge transfer complexes or donor-acceptor complexes in which the donor component is an organic compound and the acceptor component is a halogen. A minor proportion of graphite added to these composition helps reduce the resistivity.

  5. Primary cells utilize halogen-organic charge transfer complex

    NASA Technical Reports Server (NTRS)

    Gutmann, F.; Hermann, A. M.; Rembaum, A.

    1966-01-01

    Electrochemical cells with solid state components employ charge transfer complexes or donor-acceptor complexes in which the donor component is an organic compound and the acceptor component is a halogen. A minor proportion of graphite added to these composition helps reduce the resistivity.

  6. Charge-transfer complexation between naphthalene diimides and aromatic solvents.

    PubMed

    Kulkarni, Chidambar; Periyasamy, Ganga; Balasubramanian, S; George, Subi J

    2014-07-28

    Naphthalene diimides (NDIs) form emissive ground-state charge-transfer (CT) complexes with various electron rich aromatic solvents like benzene, o-xylene and mesitylene. TD-DFT calculation of the complexes suggests CT interaction and accounts for the observed ground-state changes.

  7. Spectrophotometric determination of moclobemide by charge-transfer complexation.

    PubMed

    Adikwu, M U; Ofokansi, K C

    1997-11-01

    A simple and sensitive spectrophotometric method is described for the assay for the moclobemide. The method is based on the molecular interaction between the drug and chloranilic acid, to form a charge-transfer complex in which the drug acts as n-donor and chloranilic acid as pi-acceptor. Chloranilic acid was found to form a charge-transfer complex in a 1:1 stoichiometry with a maximum absorption band at 526 nm. Conformity with Beer's law was evident over the concentration range 4-36 mg 100 ml-1. A complete, detailed investigation of the complex formed was made with respect to its composition, association constant, molar absorptivity and free energy change. The method has been applied successfully to the analysis of commercially available moclobemide tablets with good recovery and reproducibility.

  8. Infrared Spectroscopy of Charge Transfer Complexes of Purines and Pyrimidines

    SciTech Connect

    Rathod, Pravinsinh I.; Oza, A. T.

    2011-10-20

    The FTIR spectra of charge transfer complexes of purines and pyrimidines with organic acceptors such as TCNQ, TCNE, DDQ, chloranil and iodine are obtained and studied in the present work. Adenine, guanine, thymine, cytosine and uracil are the purines and pyrimidines which are found as constituent of DNA and RNA. Charge transfer induced hydrogen bonding is concluded on the basis of indirect transitions observed in the infrared range in these CTCs. Some CTCs show gaussian bands revealing delocalization of charge carriers. The CTCs show interband transition in three-dimensions rather than two-dimensions unlike CTCs of amino acids. There is no extended hydrogen bonded network spanning the whole crystal. This leads to indirect transition due to locally deformed lattice furnishing a phonon-assisted transition.

  9. Infrared Spectroscopy of Charge Transfer Complexes of Purines and Pyrimidines

    NASA Astrophysics Data System (ADS)

    Rathod, Pravinsinh I.; Oza, A. T.

    2011-10-01

    The FTIR spectra of charge transfer complexes of purines and pyrimidines with organic acceptors such as TCNQ, TCNE, DDQ, chloranil and iodine are obtained and studied in the present work. Adenine, guanine, thymine, cytosine and uracil are the purines and pyrimidines which are found as constituent of DNA and RNA. Charge transfer induced hydrogen bonding is concluded on the basis of indirect transitions observed in the infrared range in these CTCs. Some CTCs show gaussian bands revealing delocalization of charge carriers. The CTCs show interband transition in three-dimensions rather than two-dimensions unlike CTCs of amino acids. There is no extended hydrogen bonded network spanning the whole crystal. This leads to indirect transition due to locally deformed lattice furnishing a phonon-assisted transition.

  10. Simple charge-transfer model for metallic complexes.

    PubMed

    Ramírez-Ramírez, José-Zeferino; Vargas, Rubicelia; Garza, Jorge; Gázquez, José L

    2010-08-05

    In the chemistry of metallic complexes, two important concepts have been used to rationalize the recognition and selectivity of a host by a guest: preorganization and complementarity. Both of these concepts stem from geometrical features. Less explored in the literature has been the interactional complementarity, where mainly the electronic factors in the intermolecular forces are involved. Because the charge transfer between a species rich in electrons (ligand) and another deficient in them (cation) is one of the main intermolecular factors that control the binding energies in metallic complexes, for such systems, we propose a simple model based on density functional theory. We define an interactional energy in which the geometrical energy changes are subtracted from the binding energies and just the electronic factors are taken into account. The model is tested for the complexation between bidentate and cyclic ligands and Ca, Pb, and Hg metal dications. The charge-transfer energy described by our model fits nicely with the interactional energy. Thus, when the geometrical changes do not contribute in a significant way to the complexation energy, the interactional energy is dominated by charge-transfer effects.

  11. Positron annihilation studies of some charge transfer molecular complexes

    NASA Astrophysics Data System (ADS)

    El-Sayed, A. M. A.; Mohamed, Hamdy F. M.; Boraei, Anmed A. A.

    2000-06-01

    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 from the IR-spectral data.

  12. The charge-transfer complex trans-STB-TCNQF4.

    PubMed

    Sato, A; Okada, M; Saito, K; Sorai, M

    2001-05-01

    In the crystal structure of the title charge-transfer complex, namely trans-stilbene-2,2'-(2,3,5,6-tetrafluorobenzene-1,4-diylidene)propanedinitrile (1/1) (trans-STB-TCNQF(4)), C(14)H(12).C(12)F(4)N(4), the planar STB and TCNQF(4) molecules are stacked alternately. The structure is not isostructural with that of STB-TCNQ. No anomaly was found in the displacement parameters of any atoms, while the bond length of the central C=C moiety was shorter than the corresponding bond in ethylene. This suggests that the central C=C moiety of the STB molecule vibrates with a large amplitude, similar to the case in free STB and STB-TCNQ.

  13. Quantum ferroelectricity in charge-transfer complex crystals

    PubMed Central

    Horiuchi, Sachio; Kobayashi, Kensuke; Kumai, Reiji; Minami, Nao; Kagawa, Fumitaka; Tokura, Yoshinori

    2015-01-01

    Quantum phase transition achieved by fine tuning the continuous phase transition down to zero kelvin is a challenge for solid state science. Critical phenomena distinct from the effects of thermal fluctuations can materialize when the electronic, structural or magnetic long-range order is perturbed by quantum fluctuations between degenerate ground states. Here we have developed chemically pure tetrahalo-p-benzoquinones of n iodine and 4–n bromine substituents (QBr4–nIn, n=0–4) to search for ferroelectric charge-transfer complexes with tetrathiafulvalene (TTF). Among them, TTF–QBr2I2 exhibits a ferroelectric neutral–ionic phase transition, which is continuously controlled over a wide temperature range from near-zero kelvin to room temperature under hydrostatic pressure. Quantum critical behaviour is accompanied by a much larger permittivity than those of other neutral–ionic transition compounds, such as well-known ferroelectric complex of TTF–QCl4 and quantum antiferroelectric of dimethyl–TTF–QBr4. By contrast, TTF–QBr3I complex, another member of this compound family, shows complete suppression of the ferroelectric spin-Peierls-type phase transition. PMID:26076656

  14. Quantum ferroelectricity in charge-transfer complex crystals

    NASA Astrophysics Data System (ADS)

    Horiuchi, Sachio; Kobayashi, Kensuke; Kumai, Reiji; Minami, Nao; Kagawa, Fumitaka; Tokura, Yoshinori

    2015-06-01

    Quantum phase transition achieved by fine tuning the continuous phase transition down to zero kelvin is a challenge for solid state science. Critical phenomena distinct from the effects of thermal fluctuations can materialize when the electronic, structural or magnetic long-range order is perturbed by quantum fluctuations between degenerate ground states. Here we have developed chemically pure tetrahalo-p-benzoquinones of n iodine and 4-n bromine substituents (QBr4-nIn, n=0-4) to search for ferroelectric charge-transfer complexes with tetrathiafulvalene (TTF). Among them, TTF-QBr2I2 exhibits a ferroelectric neutral-ionic phase transition, which is continuously controlled over a wide temperature range from near-zero kelvin to room temperature under hydrostatic pressure. Quantum critical behaviour is accompanied by a much larger permittivity than those of other neutral-ionic transition compounds, such as well-known ferroelectric complex of TTF-QCl4 and quantum antiferroelectric of dimethyl-TTF-QBr4. By contrast, TTF-QBr3I complex, another member of this compound family, shows complete suppression of the ferroelectric spin-Peierls-type phase transition.

  15. Photo-Induced Atom-Transfer Radical Reactions Using Charge-Transfer Complex between Iodine and Tertiary Amine.

    PubMed

    Yoshioka, Eito; Kohtani, Shigeru; Hashimoto, Takurou; Takebe, Tomoko; Miyabe, Hideto

    2017-01-01

    In the presence of charge-transfer complexes between iodine and tertiary amines, the aqueous-medium atom-transfer radical reactions proceeded under visible light irradiation without the typical photocatalysts.

  16. Conducting molecular nanostructures assembled from charge-transfer complexes grafted onto silicon surfaces

    NASA Astrophysics Data System (ADS)

    Stires, John C., IV; Kasibhatla, Bala S. T.; Siegel, Dustin S.; Kwong, Jinny C.; Caballero, Jonathan B.; Labonte, Andre P.; Reifenberger, Ronald G.; Datta, Supriyo; Kubiak, Clifford P.

    2003-12-01

    Heterodimeric electon-donor/electron-acceptor charge-transfer complexes chemisorbed onto Au(111) by attachment of the electron-donor to the surface have been characterized by scanning tunneling microscopy and Kelvin probe experiments. Conductance measurements exhibit nearly Ohmic I(V) responses at low bias. The electrical properties of the charge-transfer complex are vastly different than those of the electron-donor alone which exhibits insulating behavior at low bias. In an extension of this work, strategies are being developed for attachment of charge-transfer complexes to semiconducting or insulating surfaces. Fabrication of nanoscale molecular electronic devices is being investigated by attaching one component of a charge-transfer complex to a silicon surface by chemically directed self-assembly. The single component-functionalized surface is then used as a substrate on which the second component of the charge-transfer complex is deposited by the atomic force microscopy method, dip-pen nanolithography (DPN). Derivatives of hexamethylbenze (electron-donor) with terminal olefins attached to crystalline silicon surfaces via hydrosilylation form monolayer-functionalized silicon surfaces that are expected to have insulating properties. Well-defined features can be "drawn" onto the donor-functionalized surfaces by DPN using tetracyanoethylene (electron-acceptor) as the "ink." The resulting charge-transfer complex nanostructures have conducting properties suitable for device function and are flanked by an insulating monolayer, thus creating "wires" made from charge-transfer complexes.

  17. Low-temperature reflectance spectrum of the benzidine-TCNQ charge-transfer complex

    NASA Astrophysics Data System (ADS)

    Yakushi, Kyuya; Kuroda, Haruo

    1984-10-01

    Reflectance spectra of a single crystal of the charge-transfer complex between benzidine and 7,7,8,8-tetracyano- p-quino-dimethane (TCNQ) were measured at 30 K. The vibrational structure of the first charge-transfer band was found to be associated mainly with the intramolecular vibration of TCNQ. From its oscillator strength, the degree of charge transfer was estimated to be 0.28 at room temperature and 0.43 at 30 K. It is concluded that the charge-transfer exciton in this crystal is of localized nature.

  18. On the structure of iodine charge-transfer complexes in solution

    NASA Astrophysics Data System (ADS)

    Walker, Larry A., II; Pullen, Stuart; Donovan, Brent; Sension, Roseanne J.

    1995-08-01

    Femtosecond transient absorption studies of charge-transfer complexes of I 2 with hexamethylbenzene have been performed in a series of noncomplexing solvents. Anisotropy measurements of the bleach of the charge-transfer absorption band indicate that the geometry and electronic structure of the complex is dependent upon the solvent environment. The results are interpreted as favoring an oblique, nearly axial, geometry in alkanes and a resting geometry in chlorinated methanes.

  19. Spectrophotometric study of the charge-transfer complexes of iodine with antipyrine in organic solvents

    NASA Astrophysics Data System (ADS)

    Hasani, Masoumeh; Rezaei, Alireza

    2006-12-01

    The charge-transfer complex formation of iodine with antipyrine has been studied spectrophotometrically in chloroform, dichloromethane (DCM) and 1,2-dichloroethane (DCE) solutions at 25 °C. The results indicate the formation of 1:1 charge-transfer complexes. The observed time dependence of the charge-transfer band and subsequent formation of I 3- in solution were related to the slow transformation of the initially formed 1:1 antipyrine:I 2 outer complex to an inner electron donor-acceptor (EDA) complex, followed by fast reaction of the inner complex with iodine to form a triiodide ion. The values of the equilibrium constant, K, are calculated for each complex and the influence of the solvent properties on the formation of EDA complexes and the rates of subsequent reaction is evaluated.

  20. Spectrophotometric study of the charge-transfer complexes of iodine with antipyrine in organic solvents.

    PubMed

    Hasani, Masoumeh; Rezaei, Alireza

    2006-12-01

    The charge-transfer complex formation of iodine with antipyrine has been studied spectrophotometrically in chloroform, dichloromethane (DCM) and 1,2-dichloroethane (DCE) solutions at 25 degrees C. The results indicate the formation of 1:1 charge-transfer complexes. The observed time dependence of the charge-transfer band and subsequent formation of I(3)(-) in solution were related to the slow transformation of the initially formed 1:1 antipyrine:I(2) outer complex to an inner electron donor-acceptor (EDA) complex, followed by fast reaction of the inner complex with iodine to form a triiodide ion. The values of the equilibrium constant, K, are calculated for each complex and the influence of the solvent properties on the formation of EDA complexes and the rates of subsequent reaction is evaluated.

  1. Spectrophotometric study of the charge transfer complex between 2-amino-4-picoline with chloranilic acid

    NASA Astrophysics Data System (ADS)

    Alghanmi, Reem M.; Al-Attas, Amirah S.; Habeeb, Moustafa M.

    2013-02-01

    Charge transfer complex formation between 2-amino-4-picoline (2A4P) as the electron donor with chloranilic acid (CLA) as the electron acceptor has been studied spectrophotometrically in different polar solvents included acetone (AcN), ethanol (EtOH) and acetonitrile (AN). The molecular composition of the formed complex was recognized utilizing Job's, photometric and conductometric titration methods to be 1:1. The formation constants and molecular extinction coefficients were estimated using Benesi-Hildebrand equation; they recorded high values confirming high stability of the formed complex. Moreover, the results showed that the complex is more stable in acetone with lower electric permittivity compared with ethanol or acetonitrile of higher ones. The values of some spectroscopic physical parameters like oscillator strength f, transition dipole moment μ, resonance energy RN, charge transfer energy ECT, dissociation energy W, ionization potential IP and standard free energy ΔGo were determined and evaluated. The solid complex was isolated and its molecular composition was determined by elemental analysis to be 1:1. Furthermore, the solid complex was characterized using FTIR and 1H NMR measurements. They confirmed the presence of proton transfer beside charge transfer in the obtained complex. Molecular orbital calculations utilizing GAMESS computations were carried out to predict infrared spectra. They also confirmed the presence of proton transfer beside charge transfer in the formed complex.

  2. Why are the Interaction Energies of Charge-Transfer Complexes Challenging for DFT?

    PubMed

    Steinmann, Stephan N; Piemontesi, Cyril; Delachat, Aurore; Corminboeuf, Clemence

    2012-05-08

    The description of ground state charge-transfer complexes is highly challenging. Illustrative examples include large overestimations of charge-transfer by local and semilocal density functional approximations as well as inaccurate binding energies. It is demonstrated here that standard density functionals fail to accurately describe interaction energies of charge-transfer complexes not only because of the missing long-range exchange as generally assumed but also as a result of the neglect of weak interactions. Thus, accounting for the missing van der Waals interactions is of key importance. These assertions, based on the evaluation of the extent of stabilization due to dispersion using both DFT coupled with our recent density-dependent dispersion correction (dDsC) and high-level ab initio computations, reflect the imperfect error-cancellation between the overestimation of charge-transfer and the missing long-range interactions. An in-depth energy decomposition analysis of an illustrative series of four small ambidentate molecules (HCN, HNC, HF, and ClF) bound together with NF3 provides the main conclusions, which are validated on a prototypical organic charge-transfer complex (i.e., tetrathiafulvalene-tetracyanoquinodimethane, TTF-TCNQ). We establish that the interaction energies for charge-transfer complexes can only be properly described when using well-balanced functionals such as PBE0-dDsC, M06-2X, and LC-BOP-LRD.

  3. Spectrophotometric and some thermodynamic parameters of the charge transfer complexation between chloranilic acid and chlorpheniramine.

    PubMed

    Ofoefule, S I; Ajali, U

    2001-01-01

    The principle of charge transfer complexation involving a pi-acceptor (chloranilic acid) and an n-donor (chlorpheniramine) was utilized in the assay of the later in its pure form and in its tablet dosage forms. Some thermodynamic parameters of the complex such as association constant (Kc), molar absorptivity (epsilon c), free energy change (delta G degree), enthalpy (delta H degree) and entropy (delta S degree) changes were determined to establish the stability of the complex and the optimum conditions for the complex formation. The values obtained for these thermodynamic parameters indicated that the complex formed between this two chemical entities is highly stable. Assay of chlorpheniramine in its pure form and in its tablet dosage forms gave high percentage recoveries. The principle of charge transfer complexation could therefore be employed in the colorimetric assay of chlorpheniramine in its tablet dosage forms.

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

    PubMed

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

    2012-09-06

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

  5. Charge-transfer complexes of 4-nitrocatechol with some amino alcohols

    NASA Astrophysics Data System (ADS)

    Baniyaghoob, Sahar; Najafpour, Mohammad Mahdi; Boghaei, Davar M.

    2010-03-01

    Charge-transfer (CT) complexes formed from the reactions of 4-nitropyrocatechol (4-nCat) as an electron acceptor with four amino alcohols: 2-aminoethanol, 1-amino-2-propanol, 4-aminobutanol and N-(2-hydroxyethyl)-1,3-diaminopropane (NHEDAP) as electron donors, have been studied spectrophotometrically in H 2O and H 2O/EtOH at 20, 25, 30, 35 and 40 °C. The calculated values of the oscillator strength and transition moment confirm the formation of CT-complexes. The thermodynamic and spectroscopic parameters were also evaluated for the formation of CT-complexes. The equilibrium constants ranged from 9.00 to 2.20 l mol -1 (M -1). These interactions are exothermic and have relatively large standard enthalpy and entropy changes (Δ H values ranged from -15.58 to -3.10 kJ mol -1; Δ S ranged from 26.81 to -3.25 J K -1 mol -1). The solid CT-complexes have been synthesized and characterized by IR, NMR, mass spectrometry and thermal analysis. The photometric titration curves and other spectrometric data for the reactions indicated that the data obtained refer to the formation of 1:1 charge-transfer complex of [(4-nCat) (NHEDAP)] and 1:2 charge-transfer complexes of other amino alcohols [(4-nCat) (amino alcohol) 2]. The effect of alkali and alkaline earth metals on increasing the equilibrium constant of the CT-complexation was also investigated.

  6. Full-electron ligand-to-ligand charge transfer in a compact Re(I) complex.

    PubMed

    Yue, Yuankai; Grusenmeyer, Tod; Ma, Zheng; Zhang, Peng; Schmehl, Russell H; Beratan, David N; Rubtsov, Igor V

    2014-11-13

    Ligand-to-ligand charge transfer (LLCT) states in transition metal complexes are often characterized by fractional electron transfer due to coupling of the LLCT state with many other states via the metal. We designed and characterized a compact Re(I) complex that displays essentially full-electron charge transfer in the LLCT excited state. The complex, [Re(DCEB)(CO)3(L)](+) (DCEB = 4,4'-dicarboxyethyl-2,2'-bipyridine), referred to as ReEBA, features two redox active ligands with strong electron accepting (DCEB) and electron donating (L is 3-dimethylaminobenzonitrile (3DMABN)) properties. The lowest energy excited state formed with a ca. 10 ps time constant and was characterized as the full-electron 3DMABN → DCEB LLCT state using time-resolved infrared spectroscopy (TRIR), transient absorption spectroscopy, and DFT computations. Analysis of a range of vibrational modes helped to assign the charge transfer characteristics of the complex. The LLCT state lifetime in ReEBA shows a strong dependence on the solvent polarity and features solvent dependent frequency shifts for several vibrational reporters. The formation of a full-electron LLCT state (∼92%) was enabled by tuning the redox properties of the electron accepting ligand (DCEB) and simultaneously decoupling the redox active group of the electron donating ligand (3DMABN) from the metal center. This strategy is generally applicable for designing compact transition metal complexes that have full-electron LLCT states.

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

    NASA Astrophysics Data System (ADS)

    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.

  8. A novel spectrophotometric determination of trace copper based on charge transfer complex

    NASA Astrophysics Data System (ADS)

    Di, Junwei; Wu, Ying; Ma, Yun

    2005-03-01

    A new type of colored complex, the charge transfer complex, was used to develop the spectrophotometric determination of copper. The method was based on the formation of a colored product, the charge transfer complex of copper substituted tungstophosphate with 3,3',5,5'-tetramethybenzidine (TMB), which was stabilized and sensitized by the addition of polyvinyl alcohol (PVA) in aqueous solution. The structure of copper substituted tungstophosphate was Keggin-type according to the results of infrared (IR) spectra. The optimum reaction conditions and other important analytic parameters had been investigated. Beer's law was obeyed in the copper(II) concentration range of 0.003-0.1 μg mL -1, and the molar absorptivity at 660 nm is 2.54×10 5 L mol -1 cm -1. The proposed method was simple, selective, and sensitive. It was applied to the analytic samples with satisfactory results.

  9. Direct detection of photoinduced charge transfer complexes in polymer fullerene blends

    NASA Astrophysics Data System (ADS)

    Behrends, Jan; Sperlich, Andreas; Schnegg, Alexander; Biskup, Till; Teutloff, Christian; Lips, Klaus; Dyakonov, Vladimir; Bittl, Robert

    2012-03-01

    We report transient electron paramagnetic resonance (trEPR) measurements with submicrosecond time resolution performed on a polymer:fullerene blend consisting of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl C61-butyric acid methyl ester (PCBM) at low temperatures. The trEPR spectrum immediately following photoexcitation reveals signatures of spin-correlated polaron pairs. The pair partners (positive polarons in P3HT and negative polarons in PCBM) can be identified by their characteristic g values. The fact that the polaron pair states exhibit strong non-Boltzmann population unambiguously shows that the constituents of each pair are geminate, i.e., originate from one exciton. We demonstrate that coupled polaron pairs are present even several microseconds after charge transfer and suggest that they embody the intermediate charge transfer complexes that form at the donor/acceptor interface and mediate the conversion from excitons into free charge carriers.

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

    PubMed

    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.

  11. Dependence of (35)Cl NQR on hydrogen bonding and temperature in dichlorophenol-aniline charge transfer complexes.

    PubMed

    Ramananda, D; Ramesh, K P; Uchil, J

    2007-10-01

    The hydrogen-bonded charge transfer complexes of aniline with pi-acceptors (or proton donors) such as 2,5-, 2,6-, 3,4- and 3,5-dichlorophenol were prepared. The (35)Cl nuclear quadrupole resonance (NQR) frequencies of these charge transfer complexes in the temperature range 77-300 K were measured to ascertain the existence or otherwise of a phase transition upon complex formation. Further, the NQR frequency and asymmetry parameter of the electric field gradient at the site of quadrupole nucleus were used to estimate the chemical bond parameters, namely ionic bond, double bond character of the carbon-chlorine(C--Cl) bond and the percentage charge transfer between the donor-acceptor components in charge transfer complexes. The effect of hydrogen bonding and temperature on the charge transfer process is analysed. (c) 2007 John Wiley & Sons, Ltd.

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

    NASA Astrophysics Data System (ADS)

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

    2010-03-01

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

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

    PubMed Central

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

    2008-01-01

    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. PMID:18832175

  14. Charge-transfer complexes of bromine atoms with haloalkanes and alkanes

    SciTech Connect

    Alfassi, Z.B.; Huie, R.E.; Neta, P. ); Mittal, J.P.; Shoute, L.C.T. )

    1993-09-09

    Charge-transfer complexes of bromine atoms with haloalkanes and alkanes were produced by pulse radiolysis and by laser-flash photolysis in various organic solvents. Br atoms were produced by photolysis of Br[sub 2] (at 351 or 248 nm), by photolysis of bromoalkanes (at 248 nm), or by radiolysis of bromoalkanes (either in liquid form or in cyclohexane solutions). The transient spectra, monitored within microseconds after the pulse, had absorption maxima that varied between 300 and 500 nm and are ascribed to complexes of Br atoms with the various solvents or other solutes present. The absorption maxima for Br atom complexes with alkanes and chloroalkanes correlate with the ionization potential of these molecules, suggesting the existence of charge-transfer complexes. The correlation for the bromoalkanes was more complex. CBr[sub 4]Br and CHBr[sub 3][center dot]Br were observed to react rapidly (k = 10[sup 8]-10[sup 9] L mol[sup [minus]1] s[sup [minus]1]) with Br[sub 2] and with HBr to transfer their Br atom to these latter molecules. 16 refs., 5 figs., 2 tabs.

  15. Spectroscopic evidence for charge-transfer complexation in monoclonal antibodies that bind opiates.

    PubMed

    Droupadi, P R; Meyers, E A; Linthicum, D S

    1994-04-01

    Molecular complexes of four monoclonal anti-morphine antibodies (mAb) with the opiate ligands morphine, oxymorphone, and naloxone were studied using UV-VIS absorption spectroscopy. Although strong overlaps in the absorption spectra of the antibodies, ligands, and complexes were observed, a curve-fitting method was developed to correlate the absorbance with the concentration of the ligand-antibody complex. Using this technique, we determined the intrinsic association constants for the mAb with morphine to be in the nanomolar range, while association constants for oxymorphone and naloxone were in the micromolar range. These values were found to be in agreement with previous radioimmunoassay determinations. We also observed different changes in the absorbancy of the mAb upon complexation with different ligands and such changes were found to be different for all four mAb examined. Upon complexation with the ligand morphine, two of the mAb (clone numbers MOR368-21 and MOR10.5) displayed distinct charge-transfer spectral bands in the 320-nm region. These observations suggest that mAb binding site tryptophans may participate in the formation of the antibody-ligand complex and such complexation involves a charge-transfer interaction.

  16. Theoretical Investigation of OCN(-) Charge Transfer Complexes in Condensed Phase Media: Spectroscopic Properties in Amorphous Ice

    NASA Technical Reports Server (NTRS)

    Park, Jin-Young; Woon, David E.

    2004-01-01

    Density functional theory (DFT) calculations of cyanate (OCN(-)) charge-transfer complexes were performed to model the "XCN" feature observed in interstellar icy grain mantles. OCN(-) charge-transfer complexes were formed from precursor combinations of HNCO or HOCN with either NH3 or H2O. Three different solvation strategies for realistically modeling the ice matrix environment were explored, including (1) continuum solvation, (2) pure DFT cluster calculations, and (3) an ONIOM DFT/PM3 cluster calculation. The model complexes were evaluated by their ability to reproduce seven spectroscopic measurements associated with XCN: the band origin of the OCN(-) asymmetric stretching mode, shifts in that frequency due to isotopic substitutions of C, N, O, and H, plus two weak features. The continuum solvent field method produced results consistent with some of the experimental data but failed to account for other behavior due to its limited capacity to describe molecular interactions with solvent. DFT cluster calculations successfully reproduced the available spectroscopic measurements very well. In particular, the deuterium shift showed excellent agreement in complexes where OCN(-) was fully solvated. Detailed studies of representative complexes including from two to twelve water molecules allowed the exploration of various possible solvation structures and provided insights into solvation trends. Moreover, complexes arising from cyanic or isocyanic acid in pure water suggested an alternative mechanism for the formation of OCN(-) charge-transfer complexes without the need for a strong base such as NH3 to be present. An extended ONIOM (B3LYP/PM3) cluster calculation was also performed to assess the impact of a more realistic environment on HNCO dissociation in pure water.

  17. Theoretical Investigation of OCN(-) Charge Transfer Complexes in Condensed Phase Media: Spectroscopic Properties in Amorphous Ice

    NASA Technical Reports Server (NTRS)

    Park, Jin-Young; Woon, David E.

    2004-01-01

    Density functional theory (DFT) calculations of cyanate (OCN(-)) charge-transfer complexes were performed to model the "XCN" feature observed in interstellar icy grain mantles. OCN(-) charge-transfer complexes were formed from precursor combinations of HNCO or HOCN with either NH3 or H2O. Three different solvation strategies for realistically modeling the ice matrix environment were explored, including (1) continuum solvation, (2) pure DFT cluster calculations, and (3) an ONIOM DFT/PM3 cluster calculation. The model complexes were evaluated by their ability to reproduce seven spectroscopic measurements associated with XCN: the band origin of the OCN(-) asymmetric stretching mode, shifts in that frequency due to isotopic substitutions of C, N, O, and H, plus two weak features. The continuum solvent field method produced results consistent with some of the experimental data but failed to account for other behavior due to its limited capacity to describe molecular interactions with solvent. DFT cluster calculations successfully reproduced the available spectroscopic measurements very well. In particular, the deuterium shift showed excellent agreement in complexes where OCN(-) was fully solvated. Detailed studies of representative complexes including from two to twelve water molecules allowed the exploration of various possible solvation structures and provided insights into solvation trends. Moreover, complexes arising from cyanic or isocyanic acid in pure water suggested an alternative mechanism for the formation of OCN(-) charge-transfer complexes without the need for a strong base such as NH3 to be present. An extended ONIOM (B3LYP/PM3) cluster calculation was also performed to assess the impact of a more realistic environment on HNCO dissociation in pure water.

  18. Atomic dipole polarization in charge-transfer complexes with halogen bonding.

    PubMed

    Bartashevich, E V; Tsirelson, V G

    2013-02-21

    The polarization effects associated with halogen bonding for the series of charge-transfer complexes D(m)···X-Y, where donor molecules D(m) = NH(3), H(2)O, H(2)S, C(2)H(4), CO and X-Y = Cl(2), ClF, Br(2), BrCl, ICl, I(2), are characterized in terms of the quantum theory of atoms in molecules using the B3LYP/6-311** Kohn-Sham wave functions. We study the electrostatic potential features of separate donor and acceptor molecules, the change in atomic charges as well as the atomic electric dipole moments and their components, and the intra-atomic electron density dipole polarization and the bonding dipole moments resulting from the electron density redistribution between the molecules in the charge-transfer complexes. The equation linking the most negative electrostatic potential values in the donor molecules and the most positive values in dihalogen molecules with the stretching force constants was found using two-factor regression. It is demonstrated that the dipole polarization of the acceptor atom mirrors the strength of halogen bonding in complexes in a series of different donors and acceptors. An exponential relationship between the magnitude of the total atomic electric dipole moment of the acceptor atom and the intermolecular stretching force constant is established for weakly bounded complexes.

  19. Charge-transfer complexes of Cu(II)/HD analogue in sol gel sensors

    NASA Astrophysics Data System (ADS)

    Brinkley, J. F.; Kirkey, M. L.; Marques, A. D. S.; Lin, C. T.

    2003-01-01

    An optically transparent xerogel encapsulating Cu(II) acetate is fabricated to detect mustard gas (HD) analogues via a charge-transfer mechanism. A fast response (color change from sky blue to canary yellow) is observed for the chlorinated sulfide, and is accompanied by an absorption band at 370-420 nm. MO calculations revealed that the chlorinated HD analogue displays a charge-transfer transition extended from sulfur to chlorine atom. A 1:1 complex of Cu(II)/HD analogue is preferred. For a colorimetric sol-gel detector prepared at pH 3, the detection limit of HD analogue is calibrated at 0.03 μl per 1.5 ml sensor volume.

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

    NASA Astrophysics Data System (ADS)

    Shukla, Madhulata; Srivastava, Nitin; Saha, Satyen

    2012-08-01

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

  1. From charge transfer to electron transfer in halogen-bonded complexes of electrophilic bromocarbons with halide anions.

    PubMed

    Rosokha, Sergiy V; Traversa, Alfredo

    2015-02-21

    Experimental and computational studies of the halogen-bonded complexes, [R-Br, X(-)], of bromosubstituted electrophiles, R-Br, and halide anions, X(-), revealed that decrease of a gap between the frontier orbitals of interacting species led to reduction of the energy of the optical charge-transfer transition and to increase in the ground-state charge transfer (X(-) → R-Br) in their associates. These variations were accompanied by weakening of the intramolecular, C-Br, and strengthening of the intermolecular, BrX(-), bonds. In the limit of the strongest electron donor-acceptor pairs, formation of the halogen-bonded complexes was followed by the oxidation of iodide to triiodide, which took place despite the fact that the I(-) → R-Br electron-transfer step was highly endergonic and the calculated outer-sphere rate constant was negligibly small. However, the calculated barrier for the inner-sphere electron transfer accompanied by the halogen transfer, R-BrI(-) → R˙Br-I(-)˙, was nearly 24 kcal mol(-1) lower as compared to that calculated for the outer-sphere process and the rate constant of such reaction was consistent with the experimental kinetics. A dramatic decrease of the electron-transfer barriers (leading to 18-orders of magnitude increase of the rate constant) was related to the strong electronic coupling of the donor and acceptor within the halogen-bonded precursor complex, as well as to the lower solvent reorganization energy and the successor-complex stabilization.

  2. Study of charge transfer complexes of [70]fullerene with phenol and substituted phenols.

    PubMed

    Bhattacharya, Sumanta; Banerjee, Shrabanti; Banerjee, Manas

    2005-07-01

    To improve the understanding of the charge transfer (CT) interaction of [70]fullerene with electron donors, interaction of [70]fullerene with a series of phenols, e.g., phenol, resorcinol and p-quinol were studied in 1,4-dioxan medium using absorption spectroscopy. An absorption band due to CT transition was observed in the visible region. The experimental CT transition energies (h nuCT) are well correlated (through Mulliken's equation) with the vertical ionisation potentials (I(D)v) of the series of phenols studied. From an analysis of this correlation degrees of charge transfer for the [70]fullerene-phenol complexes were estimated. The degrees of charge transfer in the ground state of the complexes have been found to be very low (<2%). The h nuCT values change systematically as the number and position of the -OH groups change on the aromatic ring of the phenol moiety. From the trends in the h nuCT values, the Hückel parameters (h(O) and k(C-O)) for the -OH group were obtained in a straightforward way and the values so obtained, viz., 1.91 and 1.0, respectively, are close to the ones (1.8 and 0.8) recommended by Streitwieser on the basis of other evidence. Oscillator strengths, transition dipole strengths and resonance energies of the [70]fullerene-phenol complexes were determined. Formation constants of the CT complexes were determined at four different temperatures from which enthalpies and entropies of formation of the complexes were estimated.

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

    PubMed

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

    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(-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.

  4. Structure and Bonding in Nickel-Thiolate-Iodine Charge-Transfer Complexes.

    PubMed

    Beyer, Norman; Steinfeld, Gunther; Lozan, Vasile; Naumov, Sergej; Flyunt, Roman; Abel, Bernd; Kersting, Berthold

    2017-02-16

    The dinuclear nickel complexes [Ni2 L(μ-O2 CR)](ClO4 ) [R=Me (4), R=OMe (6)], where L(2-) is a 24-membered macrocyclic N6 S2 ligand, react readily with excess I2 in MeCN solution at 4 °C to form stable mono-(I2 ) and bis-(I2 ) charge-transfer (CT) adducts of the type [Ni2 L(μ-O2 CR)(I2 )n ](+) (n=1 or 2) containing linear RS-I-I linkages. Three new CT compounds, namely, [Ni2 L(OAc)(I2 )](I2 )(I3 ) (5), [Ni2 L(O2 COMe)(I2 )](I5 )⋅MeCN (7⋅MeCN), and [Ni2 L(O2 COMe)(I2 )2 ](I5 )⋅MeCN (8⋅MeCN) as well as the triiodide salt [Ni2 L(OAc)](I3 ) (9) were synthesized and fully characterized. A common feature of the CT adducts is a polyiodide matrix, which surrounds the individual complex molecules, stabilized by secondary I⋅⋅⋅I interactions with the CT linkages. The scatter in both the RS-I (2.6 to 3.0 Å) and the I-I bond lengths (2.7 to 3.0 Å) is indicative of both a variable strength of the RS(-) →I2 bond and a varying degree of charge transfer. An analysis of the structural parameters was undertaken accompanied by DFT calculations to quantify the donating ability of the bridging thiolate functions and to shed more light on the bonding in this rare sort of charge-transfer complexes. The stability of the CT complexes and the results of preliminary transport measurements are also reported.

  5. Charge-transfer optical absorption mechanism of DNA:Ag-nanocluster complexes

    NASA Astrophysics Data System (ADS)

    Longuinhos, R.; Lúcio, A. D.; Chacham, H.; Alexandre, S. S.

    2016-05-01

    Optical properties of DNA:Ag-nanoclusters complexes have been successfully applied experimentally in Chemistry, Physics, and Biology. Nevertheless, the mechanisms behind their optical activity remain unresolved. In this work, we present a time-dependent density functional study of optical absorption in DNA:Ag4. In all 23 different complexes investigated, we obtain new absorption peaks in the visible region that are not found in either the isolated Ag4 or isolated DNA base pairs. Absorption from red to green are predominantly of charge-transfer character, from the Ag4 to the DNA fragment, while absorption in the blue-violet range are mostly associated to electronic transitions of a mixed character, involving either DNA-Ag4 hybrid orbitals or intracluster orbitals. We also investigate the role of exchange-correlation functionals in the calculated optical spectra. Significant differences are observed between the calculations using the PBE functional (without exact exchange) and the CAM-B3LYP functional (which partly includes exact exchange). Specifically, we observe a tendency of charge-transfer excitations to involve purines bases, and the PBE spectra error is more pronounced in the complexes where the Ag cluster is bound to the purines. Finally, our results also highlight the importance of adding both the complementary base pair and the sugar-phosphate backbone in order to properly characterize the absorption spectrum of DNA:Ag complexes.

  6. Preparation of metal-TCNQ charge-transfer complexes on conducting and insulating surfaces by photocrystallization.

    PubMed

    O'Mullane, Anthony P; Fay, Nigel; Nafady, Ayman; Bond, Alan M

    2007-02-21

    A generic method for the synthesis of metal-7,7,8,8-tetracyanoquinodimethane (TCNQ) charge-transfer complexes on both conducting and nonconducting substrates is achieved by photoexcitation of TCNQ in acetonitrile in the presence of a sacrificial electron donor and the relevant metal cation. The photochemical reaction leads to reduction of TCNQ to the TCNQ(-) monoanion. In the presence of M(x+)(MeCN), reaction with TCNQ(-)(MeCN) leads to deposition of M(x+)[TCNQ]x crystals onto a solid substrate with morphologies that are dependent on the metal cation. Thus, CuTCNQ phase I photocrystallizes as uniform microrods, KTCNQ as microrods with a random size distribution, AgTCNQ as very long nanowires up to 30 mum in length and with diameters of less than 180 nm, and Co[TCNQ](2)(H(2)O)(2) as nanorods and wires. The described charge-transfer complexes have been characterized by optical and scanning electron microscopy and IR and Raman spectroscopy. The CuTCNQ and AgTCNQ complexes are of particular interest for use in memory storage and switching devices. In principle, this simple technique can be employed to generate all classes of metal-TCNQ complexes and opens up the possibility to pattern them in a controlled manner on any type of substrate.

  7. Complex and charge transfer between TiO2 and pyrroloquinoline quinone.

    PubMed

    Dimitrijevic, Nada M; Poluektov, Oleg G; Saponjic, Zoran V; Rajh, Tijana

    2006-12-21

    Pyrroloquinoline quinone (PQQ) forms a tridentate complex with coordinatively unsaturated titanium atoms on the surface of approximately 4.5 nm TiO2 particles; an association constant of K = 550 M-1 per Ti(IV)surf has been determined. Low-temperature electron paramagnetic resonance was employed in identification of localized charges and consequently produced radicals and in determination of charge-transfer processes. The photoexcitation of the PQQ-TiO2 complex results in the transfer of conduction band electrons from TiO2 to bound PQQ and the formation of the semiquinone radical. Attaching dopamine (DA) as an electron donor and PQQ as an electron acceptor on the surface of TiO2 results in spatial separation of photogenerated charges; the holes localize on dopamine and electrons on PQQ, with higher yields than for each component separately. In this triad-type assembly (PQQ-TiO2/DA) the PQQ that is bound to the particles acts as a sink for electrons allowing their almost complete scavenging even at temperature as low as 4 K.

  8. Spectroscopic studies of charge transfer complexes between colchicine and some π acceptors

    NASA Astrophysics Data System (ADS)

    Arslan, Mustafa; Duymus, Hulya

    2007-07-01

    Charge transfer complexes between colchicine as donor and π acceptors such as tetracyanoethylene (TCNE), 2,3-dichloro-5,6-dicyano- p-benzoquinone (DDQ), p-chloranil ( p-CHL) have been studied spectrophotometrically in dichloromethane at 21 °C. The stoichiometry of the complexes was found to be 1:1 ratio by the Job method between donor and acceptors with the maximum absorption band at a wavelength of 535, 585 and 515 nm. The equilibrium constant and thermodynamic parameters of the complexes were determined by Benesi-Hildebrand and van't Hoff equations. Colchicine in pure form and in dosage form was applied in this study. The formation constants for the complexes were shown to be dependent on the structure of the electron acceptors used.

  9. Potential Energy Surfaces and Charge Transfer of PAH-Sodium-PAH Complexes.

    PubMed

    Hjertenaes, Eirik; Andersson, Stefan; Koch, Henrik

    2016-09-19

    To further understanding of the role of sodium in carbon cathode degradation in Hall-Héroult cells, potential-energy surfaces and charge-transfer curves are presented for finite-size complexes of sodium intercalated between various polycyclic aromatic hydrocarbons. Calculations for lithium and potassium are included to highlight the disparate intercalation behaviour of the alkali metals in graphite intercalation compounds. Static energy barriers from DFT are used to compute macroscopic diffusion coefficients according to transition-state theory. Comparing the calculated diffusion coefficient to experimental values from the literature sheds light on the role of lattice diffusion of sodium-graphite intercalation compounds in sodium intrusion in graphitic carbon cathodes.

  10. Formation of charge-transfer-complex in organic:metal oxides systems

    NASA Astrophysics Data System (ADS)

    Wu, S. P.; Kang, Y.; Liu, T. L.; Jin, Z. H.; Jiang, N.; Lu, Z. H.

    2013-04-01

    It is found that composite systems consisting of 4,4'-bis(carbazol-9-yl)biphenyl (CBP) and molybdenum trioxide (MoO3) form an IR absorption band around 847 nm. It is also found that the vibrational modes of the CBP, as measured by Fourier Transform Infrared Spectroscopy, are quenched upon the formation of charge-transfer-complex (CTC) between CBP and MoO3. By examining several sets of organic:metal oxides systems, we discovered that the IR absorption band of the CTCs follow two distinct mechanisms depending on the nature and location of the HOMOs in the organic molecules.

  11. Charge-transfer complexation as a general phenomenon in the copigmentation of anthocyanins.

    PubMed

    Ferreira da Silva, Palmira; Lima, João C; Freitas, Adilson A; Shimizu, Karina; Maçanita, Antonio L; Quina, Frank H

    2005-08-18

    Color intensification of anthocyanin solutions in the presence of natural polyphenols (copigmentation) is re-interpreted in terms of charge transfer from the copigment to the anthocyanin. Flavylium cations are shown to be excellent electron acceptors (E(red) approximately -0.3 V vs SCE). It is also demonstrated, for a large series of anthocyanin-copigment pairs, that the standard Gibbs free energy of complex formation decreases linearly with EA(Anthoc) - IP(Cop), the difference between the electron affinity of the anthocyanin, EA(Anthoc), and the ionization potential of the copigment, IP(Cop). Based on this correlation, copigmentation strengths of potential candidates for copigments can be predicted.

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

    NASA Astrophysics Data System (ADS)

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

    2011-06-01

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

  13. Identifying the magnetoconductance responses by the induced charge transfer complex states in pentacene-based diodes

    NASA Astrophysics Data System (ADS)

    Huang, Wei-Shun; Lee, Tsung-Hsun; Guo, Tzung-Fang; Huang, J. C. A.; Wen, Ten-Chin

    2012-07-01

    We investigate the magnetoconductance (MC) responses in photocurrent, unipolar injection, and bipolar injection regimes in pentacene-based diodes. Both photocurrent and bipolar injection contributed MC responses show large difference in MC line shape, which are attributed to triplet-polaron interaction modulated by the magnetic field dependent singlet fission and the intersystem crossing of the polaron pair, respectively. By blending 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane into pentacene, all the MC responses are suppressed but the MC response at unipolar injection regime is enhanced, which is attributed to the induced charge transfer complex states (CT complex states). This work identify the MC responses between single carrier contributed MC and exciton related MC by the induced CT complex states.

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

    NASA Astrophysics Data System (ADS)

    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.

  15. Charge transfer in deoxyribonucleic acid (DNA): Static disorder, dynamic fluctuations and complex kinetic

    NASA Astrophysics Data System (ADS)

    Edirisinghe Pathirannehelage, Neranjan S.

    The fact that loosely bonded DNA bases could tolerate large structural fluctuations, form a dissipative environment for a charge traveling through the DNA. Nonlinear stochastic nature of structural fluctuations facilitates rich charge dynamics in DNA. We study the complex charge dynamics by solving a nonlinear, stochastic, coupled system of differential equations. Charge transfer between donor and acceptor in DNA occurs via different mechanisms depending on the distance between donor and acceptor. It changes from tunneling regime to a polaron assisted hopping regime depending on the donor-acceptor separation. Also we found that charge transport strongly depends on the feasibility of polaron formation. Hence it has complex dependence on temperature and charge-vibrations coupling strength. Mismatched base pairs, such as different conformations of the G·A mispair, cause only minor structural changes in the host DNA molecule, thereby making mispair recognition an arduous task. Electron transport in DNA that depends strongly on the hopping transfer integrals between the nearest base pairs, which in turn are affected by the presence of a mispair, might be an attractive approach in this regard. I report here on our investigations, via the I-V characteristics, of the effect of a mispair on the electrical properties of homogeneous and generic DNA molecules. The I-V characteristics of DNA were studied numerically within the double-stranded tight-binding model. The parameters of the tight-binding model, such as the transfer integrals and on-site energies, are determined from first-principles calculations. The changes in electrical current through the DNA chain due to the presence of a mispair depend on the conformation of the G·A mispair and are appreciable for DNA consisting of up to 90 base pairs. For homogeneous DNA sequences the current through DNA is suppressed and the strongest suppression is realized for the G(anti)·A(syn) conformation of the G·A mispair. For

  16. Ionic Charge Transfer Complex Induced Visible Light Harvesting and Photocharge Generation in Perovskite.

    PubMed

    Ng, Tsz-Wai; Thachoth Chandran, Hrisheekesh; Chan, Chiu-Yee; Lo, Ming-Fai; Lee, Chun-Sing

    2015-09-16

    Organometal trihalide perovskite has recently emerged as a new class of promising material for high efficiency solar cells applications. While excess ions in perovskites are recently getting a great deal of attention, there is so far no clear understanding on both their formation and relating ions interaction to the photocharge generation in perovskite. Herein, we showed that tremendous ions indeed form during the initial stage of perovskite formation when the organic methylammonium halide (MAXa, Xa=Br and I) meets the inorganic PbXb2 (Xb=Cl, Br, I). The strong charge exchanges between the Pb2+ cations and Xa- anions result in formation of ionic charge transfer complexes (iCTC). MAXa parties induce empty valence electronic states within the forbidden bandgap of PbXb2. The strong surface dipole provide sufficient driving force for sub-bandgap electron transition with energy identical to the optical bandgap of forming perovskites. Evidences from XPS/UPS and photoluminescence studies showed that the light absorption, exciton dissociation, and photocharge generation of the perovskites are closely related to the strong ionic charge transfer interactions between Pb2+ and Xa- ions in the perovskite lattices. Our results shed light on mechanisms of light harvesting and subsequent free carrier generation in perovskites.

  17. Spectrophotometric and electrical studies of charge-transfer complexes of sodium flucloxacillin with π-acceptors

    NASA Astrophysics Data System (ADS)

    Refat, Moamen S.; El-Didamony, Akram M.

    2006-11-01

    The present study is interested to develop a simple, rapid and accurate spectrophotometric method for determination of sodium flucloxacillin (fluc) in pure form and pharmaceutical formulations. The charge-transfer (CT) interactions between sodium flucloxacillin as electron donor and chloranilic acid (CLA), dichloroquinone 4-chloroimide (DCQ), 2,3-dichloro-5,6-dicyano- p-benzoquinone (DDQ) and 7,7,8,8 tetracyano- p-quinodimethane (TCNQ), as π-electron acceptors have been investigated spectrophotometrically. Different variables affecting the reaction were studied and optimized. Under the optimum conditions, linear relationships with good correlation coefficients (0.9979-0.9995) were found between the absorbance and the concentration of the drug in the range 16-880 μg ml -1. The proposed methods were applied successfully to the determination of the examined drug either in pure or pharmaceutical dosage forms with good accuracy and precision. The formation of the CT-complexes and the sites of interaction were confirmed by elemental analysis CHN, UV-vis, IR, 1H NMR and mass spectra techniques. Based on Job's method of continuous variation plots, the obtained results indicate the formation of 1:1 charge-transfer complexes with the general formula [(fluc)(acceptor)]. Statistical analysis of the obtained results showed no significant difference between the proposed method and official method.

  18. Computational Confirmation of the Carrier for the "XCN" Interstellar Ice Bank: OCN(-) Charge Transfer Complexes

    NASA Technical Reports Server (NTRS)

    Park, J.-Y.; Woon, D. E.

    2004-01-01

    Recent experimental studies provide evidence that carrier for the so-called XCN feature at 2165 cm(exp -1) (4.62 micron) in young stellar objects is an OCN(-)/NH4(+) charge transfer (CT) complex that forms in energetically processed interstellar icy grain mantles. Although other RCN nitriles and RCN iosonitriles have been considered, Greenberg's conjecture that OCN(-) is associated with the XCN feature has persisted for over 15 years. In this work we report a computational investigation that thoroughly confirms the hypothesis that the XCN feature observed in laboratory studies can result from OCN(-)/NH4(+) CT complexes arising from HNCO and NH3, in a water ice environment. Density functional theory calculations with theory calculations with HNCO, NH3, and up to 12 waters reproduce seven spectroscopic measurements associated with XCN: the band origin of the asymmetric stretching mode of OCN(-), shifts due to isotopic substitutions of C, N, O, and H, and two weak features. However, very similar values are also found for the OCN(-)/NH4(+) CT complex arising from HOCN and NH3. In both cases, the complex forms by barrierless proton transfer from HNCO or HOCN to NH3 during the optimization of the solvated system. Scaled B3LYP/6-31+G** harmonic frequencies for HNCO and HOCN cases are 2181 and 2202 cm(exp -1), respectively.

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

    SciTech Connect

    Bhargavi, R.; Nair, Geetha G. E-mail: skpras@gmail.com; Krishna Prasad, S. E-mail: skpras@gmail.com; Majumdar, R.; Bag, Braja G.

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

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

    2017-02-15

    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 1140cm(-1) assigned to νs(SO2), in contrast to the same mode in the 1:1 complex at 1115cm(-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.

  2. Charge separation and energy transfer in the photosystem II core complex studied by femtosecond midinfrared spectroscopy.

    PubMed

    Pawlowicz, N P; Groot, M-L; van Stokkum, I H M; Breton, J; van Grondelle, R

    2007-10-15

    The core of photosystem II (PSII) of green plants contains the reaction center (RC) proteins D1D2-cytb559 and two core antennas CP43 and CP47. We have used time-resolved visible pump/midinfrared probe spectroscopy in the region between 1600 and 1800 cm(-1) to study the energy transfer and charge separation events within PSII cores. The absorption difference spectra in the region of the keto and ester chlorophyll modes show spectral evolution with time constants of 3 ps, 27 ps, 200 ps, and 2 ns. Comparison of infrared (IR) difference spectra obtained for the isolated antennas CP43 and CP47 and the D1D2-RC with those measured for the PSII core allowed us to identify the features specific for each of the PSII core components. From the presence of the CP43 and CP47 specific features in the spectra up to time delays of 20-30 ps, we conclude that the main part of the energy transfer from the antennas to the RC occurs on this timescale. Direct excitation of the pigments in the RC evolution associated difference spectra to radical pair formation of PD1+PheoD1- on the same timescale as multi-excitation annihilation and excited state equilibration within the antennas CP43 and CP47, which occur within approximately 1-3 ps. The formation of the earlier radical pair ChlD1+PheoD1-, as identified in isolated D1D2 complexes with time-resolved mid-IR spectroscopy is not observed in the current data, probably because of its relatively low concentration. Relaxation of the state PD1+PheoD1-, caused by a drop in free energy, occurs in 200 ps in closed cores. We conclude that the kinetic model proposed earlier for the energy and electron transfer dynamics within the D1D2-RC, plus two slowly energy-transferring antennas C43 and CP47 explain the complex excited state and charge separation dynamics in the PSII core very well. We further show that the time-resolved IR-difference spectrum of PD1+PheoD1- as observed in PSII cores is virtually identical to that observed in the isolated D1D2-RC

  3. Competition between covalent bonding and charge transfer tendencies at complex-oxides interfaces

    NASA Astrophysics Data System (ADS)

    Salafranca, J.; Tornos, J.; García-Barriocanal, J.; León, C.; Santamaria, J.; Rincón, J.; Álvarez, G.; Pennycook, S. J.; Dagotto, E.; Varela, M.

    2013-03-01

    Interfaces alter the subtle balance among different degrees of freedom responsible for exotic phenomena in complex oxides, such as cuprate-manganite interfaces. We study these interfaces by means of scanning transmission electron microscopy and theoretical calculations. Microscopy and EEL spectroscopy indicate that the interfaces are sharp, and the chemical profile is symmetric with two equivalent interfaces. Spectroscopy also allows us to establish an oxidation state profile with sub-nanometer resolution. We find an anomalous charge redistribution: a non-monotonic behavior of the occupancy of d orbitals in the manganite layers as a function of distance to the interface. Relying on model calculations, we establish that this profile is a result of the competition between standard charge transfer tendencies involving materials with different chemical potentials and strong bonding effects across the interface. The competition can be tuned by different factors (temperature, doping, magnetic fields...). As examples, we report different charge distributions as a function of doping of the manganite layers. ACKNOWLEDGEMENTS ORNL:U.S. DOE-BES, Material Sciences and Engineering Division & ORNL's ShaRE. UCM:Juan de la Cierva, Ramon y Cajal, & ERC Starting Investigator Award programs.

  4. Soft versus hard junction formation for α-terthiophene molecular wires and their charge transfer complexes

    NASA Astrophysics Data System (ADS)

    Vezzoli, Andrea; Grace, Iain M.; Brooke, Carly; Nichols, Richard J.; Lambert, Colin J.; Higgins, Simon J.

    2017-03-01

    We used a range of scanning tunnelling microscopy (STM)-based methods to conduct a detailed study of single molecule junction conductance enhancement upon charge transfer complex formation, using bis(thiaalkyl)arene molecular wires as electron donors and tetracyanoethylene (TCNE) as an electron acceptor. Using the "hard" STM break junction (STM-BJ) method, in which a Au STM tip is pushed into a Au substrate and then withdrawn in the presence of molecules, we see a single, very broad, peak in the resulting conductance histogram when all data are used; the conductance enhancement is 25-fold for a terthiophene donor and 15-fold for a phenyl group. After rational data selection, in which only current-distance curves that contain a current plateau >0.2 nm long are used in the conductance histogram, three sharper peaks are resolved in the histograms for the charge transfer complexes; two substantially lower-conductance peaks are resolved for the uncomplexed molecules. Using the "soft" STM I(s) technique, in which initial contact between tip and substrate is avoided and the current limit is about an order of magnitude lower, we were able to resolve two peaks for the uncomplexed molecules depending upon the initial set point current (i.e., tip height), one at the same value as the lower of the two data-selected STM-BJ histogram peaks and an additional peak beyond the low-current limit for the STM-BJ experiment. For the terthiophene, the low, medium, and high conductance peaks for the TCNE complex are, respectively, ca. 70, 70, and 46 times higher in conductance than the corresponding peaks for the free molecule.

  5. Biocompatible organic charge transfer complex nanoparticles based on a semi-crystalline cellulose template.

    PubMed

    Nagai, Atsushi; Miller, Jason B; Du, Jia; Kos, Petra; Stefan, Mihaela C; Siegwart, Daniel J

    2015-07-28

    Using a bio-inspired cellulose template, new charge transfer (CT) nanoparticles (NPs) with unique and intriguing emission properties are reported. Pyrene-modified 2,3-di-O-methyl cellulose formed CT complexes with small molecule acceptors, e.g. 7,7,8,8-tetracyanoquinodimethane (TCNQ), and exhibited aggregation-induced emission (AIE) in aqueous medium upon nanoparticle formation. The TCNQ-CT NPs showed multicolor fluorescence emissions at 370-400 nm, 602 nm and 777 nm, when excited at 330 nm, 485 nm and 620 nm respectively. The cellulose-TCNQ NPs are biocompatible and demonstrate an advance in the use of the CT mechanism for biomedical imaging applications both in vitro and in vivo.

  6. Spectrophotometric determination of clobetasol propionate, halobetasol propionate, quinagolide hydrochloride, through charge transfer complexation.

    PubMed

    Mostafa, Azza A; Bebawy, Lories I; Refaat, Heba H

    2002-03-01

    Two spectrophotometric procedures are described for the determination of clobetasol propionate(I), halobetasol propionate(II) (corticosteroids) and quinagolide hydrochloride(III) (prolactin inhibitor). For corticosteroid drugs, the procedures are based on the formation of phenyl hydrazones of the corticosteroids which are subsequently subjected to charge transfer complexation reaction with either 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) as pi-acceptor or with iodine as sigma-acceptor. Prolactin inhibitor was reacted directly with the previous reagents. The molar ratios of the reactants were established and the experimental conditions were studied giving maximum absorption at 588 and 290 nm with DDQ and iodine methods, respectively for the three drugs. The concentration ranges were 20-150,50-300, and 20-80 microg ml(-1) in DDQ method for (I), (II), and (III), respectively and 13-20,15-40, and 8-32 microg ml(-1) in iodine method for (I), (II) and (III), respectively.

  7. Spectrophotometric study of the charge transfer complexation of some porphyrin derivatives as electron donors with tetracyanoethylene.

    PubMed

    El-Zaria, Mohamed E

    2008-01-01

    Charge transfer complexes (CTC) of 5,10,15,20-tetraphenylporphyrin (TPP), 5,10,15,20-tetra(4-tolyl)porphyrin (TTP), 5,10,15,20-tetra(4-methoxyphenyl)porphyrin (TMP), Zn-5,10,15,20-tetraphenylporphyrin (Zn-TPP), and Zn-5,10,15,20-tetra(4-tolyl)porphyrin (Zn-TTP) with tetracyanoethylene (TCNE) have been studied at various temperatures in CH(2)Cl(2) and CCl(4). The data are discussed in terms of equilibrium constant (K(CT)), molar extinction coefficient (epsilon(CT)), thermodynamic standard reaction quantities (DeltaG degrees , DeltaH degrees and DeltaS degrees ), oscillator strength (f), and transition dipole moment (mu). The spectrum obtained for TPP/TCNE, TTP/TCNE, and TMP/TCNE systems shows two main absorption bands at 475 and 690nm, which are not due to the absorption of any of the reactants. These bands are characteristic of an intermolecular charge transfer involving the overlap of the lowest unoccupied molecular orbital (LUMO) of the acceptor with the highest occupied molecular orbital (HOMO) of the donor. The results reveal that the interaction between the donors and acceptor is due to pi-pi(*) transitions by the formation of radical ion pairs. The stoichiometry of the complexes was found to be 1:1 ratio by the Job and straight line methods between donors and acceptor with the maximum absorption bands at wavelengths of 475 and 690nm. The observed data show salvation effects on the spectral and thermodynamics properties of CTC. The ionization potential of the donors and the dissociation energy of the CTC were also determined and are found to be constant.

  8. Spectrophotometric study of the charge transfer complexation of some porphyrin derivatives as electron donors with tetracyanoethylene

    NASA Astrophysics Data System (ADS)

    El-Zaria, Mohamed E.

    2008-01-01

    Charge transfer complexes (CTC) of 5,10,15,20-tetraphenylporphyrin (TPP), 5,10,15,20-tetra(4-tolyl)porphyrin (TTP), 5,10,15,20-tetra(4-methoxyphenyl)porphyrin (TMP), Zn-5,10,15,20-tetraphenylporphyrin (Zn-TPP), and Zn-5,10,15,20-tetra(4-tolyl)porphyrin (Zn-TTP) with tetracyanoethylene (TCNE) have been studied at various temperatures in CH 2Cl 2 and CCl 4. The data are discussed in terms of equilibrium constant ( KCT), molar extinction coefficient ( ɛCT), thermodynamic standard reaction quantities (Δ G°, Δ H° and Δ S°), oscillator strength ( f), and transition dipole moment ( μ). The spectrum obtained for TPP/TCNE, TTP/TCNE, and TMP/TCNE systems shows two main absorption bands at 475 and 690 nm, which are not due to the absorption of any of the reactants. These bands are characteristic of an intermolecular charge transfer involving the overlap of the lowest unoccupied molecular orbital (LUMO) of the acceptor with the highest occupied molecular orbital (HOMO) of the donor. The results reveal that the interaction between the donors and acceptor is due to π-π * transitions by the formation of radical ion pairs. The stoichiometry of the complexes was found to be 1:1 ratio by the Job and straight line methods between donors and acceptor with the maximum absorption bands at wavelengths of 475 and 690 nm. The observed data show salvation effects on the spectral and thermodynamics properties of CTC. The ionization potential of the donors and the dissociation energy of the CTC were also determined and are found to be constant.

  9. Chemical mechanism of surface-enhanced Raman scattering via charge transfer in fluorenone-Ag complex

    NASA Astrophysics Data System (ADS)

    Wang, Jing; Li, Yafei; Wu, Shiwei; Song, Peng; Xia, Lixin

    2016-06-01

    The intermolecular interaction between fluorenone (FN) and silver surfaces was investigated experimentally and theoretically. The structural, electronic and optical properties of the FN-Ag complex indicate that the carbonyl group O atom in FN molecules is the adsorbed position site to attach the silver substrate through the weak bond O…Ag. The analysis of vibrational modes and Raman activity of the largely enhanced Raman peaks using two FN-Ag4-x (x  =  l, s) complex models reveals that only the a1 vibrational modes with C 2v symmetry are selectively enhanced, from the point view of the change of dipole moment and polarizability induced by the interaction between FN and Ag4 substrate. Furthermore, the direct visualized evidence of the surface-enhanced Raman scattering (SERS) chemical enhancement mechanism for the FN-Ag complex is presented. The results reveal that only the intermolecular charge transfer with π-π transition characterization between FN and an Ag4 cluster facilitates the resonance Raman process and is directly responsible for chemical enhancement of Raman scattering of the FN-Ag complex.

  10. Bonding and charge transfer in nitrogen-donor uranyl complexes: insights from NEXAFS spectra.

    PubMed

    Pemmaraju, C D; Copping, Roy; Wang, Shuao; Janousch, Markus; Teat, Simon J; Tyliszcak, Tolek; Canning, Andrew; Shuh, David K; Prendergast, David

    2014-11-03

    We investigate the electronic structure of three newly synthesized nitrogen-donor uranyl complexes [(UO2)(H2bbp)Cl2], [(UO)2(Hbbp)(Py)Cl], and [(UO2)(bbp)(Py)2] using a combination of near-edge X-ray absorption fine structure (NEXAFS) spectroscopy experiments and simulations. The complexes studied feature derivatives of the tunable tridentate N-donor ligand 2,6-bis(2-benzimidazyl)pyridine (bbp) and exhibit discrete chemical differences in uranyl coordination. The sensitivity of the N K-edge X-ray absorption spectrum to local bonding and charge transfer is exploited to systematically investigate the evolution of structural as well as electronic properties across the three complexes. A thorough interpretation of the measured experimental spectra is achieved via ab initio NEXAFS simulations based on the eXcited electron and Core-Hole (XCH) approach and enables the assignment of spectral features to electronic transitions on specific absorbing sites. We find that ligand-uranyl bonding leads to a signature blue shift in the N K-edge absorption onset, resulting from charge displacement toward the uranyl, while changes in the equatorial coordination shell of the uranyl lead to more subtle modulations in the spectral features. Theoretical simulations show that the flexible local chemistry at the nonbinding imidazole-N sites of the bbp ligand is also reflected in the NEXAFS spectra and highlights potential synthesis strategies to improve selectivity. In particular, we find that interactions of the bbp ligand with solvent molecules can lead to changes in ligand-uranyl binding geometry while also modulating the K-edge absorption. Our results suggest that NEXAFS spectroscopy combined with first-principles interpretation can offer insights into the coordination chemistry of analogous functionalized conjugated ligands.

  11. Spectrophotometric determination of lamotrigine in pharmaceutical preparations and urine by charge-transfer complexation.

    PubMed

    Alizadeh, N; Khakinahad, R; Jabbari, A

    2008-11-01

    Rapid and sensitive spectrophotometric methods are developed for the determination of lamotrigine (LTG) in pharmaceutical dosage forms and urine samples, based on the formation of the charge-transfer (CT) complexes between LTG as an n-donor and the acceptors: bromocresol green (BCG), bromocresol purple (BCP), and chlorophenol red (CPR). These complexes are studied spectrophotometrically in chloroform solution in order to obtain some information about their stoichiometry and stability of complexation. The analytical parameters and their effects on the extraction of drug from urine samples are investigated. The reactions were extremely rapid at room temperature, and the absorbance values remained unchanged after 24 h for all reactions. Beer's law was obeyed in the concentration ranges 0.15-19.8, 0.15-19.8 and 0.05-34.1 microg x ml(-1) for CPR, BCP and BCG, respectively. The proposed methods were applied successfully for the determination of LTG in pharmaceutical formulations, and human urine samples in the presence of other antiepileptic drugs such as carbamazepine, oxcarbazepine and phenobarbital, with good accuracy and precision.

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

    NASA Astrophysics Data System (ADS)

    Shaw, Bikash Kumar; Saha, Shyamal K.

    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 [Co2(II)-(5-(4-PhMe)-1,3,4-oxadiazole-H+-2-thiolate)5](OAc)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.

  13. Potential energy curves crossing and low-energy charge transfer dynamics in (BeH2O)2+ complex

    NASA Astrophysics Data System (ADS)

    Sun, QiXiang; Yan, Bing

    2012-07-01

    The singlet rigid Be—O dissociation potential energy curves correlating to the first four molecular limits of (BeH2O)2+ complex were calculated using the multi-reference single and double excitation configuration interaction theory. The radial couplings of three low-lying 1A1 states were calculated and combined with adiabatic potential energy curves to investigate and charge-transfer collision dynamics by using quantum-mechanical molecular orbital close-coupling methods. It is found that the total charge-transfer cross sections are dominated by the Be+(2S)+H2O+(Ã2A1) channel. The rate coefficients in the range of 10-17-10-12 cm3/s are very sensitive to temperature below 1000 K. The complexation energy without charge-transfer was determined to be 143.6 kcal/mol, including zero-point vibration energy corrections. This is in good agreement with the previous results.

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

    PubMed

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

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

    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 524 nm. The second method depends on the reaction of VP with dichlone (DC) in dimethylformamide forming a reddish orange product measured at 490 nm. 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 415 nm. The fourth method involves the formation of a yellow complex peaking at 361 nm 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 1-8 μg/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.

  16. Manipulating charge transfer excited state relaxation and spin crossover in iron coordination complexes with ligand substitution

    DOE PAGES

    Zhang, Wenkai; Kjaer, Kasper S.; Alonso-Mori, Roberto; ...

    2016-08-25

    Developing light-harvesting and photocatalytic molecules made with iron could provide a cost effective, scalable, and environmentally benign path for solar energy conversion. To date these developments have been limited by the sub-picosecond metal-to-ligand charge transfer (MLCT) electronic excited state lifetime of iron based complexes due to spin crossover – the extremely fast intersystem crossing and internal conversion to high spin metal-centered excited states. We revitalize a 30 year old synthetic strategy for extending the MLCT excited state lifetimes of iron complexes by making mixed ligand iron complexes with four cyanide (CN–) ligands and one 2,2'-bipyridine (bpy) ligand. This enables MLCTmore » excited state and metal-centered excited state energies to be manipulated with partial independence and provides a path to suppressing spin crossover. We have combined X-ray Free-Electron Laser (XFEL) Kβ hard X-ray fluorescence spectroscopy with femtosecond time-resolved UV-visible absorption spectroscopy to characterize the electronic excited state dynamics initiated by MLCT excitation of [Fe(CN)4(bpy)]2–. The two experimental techniques are highly complementary; the time-resolved UV-visible measurement probes allowed electronic transitions between valence states making it sensitive to ligand-centered electronic states such as MLCT states, whereas the Kβ fluorescence spectroscopy provides a sensitive measure of changes in the Fe spin state characteristic of metal-centered excited states. Here, we conclude that the MLCT excited state of [Fe(CN)4(bpy)]2– decays with roughly a 20 ps lifetime without undergoing spin crossover, exceeding the MLCT excited state lifetime of [Fe(2,2'-bipyridine)3]2+ by more than two orders of magnitude.« less

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

    PubMed

    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.

  18. Manipulating charge transfer excited state relaxation and spin crossover in iron coordination complexes with ligand substitution

    SciTech Connect

    Zhang, Wenkai; Kjaer, Kasper S.; Alonso-Mori, Roberto; Bergmann, Uwe; Chollet, Matthieu; Fredin, Lisa A.; Hadt, Ryan G.; Hartsock, Robert W.; Harlang, Tobias; Kroll, Thomas; Kubicek, Katharina; Lemke, Henrik T.; Liang, Huiyang W.; Liu, Yizhu; Nielsen, Martin M.; Persson, Petter; Robinson, Joseph S.; Solomon, Edward I.; Sun, Zheng; Sokaras, Dimosthenis; van Driel, Tim B.; Weng, Tsu -Chien; Zhu, Diling; Warnmark, Kenneth; Sundstrom, Villy; Gaffney, Kelly J.

    2016-08-25

    Developing light-harvesting and photocatalytic molecules made with iron could provide a cost effective, scalable, and environmentally benign path for solar energy conversion. To date these developments have been limited by the sub-picosecond metal-to-ligand charge transfer (MLCT) electronic excited state lifetime of iron based complexes due to spin crossover – the extremely fast intersystem crossing and internal conversion to high spin metal-centered excited states. We revitalize a 30 year old synthetic strategy for extending the MLCT excited state lifetimes of iron complexes by making mixed ligand iron complexes with four cyanide (CN) ligands and one 2,2'-bipyridine (bpy) ligand. This enables MLCT excited state and metal-centered excited state energies to be manipulated with partial independence and provides a path to suppressing spin crossover. We have combined X-ray Free-Electron Laser (XFEL) Kβ hard X-ray fluorescence spectroscopy with femtosecond time-resolved UV-visible absorption spectroscopy to characterize the electronic excited state dynamics initiated by MLCT excitation of [Fe(CN)4(bpy)]2–. The two experimental techniques are highly complementary; the time-resolved UV-visible measurement probes allowed electronic transitions between valence states making it sensitive to ligand-centered electronic states such as MLCT states, whereas the Kβ fluorescence spectroscopy provides a sensitive measure of changes in the Fe spin state characteristic of metal-centered excited states. Here, we conclude that the MLCT excited state of [Fe(CN)4(bpy)]2– decays with roughly a 20 ps lifetime without undergoing spin crossover, exceeding the MLCT excited state lifetime of [Fe(2,2'-bipyridine)3]2+ by more than two orders of magnitude.

  19. Conductive PVDF-HFP nanofibers with embedded TTF-TCNQ charge transfer complex.

    PubMed

    Gal-Oz, Reshef; Patil, Nilesh; Khalfin, Rafail; Cohen, Yachin; Zussman, Eyal

    2013-07-10

    Tetrathiafulvalene-tetracyanoquinodimethane charge-transfer complex (TTF-TCNQ CTC) represents a promising organic conductive system. However, application of this donor-acceptor pair is highly limited, because of its ultrafast crystallization kinetics and very low solubility. In this work, conductive organic nanofibers were generated via a coelectrospinning process of poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) with embedded TTF and TCNQ in the shell and core solutions, respectively. Upon supply of the polymer solutions, a core-shell droplet was formed at the exit of the spinneret. The electron donor TTF and the electron acceptor TCNQ migrated toward each other, within the compound droplet, to produce conductive CTC crystals. In the presence of a sufficiently strong electric field, jetting set in at the droplet tip, which yielded solidified PVDF-HFP nanofibers embedded with aligned CTC. Fiber diameters ranged between 100 and 500 nm. X-ray analysis showed strong equatorial reflections (110,200) of oriented copolymer PVDF-HFP crystals (β-phase) with copolymer chains oriented along the fiber axis, and of CTC (001), indicating that the CTC molecular planes were aligned parallel to the nanofiber axis. In addition, reflections of unreacted TCNQ (120,220) and TTF (110) crystals were observed. The electrospun nanofibers were collected to form a fiber mat, which was evaluated as a working electrode in a three-electrode cell system, exhibiting differential conductance of 5.23 μmho.

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

    PubMed Central

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

    2012-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2017-10-01

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

  2. Spectroscopic studies and molecular orbital calculations of charge transfer complexation between 3,5-dimethylpyrazole with DDQ in acetonitrile.

    PubMed

    Habeeb, Moustafa M; Al-Attas, Amirah S; Al-Raimi, Doaa S

    2015-05-05

    Charge transfer (CT) interaction between 3,5-dimethylpyrazole (DMP) with the π-acceptor 2,3-dichloro-5,6-dicyano-p-benzoquinon (DDQ) has been investigated spectrophotometrically in acetonitrile (AN). Simultaneous reddish brown color has been observed upon mixing donor with acceptor solutions attributing to CT complex formation. The electronic spectra of the formed complex exhibited multi-charge transfer bands at 429, 447, 506, 542 and 589nm, respectively. Job(')s method of continuous variations and spectrophotometric titration methods confirmed the formation of the studied complex in 1:2 ratio between DMP and DDQ. Benesi-Hildebrand equation has been applied to calculate the stability constant of the formed complex where it recorded high value supporting formation of stable complex. Molecular orbital calculations using MM2 method and GAMESS (General Atomic and Molecular Electronic Structure System) interface computations as a package of ChemBio3D Ultra12 software were carried out for more analysis of the formed complex in the gas phase. The computational analysis included energy minimisation, stabilisation energy, molecular geometry, Mullikan charges, molecular electrostatic potential (MEP) surfaces of reactants and complex as well as characterization of the higher occupied molecular orbitals (HOMO) and lower unoccupied molecular orbitals (LUMO) surfaces of the complex. A good consistency between experimental and theoretical results has been recorded.

  3. Competition between covalent bonding and charge transfer at complex-oxide interfaces.

    PubMed

    Salafranca, Juan; Rincón, Julián; Tornos, Javier; León, Carlos; Santamaria, Jacobo; Dagotto, Elbio; Pennycook, Stephen J; Varela, Maria

    2014-05-16

    Here we study the electronic properties of cuprate-manganite interfaces. By means of atomic resolution electron microscopy and spectroscopy, we produce a subnanometer scale map of the transition metal oxidation state profile across the interface between the high Tc superconductor YBa2Cu3O7-δ and the colossal magnetoresistance compound (La,Ca)MnO3. A net transfer of electrons from manganite to cuprate with a peculiar nonmonotonic charge profile is observed. Model calculations rationalize the profile in terms of the competition between standard charge transfer tendencies (due to band mismatch), strong chemical bonding effects across the interface, and Cu substitution into the Mn lattice, with different characteristic length scales.

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

    PubMed

    Ramanathan, Rajesh; Walia, Sumeet; Kandjani, Ahmad Esmaielzadeh; Balendran, Sivacarendran; Mohammadtaheri, Mahsa; Bhargava, Suresh Kumar; Kalantar-zadeh, Kourosh; Bansal, Vipul

    2015-02-03

    A generalized low-temperature approach for fabricating high aspect ratio nanorod arrays of alkali metal-TCNQ (7,7,8,8-tetracyanoquinodimethane) charge transfer complexes at 140 °C is demonstrated. This facile approach overcomes the current limitation associated with fabrication of alkali metal-TCNQ complexes that are based on physical vapor deposition processes and typically require an excess of 800 °C. The compatibility of soft substrates with the proposed low-temperature route allows direct fabrication of NaTCNQ and LiTCNQ nanoarrays on individual cotton threads interwoven within the 3D matrix of textiles. The applicability of these textile-supported TCNQ-based organic charge transfer complexes toward optoelectronics and gas sensing applications is established.

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

    NASA Astrophysics Data System (ADS)

    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.

  6. Analytical studies on the charge transfer complexes of loperamide hydrochloride and trimebutine drugs. Spectroscopic and thermal characterization of CT complexes.

    PubMed

    Elqudaby, Hoda M; Mohamed, Gehad G; El-Din, Ghada M G

    2014-08-14

    Charge transfer complexes of loperamide hydrochloride (LOP.HCl) and trimebutine (TB) drugs as electron donor with 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ), tetracyanoethylene (TCNE) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) as π-acceptors in acetonitrile were investigated spectrophotometrically to determine the cited drugs in pure and dosage forms. The reaction gives highly coloured complex species which are measured spectrophotometrically at 460, 415 and 842nm in case of LOP.HCl and at 455, 414 and 842nm in case of TB using DDQ, TCNE and TCNQ reagents, respectively. The optimum experimental conditions have been studied carefully and optimized. Beer's law was obeyed over the concentration ranges of 47.70-381.6, 21.50-150.5 and 10.00-100.0μgmL(-1) for LOP.HCl and 37.85-264.9, 38.75-310.0 and 7.75-155.0μgmL(-1) for TB using DDQ, TCNE and TCNQ reagents, respectively. Sandell sensitivity, standard deviation, relative standard deviation, limit of detection and quantification were calculated. The obtained data refer to high accuracy and precision of the proposed method. These results are also confirmed by inter and intra-day precision with percent recovery of 99.18-101.1% and 99.32-101.4% in case of LOP.HCl and 98.00-102.0% and 97.50-101.4% in case of TB using DDQ, TCNE and TCNQ reagents for intra- and inter-day, respectively. These data were compared with those obtained using official methods for the determination of the cited drugs. The stability constants of the CT complexes were determined. The final products of the reaction were isolated and characterized using FT-IR, (1)H NMR, elemental analysis and thermogravimetric analysis (TG). The stoichiometry and apparent formation constant of the complexes formed were determined by applying the conventional spectrophotometric molar ratio method.

  7. Charge Transfer as a Probe for the Interfacial Properties of Quantum Dot-Ligand Complexes

    NASA Astrophysics Data System (ADS)

    Weinberg, David Joseph

    This dissertation describes the study of charge transfer interactions between colloidal quantum dots (QDs) and molecular redox partners in the context of both fundamental investigations of charge recombination mechanisms in nanocrystal-molecule systems, and as a technique to probe the properties of the QD ligand shell. Charge separation in a system of CdS nanocrystals and organic hole acceptors results in the formation of a spin-correlated radical ion pair. Interrogating this photogenerated species with EPR and magnetic field effect transient absorption techniques reveals that the charge recombination dynamics of this donor-acceptor system are dictated by the radical pair intersystem crossing mechanism on the nanosecond timescale. These experiments also indicate that the photoinjected electron localizes at a CdS QD surface trap state, and the coupling between the electron and hole in this spin-correlated system is low. Additional studies involving the CdS QDs and organic hole acceptors are proposed which would investigate the exchange of charge and energy within the nanocrystal organic adlayer. Collisional charge transfer interactions between substituted benzoquinone molecules and PbS QDs coated with mixed monolayers of oleic acid and perfluorodecanethiol are monitored via photoluminescence and transient absorption spectroscopies. These experiments reveal that partially fluorinated ligand shells are less permeable to solution phase molecules and offer greater protection of the nanocrystal surface than their aliphatic counterparts. Only a small amount of fluorinated surfactant ( 20% surface coverage) is necessary to profoundly change the permeability of the ligand shell, and the protective nature of these fluorinated molecules is likely a combination of the molecular volume and oleophobicity of these ligands. Follow up work is discussed which would elucidate the influence of solvent and extent of surfactant fluorination on the permeability of these ligand shells, as

  8. Synthesis and spectrophotometric studies of charge transfer complexes of p-nitroaniline with benzoic acid in different polar solvents

    NASA Astrophysics Data System (ADS)

    Singh, Neeti; Ahmad, Afaq

    2014-09-01

    The charge transfer complexes of the donor p-nitroaniline (PNA) with the π-acceptor benzoic acid (BEA) have been studied spectrophotometrically in various solvents such as acetone, ethanol, and methanol at room temperature using an absorption spectrophotometer. The outcome suggests that the formation of the CT-complex is comparatively high in less polar solvent. The stoichiometry of the CT-complex was found to be 1:1. The physical parameters of the CT-complex were evaluated by the Benesi-Hildebrand equation. The data are discussed in terms of the formation constant (KCT), molar extinction coefficient (ɛCT), Standard Gibbs free energy (ΔG0), oscillator strength (f), transition dipole moment (μEN), resonance energy (RN) and ionization potential (ID). The formation constant (KCT) of the complex was depends upon the nature of electron acceptor, donor, and polarity of solvents used. It is also observed that a charge transfer molecular complex is stabilized by hydrogen bonding. The formation of the complex has been confirmed by UV-visible, FT-IR, 1H NMR and TGA/DTA. The structure of the CT-complex is [(PNA)+ (BEA)-]. A general mechanism for its formation of the complex has also been proposed.

  9. Analytical studies on the charge transfer complexes of loperamide hydrochloride and trimebutine drugs. Spectroscopic and thermal characterization of CT complexes

    NASA Astrophysics Data System (ADS)

    Elqudaby, Hoda M.; Mohamed, Gehad G.; El-Din, Ghada M. G.

    2014-08-01

    Charge transfer complexes of loperamide hydrochloride (LOP.HCl) and trimebutine (TB) drugs as electron donor with 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ), tetracyanoethylene (TCNE) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) as π-acceptors in acetonitrile were investigated spectrophotometrically to determine the cited drugs in pure and dosage forms. The reaction gives highly coloured complex species which are measured spectrophotometrically at 460, 415 and 842 nm in case of LOP.HCl and at 455, 414 and 842 nm in case of TB using DDQ, TCNE and TCNQ reagents, respectively. The optimum experimental conditions have been studied carefully and optimized. Beer’s law was obeyed over the concentration ranges of 47.70-381.6, 21.50-150.5 and 10.00-100.0 μg mL-1 for LOP.HCl and 37.85-264.9, 38.75-310.0 and 7.75-155.0 μg mL-1 for TB using DDQ, TCNE and TCNQ reagents, respectively. Sandell sensitivity, standard deviation, relative standard deviation, limit of detection and quantification were calculated. The obtained data refer to high accuracy and precision of the proposed method. These results are also confirmed by inter and intra-day precision with percent recovery of 99.18-101.1% and 99.32-101.4% in case of LOP.HCl and 98.00-102.0% and 97.50-101.4% in case of TB using DDQ, TCNE and TCNQ reagents for intra- and inter-day, respectively. These data were compared with those obtained using official methods for the determination of the cited drugs. The stability constants of the CT complexes were determined. The final products of the reaction were isolated and characterized using FT-IR, 1H NMR, elemental analysis and thermogravimetric analysis (TG). The stoichiometry and apparent formation constant of the complexes formed were determined by applying the conventional spectrophotometric molar ratio method.

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

    PubMed

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

    2012-11-14

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

  11. Exploiting charge-transfer complexation for selective measurement of gas-phase olefins with nanoparticle-coated chemiresistors.

    PubMed

    Rowe, Michael P; Steinecker, William H; Zellers, Edward T

    2007-02-01

    Charge-transfer-mediated olefin-selective sensing by use of chemiresistors (CR) coated with composite films of n-octanethiolate-monolayer-protected gold nanoparticles (C8-MPN) and each of several square-planar PtCl2(olefin)(pyridine) coordination complexes is described. Where the gas-phase olefin analyte differs from that initially coordinated to Pt, olefin substitution occurs and is accompanied by a persistent shift in the composite film resistance. Commensurate changes in film mass are also observed with a similarly coated thickness shear mode resonator. Regeneration is possible by exposure to the initially complexed olefin gas or vapor. If the olefin analyte is the same as that initially coordinated to Pt, then a reversible charge-transfer interaction occurs that is accompanied by a decrease in film resistance (increase in film mass), which recovers spontaneously after removal of the olefin from the atmosphere above the sensor. This behavior differs from that of MPN-coated CRs lacking such Pt complexes, which invariably yield resistance increases upon exposure to nonpolar vapors. Red shifts in the UV-vis absorbance spectra of the PtCl2(olefin)(pyridine) complexes in solution upon addition of free olefin support the hypothesis that Pt-olefin coordination in the composite films creates temporary low-resistance pathways that compete effectively with the concurrent increase in tunneling resistance associated with swelling-induced separation of C8-MPN cores. Structurally analogous non-olefins produce only increases in film resistance. Selective measurement of styrene, ethylene, 1-octene, and 1,3-butadiene is illustrated. Olefin detection limits are reduced as much as 23 000-fold by inclusion of the corresponding Pt complex in the CR interface film. Composite films suffer a gradual loss of selectivity from decomposition of the Pt-olefin complex, apparently facilitated by a Au-Pt charge transfer.

  12. Coarse-grained time-dependent density functional simulation of charge transfer in complex systems: application to hole transfer in DNA.

    PubMed

    Kubar, Tomás; Elstner, Marcus

    2010-09-02

    We present a coarse-grained tight-binding method based on density functional theory (DFT) for the simulation of charge transfer in complex materials. The charge-transfer parameters are computed using a fragment-orbital approach combined with the approximative DFT method self-consistent charge density functional tight binding (SCC-DFTB), which allows to follow the dynamics of excess charge along nanosecond MD trajectories, still accounting for the important impact of structural fluctuations and solvent effects. Since DFT suffers from the self-interaction error, which would lead to a delocalization of the hole charge over the entire system, we study the effect of an empirical self-interaction correction in detail. The wave function of the excess charge is propagated within the framework of time-dependent DFT, where the electron (hole) and the atomic system are propagated simultaneously according to the derived coupled equations of motion. In the case of DNA, the solvent polarization effects are a dominant factor affecting the hole transport. The hole charge polarizes the surrounding water, which in turn supports a localization of the hole charge--a water polaron is formed, extended dynamically over several nucleobases. As this polarization of water accompanies the migrating hole, the motion of hole is significantly slowed down due to the solvent reorganization energy involved. The estimated hopping rate between neighboring adenines in poly(A)-DNA is in the order of 100 ns(-1), and our simulations clearly show that the charge transfer occurs in a nonadiabatic fashion, due to the small average electronic coupling of around 0.06 eV.

  13. (Fluoren-9-ylidene)methanedithiolato complexes of gold: synthesis, luminescence, and charge-transfer adducts.

    PubMed

    Vicente, José; González-Herrero, Pablo; García-Sánchez, Yolanda; Jones, Peter G; Bardají, Manuel

    2004-11-15

    Piperidinium 9H-fluorene-9-carbodithioate and its 2,7-di-tert-butyl-substituted analogue [(pipH)(S(2)CCH(C(12)H(6)R(2)-2,7)), R = H (1a), t-Bu (1b)] and 2,7-bis(octyloxy)-9H-fluorene-9-carbodithioic acid [HS(2)CCH(C(12)H(6)(OC(8)H(17))(2)-2,7), 2] and its tautomer [2,7-bis(octyloxy)fluoren-9-ylidene]methanedithiol [(HS)(2)C=C(C(12)H(6)(OC(8)H(17))(2)-2,7), 3] were employed for the preparation of gold complexes with the (fluoren-9-ylidene)methanedithiolato ligand and its substituted analogues. The gold(I) compounds Q(2)[Au(2)(mu-kappa(2)-S,S-S(2)C=C(C(12)H(6)R(2)-2,7))(2)], where Q(+) = PPN(+) or Pr(4)N(+) for R = H (Q(2)4a) or Q(+) = Pr(4)N(+) for R = OC(8)H(17) [(Pr(4)N)(2)4c], were synthesized by reacting Q[AuCl(2)] with 1a or 2 (1:1) and excess piperidine or diethylamine. Complexes of the type [(Au(PR'3))(2)(mu-kappa(2)-S,S-S(2)C=C(C(12)H(6)R(2)-2,7))(2)] with R = H and R' = Me (5a), Et (5b), Ph (5c), and Cy (5d) or R = t-Bu and R' = Me (5e), Et (5f), Ph (5g), and Cy (5h) were obtained by reacting [AuCl(PR'(3))] with 1a,b (1:2) and piperidine. The reactions of 1a,b or 2 with Q[AuCl(4)] (2:1) and piperidine or diethylamine gave Q[Au(kappa(2)-S,S-S(2)C=C(C(12)H(6)R(2)-2,7))(2)] with Q(+) = PPN(+) for R = H [(PPN)6a], Q(+) = PPN(+) or Bu(4)N(+) for R = t-Bu (Q6b), and Q(+) = Bu(4)N(+) for R = OC(8)H(17) [(Bu(4)N)6c]. Complexes Q6a-c reacted with excess triflic acid to give [Au(kappa(2)-S,S-S(2)C=C(C(12)H(6)R(2)-2,7))(kappa(2)-S,S-S(2)CCH(C(12)H(6)R(2)-2,7))] [R = H (7a), t-Bu (7b), OC(8)H(17) (7c)]. By reaction of (Bu(4)N)6b with PhICl(2) (1:1) the complex Bu(4)N[AuCl(2)(kappa(2)-S,S-S(2)C=C(C(12)H(6)(t-Bu)(2)-2,7))] [(Bu(4)N)8b] was obtained. The dithioato complexes [Au(SC(S)CH(C(12)H(8)))(PCy(3))] (9) and [Au(n)(S(2)CCH(C(12)H(8)))(n)] (10) were obtained from the reactions of 1a with [AuCl(PCy(3))] or [AuCl(SMe(2))], respectively (1:1), in the absence of a base. Charge-transfer adducts of general composition Q[Au(kappa(2)-S,S-S(2)C=C(C(12)H(6)R(2

  14. Physico-chemical studies on the charge-transfer complex formed between sulfadoxine and pyrimethamine with chloranilic acid.

    PubMed

    Onah, Johnson Ogoda; Odeiani, James Eromi

    2002-07-20

    Thermodynamic studies on the charge-transfer complexes of sulfadoxine and pyrimethamine with chloranilic acid in non-aqueous 1,4-dioxan were investigated by spectrophotometric method. The absorption maxima for sulfadoxine and pyrimethamine were observed at 500 and 520 nm, respectively. We observed a bathochromic shift in the transitions of these complexes with respect to chloranilic acid, which absorb at 420 nm. The enthalpy of complexation was found to be -3.044 kJ/mole for pyrimethamine and -5.934 kJ/mole for sulfadoxine. Equilibrium constant values were generally high, that is 261.202 l/mole and 344.29 l/mole for pyrimethamine and sulfadoxine, respectively, at 303 K. Free energy values were negative, of the order of -14.420 kJ/mole for pyrimethamine and -15.384 kJ/mole for sulfadoxine, indicating that complex formations were exothermic. These data suggest that the complexes are very stable. Arguments are presented to support the application of charge-transfer interactions in the quantitative analysis of these drugs.

  15. Synthesis, characterization and pharmacological investigation of a new charge-transfer complex of 3-aminopyridinum-p-toluenesulfonate

    NASA Astrophysics Data System (ADS)

    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.

  16. Spectrophotometric determination of some pharmaceutical piperazine derivatives through charge-transfer and ion-pair complexation reactions.

    PubMed

    Abdel-Gawad, F M

    1997-07-01

    Simple and sensitive spectrophotometric methods are described for the assay of three piperazine derivatives; ketoconazole, piribedil and prazosin hydrochloride based on charge-transfer and ion-pair complexation reactions. The first method is based on the reaction of the basic drug with 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) in acetonitrile. The orange-red colour formed due to the formation of charge-transfer complex showed maximum absorbance at 460 nm. The second method is based upon the interaction of the basic drug in dry chloroform with bromophenol blue (BPB) in the same solvent to produce a stable yellow ion-pair complex which absorbs at 410 nm. Beer's law was obeyed for both methods and the relative standard deviations were found to be less than 1%. The two methods can be applied to the analysis of tablets, with no evidence of interference from excipients. A more detailed investigation of the complex was made with respect to its composition, association constant and free energy change.

  17. Contact charge-transfer lasers

    SciTech Connect

    Dharamsi, A.N.; Tulip, J.

    1981-07-01

    A mechanism for sustaining population inversions in contact charge-transfer complexes in which the ground electronic state is not bound is described. The mechanism relies on picosecond radiationless depletion of the lower laser state. This generates an inversion even when the ground-state potential curve, as plotted against the donor-acceptor distance, is not repulsive vertically below the excited state minimum. Contact charge-transfer lasers would offer high gain, high-energy density, and tunable sources of coherent radiation in the uv and visible. A method for pumping such a laser is examined and applied to the pyrrole-oxygen complex. A rate equation analysis is done and estimates for gain and energy density are presented.

  18. 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

    NASA Astrophysics Data System (ADS)

    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 .

  19. Charge-Disproportionation Symmetry Breaking Creates a Heterodimeric Myoglobin Complex with Enhanced Affinity and Rapid Intracomplex Electron Transfer

    PubMed Central

    Trana, Ethan N; Nocek, Judith M; Woude, Jon Vander; Span, Ingrid; Smith, Stephen M; Rosenzweig, Amy C; Hoffman, Brian M

    2016-01-01

    We report rapid photo-initiated intra-complex electron transfer (ET) within a `charge-disproportionated' myoglobin (Mb) dimer with greatly enhanced affinity. Two mutually supportive Brownian Dynamics (BD) interface redesign strategies, one a new `heme-filtering' approach, were employed to `break the symmetry' of a Mb homodimer by pairing Mb constructs with complementary highly positive and highly negative net surface charges, introduced through D/E → K and K → E mutations, respectively. BD simulations using a previously developed positive mutant, Mb(+6) = Mb(D44K/D60K/E85K) led to construction of the complementary negative mutant Mb(−6) = Mb(K45E, K63E, K95E). Simulations predict the pair will form a well-defined complex comprising a tight ensemble of conformations with nearly parallel hemes, at a metal-metal distance ~ 18-19 Å. Upon expression and X-ray characterization of the partners, BD predictions were verified through ET photocycle measurements enabled by Zn-Deutoroporphyrin substitution, forming the [ZnMb(−6), Fe3+Mb(+6)] complex. Triplet ET quenching shows charge disproportionation increases the binding constant by no less than ~ 5 orders of magnitude relative to wild-type Mb values. All progress curves for charge separation (CS) and charge recombination (CR) are reproduced by a generalized kinetic model for the inter-protein ET photocycle. The intracomplex ET rate constants for both CS and CR are increased by over 5 orders of magnitude, and their viscosity independence is indicative of true inter-protein ET, rather than dynamic gating as seen in previous studies. The complex displays an unprecedented timecourse for CR of the CS intermediate I. After a laser flash, I forms through photo-induced CS, accumulates to a maximum concentration, then dies away through CR. However, before completely disappearing, I re-appears without another flash and reaches a second maximum before disappearing completely. PMID:27646786

  20. Lutein can act as a switchable charge transfer quencher in the CP26 light-harvesting complex.

    PubMed

    Avenson, Thomas J; Ahn, Tae Kyu; Niyogi, Krishna K; Ballottari, Matteo; Bassi, Roberto; Fleming, Graham R

    2009-01-30

    Energy-dependent quenching of excitons in photosystem II of plants, or qE, has been positively correlated with the transient production of carotenoid radical cation species. Zeaxanthin was shown to be the donor species in the CP29 antenna complex. We report transient absorbance analyses of CP24 and CP26 complexes that bind lutein and zeaxanthin in the L1 and L2 domains, respectively. For CP24 complexes, the transient absorbance difference profiles give a reconstructed transient absorbance spectrum with a single peak centered at approximately 980 nm, consistent with zeaxanthin radical cation formation. In contrast, CP26 gives constants for the decay components probed at 940 and 980 nm of 144 and 194 ps, a transient absorbance spectrum that has a main peak at 980 nm, and a substantial shoulder at 940 nm. This suggests the presence of two charge transfer quenching sites in CP26 involving zeaxanthin radical cation and lutein radical cation species. We also show that lutein radical cation formation in CP26 is dependent on binding of zeaxanthin to the L2 domain, implying that zeaxanthin acts as an allosteric effector of charge transfer quenching involving lutein in the L1 domain.

  1. Evolving the [myoglobin, cytochrome b(5)] complex from dynamic toward simple docking: charging the electron transfer reactive patch.

    PubMed

    Trana, Ethan N; Nocek, Judith M; Knutson, Amanda K; Hoffman, Brian M

    2012-10-30

    We describe photoinitiated electron transfer (ET) from a suite of Zn-substituted myoglobin (Mb) variants to cytochrome b(5) (b(5)). An electrostatic interface redesign strategy has led to the introduction of positive charges into the vicinity of the heme edge through D/E → K charge-reversal mutation combinations at "hot spot" residues (D44, D60, and E85), augmented by the elimination of negative charges from Mb or b(5) by neutralization of heme propionates. These variations create an unprecedentedly large range in the product of the ET partners' total charges (-5 < -q(Mb)q(b(5)) < 40). The binding affinity (K(a)) increases 1000-fold as -q(Mb)q(b(5)) increases through this range and exhibits a surprisingly simple, exponential dependence on -q(Mb)q(b(5)). This is explained in terms of electrostatic interactions between a "charged reactive patch" (crp) on each partner's surface, defined as a compact region around the heme edge that (i) contains the total protein charge of each variant and (ii) encompasses a major fraction of the "reactive region" (Rr) comprising surface atoms with large matrix elements for electron tunneling to the heme. As -q(Mb)q(b(5)) increases, the complex undergoes a transition from fast to slow-exchange dynamics on the triplet ET time scale, with a correlated progression in the rate constants for intracomplex (k(et)) and bimolecular (k(2)) ET. This progression is analyzed by integrating the crp and Rr descriptions of ET into the textbook steady-state treatment of reversible binding between partners that undergo intracomplex ET and found to encompass the full range of behaviors predicted by the model. The generality of this approach is demonstrated by its application to the extensive body of data for the ET complex between the photosynthetic reaction center and cytochrome c(2). Deviations from this model also are discussed.

  2. Evolving the [Myoglobin, Cytochrome b5] Complex from Dynamic Toward Simple Docking: Charging the Electron-Transfer Reactive Patch

    PubMed Central

    Trana, Ethan N.; Nocek, Judith M.; Knutson, Amanda K.; Hoffman, Brian M.

    2012-01-01

    We describe photo-initiated electron transfer (ET) from a suite of Zn-substituted myoglobin (1Mb) variants to cytochrome b5 (b5). An electrostatic interface redesign strategy has led to the introduction of positive charges in the vicinity of the heme edge through D/E → K charge-reversal mutation combinations at `hotspot' residues (D44, D60, E85), augmented by the elimination of negative charges from Mb or b5 by neutralization of heme propionates. These variations create an unprecedentedly large range in the product of the ET partners' total charges: −5 < −qMbqb5 < 40. The binding affinity (Ka) increases a thousand-fold as −qMbqb5 increases through this range, and exhibits a surprisingly simple, exponential dependence on −qMbqb5. This is explained in terms of electrostatic interactions between a `charged reactive patch' (crp) on each partner's surface, defined as a compact region around the heme edge that (i) contains the total protein charge of each variant, and (ii) encompasses a major fraction of the `reactive region' (Rr) comprising surface atoms with large matrix elements for electron tunneling to the heme. As −qMbqb5 increases, the complex undergoes a transition from fast to slow exchange dynamics on the triplet ET timescale, with a correlated progression in the rate constants for intracomplex (ket) and bimolecular (k2) ET. This progression is analyzed by integrating the crp and Rr descriptions of ET into the textbook steady-state treatment of reversible binding between partners that undergo intracomplex ET, and found to encompass the full range of behaviors predicted by the model. The generality of this approach is demonstrated by applying it to the extensive body of data for the ET complex between the photosynthetic reaction center and cytochrome c2. Deviations from this model also are discussed. PMID:23067206

  3. N-type molecular electrical doping in organic semiconductors: formation and dissociation efficiencies of charge transfer complex

    NASA Astrophysics Data System (ADS)

    Kim, Jae-Min; Yoo, Seung-Jun; Moon, Chang-Ki; Sim, Bomi; Lee, Jae-Hyun; Lim, Heeseon; Kim, Jeong Won; Kim, Jang-Joo

    2016-09-01

    Electrical doping is an important method in organic electronics to enhance device efficiency by controlling Fermi level, increasing conductivity, and reducing injection barrier from electrode. To understand the charge generation process of dopant in doped organic semiconductors, it is important to analyze the charge transfer complex (CTC) formation and dissociation into free charge carrier. In this paper, we correlate charge generation efficiency with the CTC formation and dissociation efficiency of n-dopant in organic semiconductors (OSs). The CTC formation efficiency of Rb2CO3 linearly decreases from 82.8% to 47.0% as the doping concentration increases from 2.5 mol% to 20 mol%. The CTC formation efficiency and its linear decrease with doping concentration are analytically correlated with the concentration-dependent size and number of dopant agglomerates by introducing the degree of reduced CTC formation. Lastly, the behavior of dissociation efficiency is discussed based on the picture of the statistical semiconductor theory and the frontier orbital hybridization model.

  4. Ni(II)-tetrahedral complexes: Characterization, antimicrobial properties, theoretical studies and a new family of charge-transfer transitions

    NASA Astrophysics Data System (ADS)

    Sarı, Nurşen; Şahin, Songül Çiğdem; Öğütcü, Hatice; Dede, Yavuz; Yalcin, Soydan; Altundaş, Aliye; Doğanay, Kadir

    2013-04-01

    A new amine containing selenium and their five imine, (SeSchX)(X: -H, F, Cl, Br, CH3), and Ni (II) complexes, [Ni(SeSchX)(H2O)2]Cl/[Ni(SeSchCl)(H2O)Cl], were synthesized. The compounds were characterized by means of elemental analyses, 13C and 1H NMR (for imine), FT-IR, UV-Visible spectroscopy, TGA/DTA and elemental analyses. [Ni(SeSchCl)(H2O)Cl] complex from Ni(II) complexes changes color from yellow to orange in the range pH 5-7. [Ni(SeSchCl)(H2O)Cl] complex has ligand-to-metal charge-transfer (LMCT) transitions in the basic medium. Excitation characteristics and energetic of [Ni(SeSchCl)(H2O)Cl] complex, examined via TD-DFT calculations, reveals transitions of LMCT and π → π* character that matches the experimental values. [Ni(SeSchCl)(H2O)Cl] complex showed the highest antibacterial activity when compared to other complexes reported in this work.

  5. Spectrofluorimetric study of the charge-transfer complexation of certain fluoroquinolones with 7,7,8,8-tetracyanoquinodimethane

    NASA Astrophysics Data System (ADS)

    Du, Li Ming; Yao, Hai Yan; Fu, Mi

    2005-01-01

    Simple, rapid and sensitive spectrofluorimetric methods are described, for the first time, for the determination of ciprofloxacin (CIP), norfloxacin (NOR), pefloxacin (PEF) and fleroxacin (FLE). The methods are based on the charge-transfer (CT) reaction of these drugs as n-electron donors with 7,7,8,8-tetracyanoquinodimethane (TCNQ) as π-electron acceptor. TCNQ was found to react with these drugs to produce intensely transfer reaction complexes and the fluorescence intensity of the complexes was enhanced in 21-35 fold higher than that of the studied fluoroquinolones itself. The formation of such complexes was also confirmed by both infrared and ultraviolet-visible measurements. The different experimental parameters that affect the fluorescence intensity were carefully studied. At the optimum reaction conditions, the drug-TCNQ complexes showed excitation maxima ranging from 277 to 284 nm and emission maxima ranging from 451 to 458 nm. Rectilinear calibration graphs were obtained in the concentration range of 0.03-0.9, 0.04-1.2, 0.04-1.3 and 0.08-2.4 μg ml -1 for CIP, NOR, PEF and FLE, respectively. The developed methods were applied successfully for the determination of the studied drugs in their pharmaceutical dosage forms with a good precision and accuracy compared to official and reported methods as revealed by t- and F-tests.

  6. Side chain effects in reactions of the potassium-tyrosine charge transfer complex

    NASA Astrophysics Data System (ADS)

    da Silva, F. Ferreira; Meneses, G.; Ingólfsson, O.; Limão-Vieira, P.

    2016-10-01

    Fragmentation of transient negative ions of tyrosine formed through electron transfer in collisions with neutral potassium atoms is presented in the collision energy range from 30 to 75 eV. At low collision energies the dominating side chain channel observed corresponds to the cleavage of the bond from the para-position of the phenyl ring to the β-C of the remaining moiety, but cleavage of the Cαsbnd Cβ bond is also observed. Further fragments are formed through cleavage of the Cα bond to the carbonyl group, through decomposition of the carboxyl group or through significant decomposition of the backbone. The dehydrogenated molecular anion is also observed with appreciable intensity. These results are discussed in the context of earlier studies on dissociative electron attachment to tyrosine and other amino acids, as well as within the role of the side chain in electron induced decomposition of this aromatic amino acid. Stabilization of the temporary molecular anion in the transient collision complex is discussed and we argue that this may have significant influence on the branching ratios observed.

  7. Charge transfer in MOH(H2O)(+) (M = Mn, Fe, Co, Ni, Cu, Zn) complexes revealed by vibrational spectroscopy of mass-selected ions.

    PubMed

    Marsh, Brett M; Zhou, Jia; Garand, Etienne

    2015-10-21

    Charge transfer between a metal and its ligand is fundamental for the structure and reactivity of a metal complex as it directly dictates the distribution of electron density within the complex. To better understand such charge transfer interactions, we studied the vibrational spectra of mass-selected MOH(H2O)(+) (M = Mn, Fe, Co, Ni, Cu, or Zn) complexes, acquired using cryogenic ion infrared predissociation spectroscopy. We find that there is a partial charge transfer from the hydroxide anion to the metal center for these first-row transition metals, the extent of which is in the order of Mn < Fe < Co < Ni < Cu > Zn, dictated by the 2nd ionization energy of the bare metal. This gradual change across the metal series points to the complexity in the electronic structures of these transition metal complexes. Interestingly, the hydroxide ligand in these complexes can serves as a sensitive in situ probe of this charge transfer. Its vibrational frequency varies by >150 cm(-1) for different metal species, and it is dependent on the electric field produced by the charged metal center. This dramatic vibrational Stark shift is further modulated by the charge present on the hydroxide itself, providing a well-defined relationship between the observed hydroxide frequency and the effective electric field.

  8. Charge transfer complex studies between some non-steroidal anti-inflammatory drugs and π-electron acceptors

    NASA Astrophysics Data System (ADS)

    Duymus, Hulya; Arslan, Mustafa; Kucukislamoglu, Mustafa; Zengin, Mustafa

    2006-12-01

    Charge transfer (CT) complexes of some non-steroidal anti-inflammatory drugs, naproxen and etodolac which are electron donors with some π-acceptors, such as tetracyanoethylene (TCNE), 2,3-dichloro-5,6-dicyano- p-benzoquinone (DDQ), p-chloranil ( p-CHL), have been investigated spectrophotometrically in chloroform at 21 °C. The coloured products are measured spectrophotometrically at different wavelength depending on the electronic transition between donors and acceptors. Beer's law is obeyed and colours were produced in non-aqueous media. All complexes were stable at least 2 h except for etodolac with DDQ stable for 5 min. The equilibrium constants of the CT complexes were determined by the Benesi-Hildebrand equation. The thermodynamic parameters Δ H, Δ S, Δ G° were calculated by Van't Hoff equation. Stochiometries of the complexes formed between donors and acceptors were defined by the Job's method of the continuous variation and found in 1:1 complexation with donor and acceptor at the maximum absorption bands in all cases.

  9. Spectrophotometric study of the charge-transfer and ion-pair complexation of methamphetamine with some acceptors

    NASA Astrophysics Data System (ADS)

    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.

  10. Spectral, crystal structure, thermal and antimicrobial characterisation of an organic charge transfer complex-3,5-dimethylpyrrazolinium picrate

    NASA Astrophysics Data System (ADS)

    Dhanabal, T.; Amirthaganesan, G.; Dhandapani, M.; Das, Samar K.

    2013-03-01

    A novel organic charge transfer complex, 3,5-dimethylpyrrazolinium picrate was grown and crystallized by slow evaporation solution growth method at room temperature. The absorption of the grown crystal was studied using UV-visible spectral analysis and observed that the crystal possesses minimum absorption between 250 and 900 nm. The lower cut-off wavelength and the optical transmittance window were identified by optical transmittance study. The emission spectrum of the complex shows peaks at 505 and 758 nm are due to the green and red fluorescence emissions respectively. The thermogravimetry-differential thermal analyses (TG-DTA) were used to investigate the thermal stability of the complex. The single crystal X-ray diffraction method indicates that the complex crystallizes in monoclinic system with space group P2(1)/C. The FTIR and polarised Raman spectra were used to confirm the presence of various functional groups. The different kinds of protons and carbons were assigned through NMR (1H and 13C) spectroscopic techniques. The nonlinear optical property (NLO) of the material was studied by modified Kurtz-Perry powder technique. The complex exhibits good antibacterial and antifungal activities against various bacteria and fungi species.

  11. Spectrophotometric study of the charge-transfer and ion-pair complexation of methamphetamine with some acceptors.

    PubMed

    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 microg 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.

  12. Spectrophotometric determination of carvedilol in pharmaceutical formulations through charge-transfer and ion-pair complexation reactions.

    PubMed

    Cardoso, S G; Ieggli, C V S; Pomblum, S C G

    2007-01-01

    Simple extraction-free spectrophotometric methods have been developed for the determination of carvedilol (CAR). The methods were based either on charge-transfer reaction of the drug with the sigma-acceptor iodine, in acetonitrile, or on ion-pair formation with the acidic sulphophthalein dyes bromothymol blue (BTB) and bromocresol green (BCG), in chloroform. The obtained complexes showed absorbance maxima at 363, 411 and 414 nm, respectively for iodine, BTB and BCG. Beer's law validation, accuracy, precision, and other aspects of analytical merit are presented in the text. The proposed methods were applied for the determination of CAR in tablets and compounded capsules. The results were in good agreement with those obtained by an established UV spectrophotometric method.

  13. Tetrapeptide-coumarin conjugate 3D networks based on hydrogen-bonded charge transfer complexes: gel formation and dye release.

    PubMed

    Guo, Zongxia; Gong, Ruiying; Jiang, Yi; Wan, Xiaobo

    2015-08-14

    Oligopeptide-based derivatives are important synthons for bio-based functional materials. In this article, a Gly-(L-Val)-Gly-(L-Val)-coumarin (GVGV-Cou) conjugate was synthesized, which forms 3D networks in ethanol. The gel nanostructures were characterized by UV-vis spectroscopy, FT-IR spectroscopy, X-ray diffraction (XRD), SEM and TEM. It is suggested that the formation of charge transfer (CT) complexes between the coumarin moieties is the main driving force for the gel formation. The capability of the gel to encapsulate and release dyes was explored. Both Congo Red (CR) and Methylene Blue (MB) can be trapped in the CT gel matrix and released over time. The present gel might be used as a functional soft material for guest encapsulation and release.

  14. Charge-transfer complex formation between o-chloranil and a series of polynuclear aromatic hydrocarbons

    NASA Astrophysics Data System (ADS)

    Chakraborty, Biswanath; Mukherjee, Asok K.; Seal, Bejoy K.

    2001-02-01

    The equilibrium constants, enthalpies and entropies of formation of molecular electron donor-acceptor (EDA) complexes of o-chloranil with a series of aromatic hydrocarbons have been determined spectrophotometrically. Spectroscopic and thermodynamic aspects of these complexes have been analysed.

  15. Ultrasonic and spectral studies on charge transfer complexes of anisole and certain aromatic amines

    NASA Astrophysics Data System (ADS)

    Rajesh, R.; Raj Muhamed, R.; Justin Adaikala Baskar, A.; Kannappan, V.

    2016-10-01

    Stability constants of two complexes of anisole with aniline and N-methylaniline (NMA) are determined from the measured ultrasonic velocity in n-hexane medium at four different temperatures. Acoustic and excess thermo acoustic parameters [excess ultrasonic velocity (uE), excess molar volume (VE), excess internal pressure (πiE)] are reported for these systems at four different temperatures. The trend in acoustic and excess parameters with concentration in the two systems establishes the formation of hydrogen bonded complexes between anisole and the two amines. Thermodynamic properties are computed for the two complexes from the variation in K with temperature. The formation of these complexes is also established by UV spectral method and their spectral characteristics and stability constants are determined. K values of these complexes obtained by ultrasonic and UV spectroscopic techniques agree well. Aniline forms more stable complex than N-methylaniline with anisole in n-hexane medium.

  16. Charge transferred in brush discharges

    NASA Astrophysics Data System (ADS)

    Talarek, M.; Kacprzyk, R.

    2015-10-01

    Electrostatic discharges from surfaces of plastic materials can be a source of ignition, when appear in explosive atmospheres. Incendivity of electrostatic discharges can be estimated using the transferred charge test. In the case of brush discharges not all the energy stored at the tested sample is released and the effective surface charge density (or surface potential) crater is observed after the discharge. Simplified model, enabling calculation of a charge transferred during electrostatic brush discharge, was presented. Comparison of the results obtained from the simplified model and from direct measurements of transferred charge are presented in the paper.

  17. Charge-Transfer Versus Charge-Transfer-Like Excitations Revisited

    SciTech Connect

    Moore, Barry; Sun, Haitao; Govind, Niranjan; Kowalski, Karol; Autschbach, Jochen

    2015-07-14

    Criteria to assess charge-transfer (CT) and `CT-like' character of electronic excitations are examined. Time-dependent density functional theory (TDDFT) with non-hybrid, hybrid, and tuned long-range corrected (LC) functionals is compared with with coupled-cluster (CC) benchmarks. The test set includes an organic CT complex, two `push-pull' donor-acceptor chromophores, a cyanine dye, and several polycyclic aromatic hydrocarbons. Proper CT is easily identified. Excitations with significant density changes upon excitation within regions of close spatial proximity can also be diagnosed. For such excitations, the use of LC functionals in TDDFT sometimes leads to dramatic improvements of the singlet energies, similar to proper CT, which has led to the concept of `CT-like' excitations. However, `CT-like' excitations are not like charge transfer, and the improvements are not obtained for the right reasons. The triplet excitation energies are underestimated for all systems, often severely. For the `CT-like' candidates, when going from a non-hybrid to an LC functional the error in the singlet-triplet (S/T) separation changes from negative to positive, providing error compensation. For the cyanine, the S/T separation is too large with all functionals, leading to the best error compensation for non-hybrid functionals.

  18. Charge-Transfer Versus Charge-Transfer-Like Excitations Revisited.

    PubMed

    Moore, Barry; Sun, Haitao; Govind, Niranjan; Kowalski, Karol; Autschbach, Jochen

    2015-07-14

    Criteria to assess charge-transfer (CT) and CT-like character of electronic excitations are examined. Time-dependent density functional theory (TDDFT) calculations with non-hybrid, hybrid, and tuned long-range corrected (LC) functionals are compared with coupled-cluster (CC) benchmarks. The test set comprises an organic CT complex, two push-pull donor-acceptor chromophores, a cyanine dye, and several polycyclic aromatic hydrocarbons. Proper CT is easily identified. Excitations with significant density changes upon excitation within regions of close spatial proximity can also be diagnosed. For such excitations, the use of LC functionals in TDDFT sometimes leads to dramatic improvements of the singlet energies, similar to proper CT. It is shown that such CT-like excitations do not have the characteristics of physical charge transfer, and improvements with LC functionals may not be obtained for the right reasons. The TDDFT triplet excitation energies are underestimated for all systems, often severely. For the CT-like candidates, the singlet-triplet (S/T) separation changes from negative with a non-hybrid functional to positive with a tuned LC functional. For the cyanine, the S/T separation is systematically too large with TDDFT, leading to better error compensation for the singlet energy with a non-hybrid functional.

  19. Reversible non-volatile switch based on a TCNQ charge transfer complex

    NASA Technical Reports Server (NTRS)

    Nagasubramanian, Ganesan (Inventor); DiStefano, Salvador (Inventor); Moacanin, Jovan (Inventor)

    1993-01-01

    A solid-state synaptic memory matrix (10) having switchable weakly conductive connections at each node (24) whose resistances can be selectably increased or decreased over several orders of magnitude by control signals of opposite polarity, and which will remain stable after the signals are removed, comprises an insulated substrate (16), a set of electrical conductors (14) upon which is deposited a layer (18) of an organic conducting polymer, which changes from an insulator to a conductor upon the transfer of electrons, such as polymerized pyrrole doped with 7,7,8,8-tetracyanoquinodimethane (TCNQ), covered by a second set of conductors (20) laid at right angles to the first.

  20. Preparation and spectroscopic studies on charge-transfer complexes of 2-hydroxypyridine with electron acceptors

    NASA Astrophysics Data System (ADS)

    Gaballa, Akmal S.

    2013-07-01

    The CT-interactions of electron acceptors such as iodine (I2), chloranilic acid (H2CA) and 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) with 2-hydroxypyridine (HPyO) have been investigated in the defined solvent. The data indicate the formation of CT-complexes with the general formula [(HPyO)(acceptor)]. The 1:1 stoichiometry of the (HPyO)-acceptors were based on elemental analysis, IR spectra and thermogravimetric analysis of the solid CT-complexes along with the photometric titration measurements for the reactions. The formation constants (KCT) for the CT-complexes are shown to be strongly dependent on the type and structure of the electron acceptors. Factors affecting the CT-processes are discussed.

  1. Preparation and spectroscopic studies on charge-transfer complexes of famciclovir drug with different electron acceptors

    NASA Astrophysics Data System (ADS)

    Gaballa, Akmal S.; Teleb, Said M.; Nour, El-Metwally

    2012-09-01

    The CT-interaction of electron acceptors such as chloranilic acid (H2CA), 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) and and 7,7',8,8'-tetracyano-p-quinodimethane (TCNQ) with the antiviral drug famciclovir (FCV) have been investigated spectrophotometrically in the defined solvent. The data indicate the formation of CT-complexes with the general formula [(FCV)(acceptor)]. The 1:1 stoichiometry of the (FCV)-acceptors were based on elemental analysis, IR spectra and thermogravimetric analysis of the solid CT-complexes along with the photometric titration measurements for the reactions. The formation constants (KCT) for the CT-complexes are shown to be strongly dependent on the type and structure of the electron acceptor. Factors affecting the CT-processes such as redox potentials and steric hinderance of reactants are discussed.

  2. Experimental studies of light-induced charge transfer and charge redistribution in (X(2)-bipyridine)Re(I)(CO)(3)Cl complexes.

    PubMed

    Walters, Keith A; Kim, Young-Jin; Hupp, Joseph T

    2002-06-03

    Stark emission spectroscopy, transient DC photoconductivity (TDCP), and ground-state dipole moment measurements have been used to evaluate charge transfer (CT) within various (X(2)-bipyridine)Re(I)(CO)(3)Cl complexes following (3)MLCT excited-state formation. The Stark technique reports on vector differences between ground-state (mu(g)) and excited-state (mu(e)) dipole moments, while TDCP, when combined with independently obtained mu(g) information, reports on scalar differences. For systems featuring collinear, same-signed ground- and excited-state dipole moments, the scalar and vector differences are equivalent. However, for the low symmetry systems studied here, they are distinctly different. The vector difference yields the effective adiabatic one-electron-transfer distance (R(12)), while the combined vector and scalar data yield information about dipole rotation upon ground-state/excited-state interconversion. For the systems examined, charge transfer distances are substantially smaller than geometric electron-donor/electron-acceptor site separation distances. The measured distances are significantly affected by changes in acceptor ligand substituent composition. Electron-donating substituents decrease CT distances, while electron-withdrawing substituents increase CT distances, as do aromatic substituents that are capable of expanding the bipyridyl ligand (acceptor ligand) pi system. The Stark measurements additionally indicate that the CT vector and the transition dipole moment are significantly orthogonal, a consequence of strong polarization of the Re-Cl bond (orthogonal to the metal/acceptor-ligand plane) in the ground electronic state and relaxation of the polarization in the upper state. The ground-state Re-Cl bond polarization is sufficiently large that the overall ground-state scalar dipole moment exceeds the overall excited-state scalar dipole moment, despite transfer of an electron from the metal center to the diimine ligand. This finding provides an

  3. Interfacial charge-transfer transitions in a TiO2-benzenedithiol complex with Ti-S-C linkages.

    PubMed

    Fujisawa, Jun-ichi; Muroga, Ryuki; Hanaya, Minoru

    2015-11-28

    Interfacial charge-transfer (ICT) transitions between organic materials and inorganic semiconductors are a new mechanism for light absorption at organic-semiconductor interfaces. ICT transitions cause one-step interfacial charge separation without loss of energy. This feature is potentially useful to realize efficient organic-inorganic hybrid solar cells. ICT transitions have been examined by employing titanium dioxide (TiO2) nanoparticles chemisorbed with π-conjugated molecules via Ti-O-C linkages. Here, we report ICT transitions in a TiO2 and 1,2-benzenedithiol (BDT) complex with Ti-S-C linkages. BDT adsorbs on TiO2 by the bridging bidentate coordination of the sulfur atoms to surface titanium atoms. The TiO2-BDT complex shows ICT transitions from the BDT moiety to the conduction band of TiO2 in the visible region. The ICT transitions occur by orbital overlaps between the d orbitals of the surface titanium atoms and the π orbitals of the benzene ring. Our density-functional-theory (DFT) analysis reveals that the 3p valence orbitals of the sulfur bridging atoms contribute to more than 50% of the highest occupied molecular orbital (HOMO) and the 3d-3p(sulfur)-π interaction via the Ti-S-C linkage enhances the electronic mixing between the titanium atoms and the benzene moiety as compared to the 3d-2p(oxygen)-πvia the Ti-O-C linkage. This result indicates the important role of the heavier-atom linkers for strong organic-inorganic electronic couplings.

  4. Charge Transfer Dissociation of Complex Oligosaccharides: Comparison with Collision-Induced Dissociation and Extreme Ultraviolet Dissociative Photoionization

    NASA Astrophysics Data System (ADS)

    Ropartz, David; Li, Pengfei; Fanuel, Mathieu; Giuliani, Alexandre; Rogniaux, Hélène; Jackson, Glen P.

    2016-10-01

    The structural characterization of oligosaccharides still challenges the field of analytical chemistry. Tandem mass spectrometry offers many advantages toward this aim, although the generic fragmentation method (low-energy collision-induced dissociation) shows clear limitations and is often insufficient to retrieve some essential structural information on these molecules. In this work, we present the first application of helium charge transfer dissociation (He-CTD) to characterize the structure of complex oligosaccharides. We compare this method with low-energy collision-induced dissociation and extreme-ultraviolet dissociative photoionization (XUV-DPI), which was shown previously to ensure the successful characterization of complex glycans. Similarly to what could be obtained by XUV-DPI, He-CTD provides a complete description of the investigated structures by producing many informative cross-ring fragments and no ambiguous fragmentation. Unlike XUV-DPI, which is performed at a synchrotron source, He-CTD has the undeniable advantage of being implementable in a conventional benchtop ion trap in a conventional laboratory setting.

  5. Evaluation of the parameters of 1:1 charge transfer complexes from spectrophotometric data by non-linear numerical method

    NASA Astrophysics Data System (ADS)

    Grebenyuk, Serhiy A.; Perepichka, Igor F.; Popov, Anatolii F.

    2002-11-01

    The non-linear numerical method for evaluation of equilibrium constants and molar extinction coefficients of molecular complexes from a spectrophotometric experiment is described, which in contrast to linear models has no limitations with respect to concentrations of the components. The proposed procedure is applied to donor-acceptor interaction in solution between N-ethyl carbazole (EtCz) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) or n-hexyl 2,5,7-trinitro-9-dicyanomethylenefluorene-4-carboxylate (HexDTFC) to evaluate the method and to obtain the parameters of charge transfer complexes (CTCs) formation. Association constants ( K) and molar extinction coefficients ( ɛ) of CTCs derived from non-linear approach (EtCz-TCNQ: K=2.49±0.19 M -1; ɛ=2950±160 M -1 cm -1. EtCz-HexDTFC: K=12.1±0.3 M -1; ɛ=1335±24 M -1 cm -1) are close to that from linear models but show lower standard errors in parameter estimations.

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

    NASA Astrophysics Data System (ADS)

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

    2013-02-01

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

  7. Charge Transfer Between Quantum Dots and Peptide-Coupled Redox Complexes

    DTIC Science & Technology

    2009-01-01

    scale ) Ruthenium complex 190 2009 NRL REVIEW NANOSCIENCE TECHNOLOGY N or m al iz ed C ur re nt (µ A ) Potential, V vs...DHLA QDs Abs 2 Ru /QD Abs 5 Ru /QD FIGURE 4 Enzymatic assay of chymotrypsin activity utilizing QD–Ru peptide conjugates, showing enzymatic ve ...0.01 0.02 0.03 0.04 Vmax = 0.04 +/- 0.02 µM/min KM = 0.83 +/- 0.16 µM KM = 2.2 +/- 0.5 µM Vmax = 0.01 +/- 0.004 µM/min No inhibitor + Chymostatin inhibitor V el oc ity (µ M C hy m -R u cl ea ve d

  8. A visible light excitable fluorescent sensor for triphosphate/pyrophosphate based on a diZn2+ complex bearing an intramolecular charge transfer fluorophore.

    PubMed

    Su, Guangyu; Liu, Zhipeng; Xie, Zhijun; Qian, Fang; He, Weijiang; Guo, Zijian

    2009-10-14

    Triphosphate or pyrophosphate can be recognised by a diZn(2+) complex of bis(BPEA)-appended intramolecular charge transfer fluorophore 4-amino-7-aminosulfonyl-2,1,3-benzoxadiazole, displaying a 5-6 fold fluorescent enhancement at 576 nm.

  9. Metal-Ligand Complex-Induced Ultrafast Charge-Carrier Relaxation and Charge-Transfer Dynamics in CdX (X=S, Se, Te) Quantum Dots Sensitized with Nitrocatechol.

    PubMed

    Singhal, Pallavi; Maity, Partha; Jha, Sanjay K; Ghosh, Hirendra N

    2017-08-04

    The present work describes the effect of interfacial complex formation on charge carrier dynamics in CdX (X=S, Se, Te) quantum dots (QDs) sensitized nitro catechol (NCAT). To compare experiments were also carried out with catechol (CAT) where no such complexation was observed. Time-resolved emission studies suggest faster charge separation in CdS(Se)/NCAT system as compared to CdS(Se)/CAT although change in Gibbs free energy for hole transfer is less in former as compared to later. This suggests that complex formation favours charge separation. Similar studies were also carried out in CdTe/NCAT system where hole transfer process was not viable thermodynamically but due to complex formation charge separation was observed. Femtosecond transient absorption studies have been carried out to monitor charge carrier dynamics in early time scale. Transient studies show faster electron cooling in QDs/NCAT system as compared to pure QDs and has been assigned to the complex formation on QDs surface. Interestingly charge recombination dynamics is much faster in QDs/NCAT system as compared to pure QDs which can be attributed to the stronger coupling between QDs and NCAT. Our results suggest a strong metal-ligand complex formation on QDs surface that controls charge carrier dynamics in QDs/molecular adsorbate system and to the best of our knowledge it has never been reported. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Catching the role of anisotropic electronic distribution and charge transfer in halogen bonded complexes of noble gases

    SciTech Connect

    Bartocci, Alessio; Cappelletti, David; Pirani, Fernando; Belpassi, Leonardo; Falcinelli, Stefano; Grandinetti, Felice; Tarantelli, Francesco

    2015-05-14

    The systems studied in this work are gas-phase weakly bound adducts of the noble-gas (Ng) atoms with CCl{sub 4} and CF{sub 4}. Their investigation was motivated by the widespread current interest for the intermolecular halogen bonding (XB), a structural motif recognized to play a role in fields ranging from elementary processes to biochemistry. The simulation of the static and dynamic behaviors of complex systems featuring XB requires the formulation of reliable and accurate model potentials, whose development relies on the detailed characterization of strength and nature of the interactions occurring in simple exemplary halogenated systems. We thus selected the prototypical Ng-CCl{sub 4} and Ng-CF{sub 4} and performed high-resolution molecular beam scattering experiments to measure the absolute scale of their intermolecular potentials, with high sensitivity. In general, we expected to probe typical van der Waals interactions, consisting of a combination of size (exchange) repulsion with dispersion/induction attraction. For the He/Ne-CF{sub 4}, the analysis of the glory quantum interference pattern, observable in the velocity dependence of the integral cross section, confirmed indeed this expectation. On the other hand, for the He/Ne/Ar-CCl{sub 4}, the scattering data unravelled much deeper potential wells, particularly for certain configurations of the interacting partners. The experimental data can be properly reproduced only including a shifting of the repulsive wall at shorter distances, accompanied by an increased role of the dispersion attraction, and an additional short-range stabilization component. To put these findings on a firmer ground, we performed, for selected geometries of the interacting complexes, accurate theoretical calculations aimed to evaluate the intermolecular interaction and the effects of the complex formation on the electron charge density of the constituting moieties. It was thus ascertained that the adjustments of the potential

  11. Catching the role of anisotropic electronic distribution and charge transfer in halogen bonded complexes of noble gases.

    PubMed

    Bartocci, Alessio; Belpassi, Leonardo; Cappelletti, David; Falcinelli, Stefano; Grandinetti, Felice; Tarantelli, Francesco; Pirani, Fernando

    2015-05-14

    The systems studied in this work are gas-phase weakly bound adducts of the noble-gas (Ng) atoms with CCl4 and CF4. Their investigation was motivated by the widespread current interest for the intermolecular halogen bonding (XB), a structural motif recognized to play a role in fields ranging from elementary processes to biochemistry. The simulation of the static and dynamic behaviors of complex systems featuring XB requires the formulation of reliable and accurate model potentials, whose development relies on the detailed characterization of strength and nature of the interactions occurring in simple exemplary halogenated systems. We thus selected the prototypical Ng-CCl4 and Ng-CF4 and performed high-resolution molecular beam scattering experiments to measure the absolute scale of their intermolecular potentials, with high sensitivity. In general, we expected to probe typical van der Waals interactions, consisting of a combination of size (exchange) repulsion with dispersion/induction attraction. For the He/Ne-CF4, the analysis of the glory quantum interference pattern, observable in the velocity dependence of the integral cross section, confirmed indeed this expectation. On the other hand, for the He/Ne/Ar-CCl4, the scattering data unravelled much deeper potential wells, particularly for certain configurations of the interacting partners. The experimental data can be properly reproduced only including a shifting of the repulsive wall at shorter distances, accompanied by an increased role of the dispersion attraction, and an additional short-range stabilization component. To put these findings on a firmer ground, we performed, for selected geometries of the interacting complexes, accurate theoretical calculations aimed to evaluate the intermolecular interaction and the effects of the complex formation on the electron charge density of the constituting moieties. It was thus ascertained that the adjustments of the potential suggested by the analysis of the

  12. A Novel Green TiO2 Photocatalyst with a Surface Charge-Transfer Complex of Ti and Hydrazine Groups.

    PubMed

    Tian, Lihong; Xu, Jilian; Alnafisah, Abrar; Wang, Ran; Tan, Xinyu; Oyler, Nathan A; Liu, Lei; Chen, Xiaobo

    2017-01-29

    The optical property of TiO2 plays an important role in its various and promising photocatalytic applications. Previous efforts in improving its optical properties include doping with various metal and/or non-metal elements, coupling with other colorful semiconductors or molecules, and hydrogenating to crystalline/disordered core/shell nanostructures. Here, we report a beautiful green TiO2 achieved by forming the charge-transfer complex of colorless hydrazine groups and surface Ti(4+) , which extends the optical absorption into the near infrared region (≈1100 nm, 1.05 eV). It shows an enhanced photocatalytic performance in hydrogen generation under simulated sunlight, and degradation of organic pollution under visible light due to an impurity state (about 0.28 eV) resulting in fast electron-hole separation and injection of electrons from the ligand to the conduction band of TiO2 . This study demonstrates an alternative approach to tune the optical, impurity state and photocatalytic properties of TiO2 nanoparticles and we believe this will spur a wide interest in related materials and applications.

  13. Room temperature deintercalation of alkali metal atoms from epitaxial graphene by formation of charge-transfer complexes

    SciTech Connect

    Shin, H.-C.; Ahn, S. J.; Kim, H. W.; Moon, Y.; Rai, K. B.; Woo, S. H.; Ahn, J. R.

    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.

  14. Enhancement Performances in White Organic Light-Emitting Diode (WOLED) by Formation of Charge-Transfer (CT) Complex.

    PubMed

    Sze, Po-Wen; Huang, Chien-Jung; Lin, Fong-Yi; Lan, Wen-How

    2015-11-01

    This study elucidates the optoelectronic properties of high efficiency white organic light-emitting diodes (WOLED) with molybdenum oxide (MoO3) doping into N, N0-di (naphthalene-1-yl)-N, N0-diphenyl-benzidine (NPB) as a p-doping hole-transport layer (p-HTL). The device with a MoO3-doping NPB layer shows a turn-on voltage of 2.01 V and the maximum power efficiency of 4.6 lm/W. The X-ray photoelectron spectroscopy (XPS) and UV-vis-NIR absorption spectra of MoO3-doping NPB layer revealed that the MoO3-doping NPB p-HTL had an improvement on holes injection. The improvement is caused by the formation of the charge transfer (CT) complex (NPB(+)-MoO3-) that is generated by doping MoO3 into NPB, markedly increasing the number of holes carrier, improving the balance of the electrons and holes in recombination zone. The pure white light emission with Commissions Internationale De L'Eclairage (CIE) coordinates of (0.335, 0.321) was achieved at the operating voltage of 6 V. This device shows the maximum luminance of 12230 cd/cm2 and the maximum luminous efficiency of 7.01 cd/A at an operating voltage of 7 V.

  15. Photoexcitation and charge-transfer-to-solvent relaxation dynamics of the I(-)(CH3CN) complex.

    PubMed

    Mak, Chun C; Timerghazin, Qadir K; Peslherbe, Gilles H

    2013-08-15

    Photoexcitation of iodide-acetonitrile clusters, I(-)(CH3CN)n, to the charge-transfer-to-solvent (CTTS) state and subsequent cluster relaxation could result in the possible formation of cluster analogues of the bulk solvated electron. In this work, the relaxation process of the CTTS excited iodide-acetonitrile binary complex, [I(-)(CH3CN)]*, is investigated using rigorous ab initio quantum chemistry calculations and direct-dynamics simulations to gain insight into the role and motion of iodine and acetonitrile in the relaxation of CTTS excited I(-)(CH3CN)n. Computed potential energy curves and profiles of the excited electron vertical detachment energy for [I(-)(CH3CN)]* along the iodine-acetonitrile distance coordinate reveal for the first time significant dispersion effects between iodine and the excited electron, which can have a significant stabilizing effect on the latter. Results of direct-dynamics simulations demonstrate that [I(-)(CH3CN)]* undergoes dissociation to iodine and acetonitrile fragments, resulting in decreased stability of the excited electron. The present work provides strong evidence of solvent translational motion and iodine ejection as key aspects of the early time relaxation of CTTS excited I(-)(CH3CN)n that can also have a substantial impact on the subsequent electron solvation processes and further demonstrates that intricate details of the relaxation process of CTTS excited iodide-polar solvent molecule clusters make it heavily solvent-dependent.

  16. Spectroscopic characterization of charge-transfer complexes of morpholine with chloranilic and picric acids in organic media: Crystal structure of bis(morpholinium 2,4,6-trinitrocyclohexanolate)

    NASA Astrophysics Data System (ADS)

    Refat, Moamen S.; El-Zayat, Lamia A.; Yeşilel, Okan Zafer

    2010-02-01

    Electron donor-acceptor interaction of morpholine (morp) with chloranilic acid (cla) and picric acid (pa) as π-acceptors was investigated spectrophotometrically and found to form stable charge-transfer (CT) complexes (n-π*) of [(Hmorp) 2(cla)] and [(Hmorp)(pa)] 2. The donor site involved in CT interaction is morpholine nitrogen. These complexes are easily synthesized from the reaction of morp with cla and pa within MeOH and CHCl 3 solvents, respectively. 1HNMR, IR, elemental analyses, and UV-vis techniques characterize the two morpholinium charge-transfer complexes. Benesi-Hildebrand and its modification methods were applied to the determination of association constant ( K), molar extinction coefficient ( ɛ). The X-ray crystal structure was carried out for the interpretation the predict structure of the [(Hmorp)(pa)] 2 complex.

  17. Kinetically stable metal ligand charge transfer complexes as crosslinks in nanogels/hydrogels: Physical properties and cytotoxicity.

    PubMed

    Wang, Rong; Both, Sanne K; Geven, Mike; Calucci, Lucia; Forte, Claudia; Dijkstra, Pieter J; Karperien, Marcel

    2015-10-01

    A terpyridine end-functionalized 8-arm poly(ethylene glycol) was prepared using the reaction of a 4'-aminopentanoxy substituted terpyridine with a p-nitrophenyl chloroformate activated PEG-(OH)8. Supramolecular complexation of the polymer terpyridine moieties by Fe(2+) ions was investigated using NMR, UV-Vis and dynamic light scattering experiments. At low concentrations addition of Fe(2+) ions to an aqueous solution of the polymer conjugate afforded nanogels with a single size distribution around 250 nm. At concentrations above 3 wt%, and at a 1:2 metal to ligand molar ratio, hydrogels were formed with increasing mechanical properties at increasing polymer concentrations. Using bovine chondrocytes, the biocompatibility and potential cytotoxicity of the polymer conjugate, nanogels and hydrogels were studied. The polymer conjugate with free ligands was toxic to the cells likely due to depletion of essential metal ions. When the terpyridine groups were complexed with Fe(2+) ions, both nanogel suspensions and hydrogels showed no cytotoxicity in direct contact with chondrocytes. Indirect contact of gels with chondrocytes using transwells revealed the absence of toxic components by leaching. A Live-Dead assay on chondrocytes encapsulated in the hydrogels indicated that the hydrogels are cytocompatible, revealing the potential use of these materials for biomedical and pharmaceutical applications. The binding between transition metal ions and ligands with multiple binding sites can be almost as strong as covalent bonds. This metal-ligand charge transfer (MLCT) complexation was used to crosslink water soluble polymers into hydrogels. This approach to novel materials may find applications in the biomedical and pharmaceutical fields. Transition metal ions are essential trace elements present in tissue but up to now no cytotoxicity data of free ligands are available. Data presented show that free ligands are toxic to cells likely by depletion of trace metal ions, whereas

  18. Methylthio- and ethanediyldithio-substituted 1,6-dithiapyrenes and their charge-transfer complexes: new organic molecular metals

    SciTech Connect

    Nakasuji, K.; Sasaki, M.; Kotani, T.; Murata, I.; Enoki, T.; Imaeda, K.; Inokuchi, H.; Kawamoto, A.; Tanaka, J.

    1987-11-11

    The synthesis and physical properties of 2,7-bis(methylthio)-1,6-diathiapyrene (MTDTPY) and 2,3:7,8-bis(ethanediyldithio)-1,6-dithiapyrene (ETDTPY) and their charge-transfer complexes are reported. MTDTPY was prepared from 1,6-dithiapyrene. ETDTPY was prepared from naphthalene-1,5-dithiol in four steps. These two new donors showed reversible two-stage redox behavior with potentials comparable to that of tetrathiafulvalene. MTDTPY produced two crystalline phases of 1:1 TCNQ complexes, the ..cap alpha..-form (monoclinic, P2/sub 1//c) and the ..beta..-form (triclinic, P anti 1), which consist of mixed stacks and uniform segregated stacks of donors and acceptors, respectively. The ..beta..-form contained short S...S contacts between adjacent donor columns (3.48 and 3.57 A). The single-crystal conductivity of the ..beta..-form was metallic (sigma/sub rt/ = 110 S cm/sup -1/, T/sub c/ = 110 K), while that of the ..cap alpha..-form was semiconductive (sigma/sub rt/ = 3.4 x 10/sup -6/ S cm/sup -1/). MTDTPY-chloranil crystallized in uniform segregated stacks of donors and acceptors (triclinic P anti 1). Relatively short interstack S...S contacts were also observed (3.60 and 3.67 A). The single-crystal conductivity was metallic (sigma/sub rt/ = 140 S cm/sup -1/, T/sub c/ = 240 K). MTDTPY-bromanil also showed metallic conductivity (sigma/sub rt/ = 230 S cm/sup -1/, T/sub c/ = 125 K). The long needle crystals of MTDTPY-I/sub 2.2/ and ETDTPY-I/sub 2.3/ showed semiconducting behavior with relatively high conductivities, 13 and 42 S cm/sup -1/, respectively.

  19. Synthesis and Electrochemical Proprieties of Novel Unsymmetrical Bis-Tetrathiafulvalenes and Electrical Conductivity of Their Charge Transfer Complexes with Tetracyanoquinodimethane (TCNQ)

    PubMed Central

    Abbaz, Tahar; Bendjeddou, Amel; Gouasmia, Abdelkrim; Regainia, Zine; Villemin, Didier

    2012-01-01

    The synthesis and properties of a series of bis-tetrathiafulvalenes (bis-TTFs) containing nitrophenyl, aminophenyl or dimethylaminophenyl is reported. The synthesis was carried out by using routes involving Wittig-type, cross-coupling, reduction and alkylation reactions. The electron donor ability of these new compounds has been measured by cyclic voltammetry (CV). Charge transfer complexes with tetracyanoquinodimethane (TCNQ) were prepared by chemical redox reactions. The complexes have been proven to give conducting materials. PMID:22942678

  20. Intermolecular interaction in the NH3-H2 and H2O-H2 complexes by molecular beam scattering experiments: the role of charge transfer.

    PubMed

    Pirani, Fernando; Cappelletti, David; Belpassi, Leonardo; Tarantelli, Francesco

    2013-11-27

    New molecular beam scattering experiments are reported for the ammonia-hydrogen system recording with unprecedented resolution "glory" quantum interferences in the total cross sections. Direct comparison with the analogous water-hydrogen complex, investigated under the same experimental conditions, highlights relevant differences in the intermolecular interaction affecting the observables. Analysis of the electronic charge displacement accompanying formation of both complexes, calculated using very accurate ab initio methods, helps to rationalize the experimental findings and unveils the selective and crucial role of charge transfer in driving water interactions and formation of a weak hydrogen bond.

  1. Catalysis: Quantifying charge transfer

    NASA Astrophysics Data System (ADS)

    James, Trevor E.; Campbell, Charles T.

    2016-02-01

    Improving the design of catalytic materials for clean energy production requires a better understanding of their electronic properties, which remains experimentally challenging. Researchers now quantify the number of electrons transferred from metal nanoparticles to an oxide support as a function of particle size.

  2. Usefulness of charge-transfer complexation for the assessment of sympathomimetic drugs: Spectroscopic properties of drug ephedrine hydrochloride complexed with some π-acceptors

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

    Recently, ephedrine (Eph) assessment in food products, pharmaceutical formulations, human fluids of athletes and detection of drug toxicity and abuse, has gained a growing interest. To provide basic data that can be used to assessment of Eph quantitatively based on charge-transfer (CT) complexation, the CT complexes of Eph with 7‧,8,8‧-tetracyanoquinodimethane (TCNQ), dichlorodicyanobenzoquinone (DDQ), 1,3-dinitrobenzene (DNB) or tetrabromothiophene (TBT) were synthesized and spectroscopically investigated. The newly synthesized complexes have been characterized via elemental analysis, IR, Raman, 1H NMR, and UV-visible spectroscopy. The formation constant (KCT), molar extinction coefficient (εCT) and other spectroscopic data have been determined using the Benesi-Hildebrand method and its modifications. The sharp, well-defined Bragg reflections at specific 2θ angles have been identified from the powder X-ray diffraction patterns. Thermal decomposition behavior of these complexes was also studied, and their kinetic thermodynamic parameters were calculated with Coats-Redfern and Horowitz-Metzger equations.

  3. Charge-Transfer Complexes and Photochemistry of Ozone with Ferrocene and n-Butylferrocene: A UV-vis Matrix-Isolation Study.

    PubMed

    Pinelo, Laura F; Kugel, Roger W; Ault, Bruce S

    2015-10-15

    The reactions of ozone with ferrocene (cp2Fe) and with n-butylferrocene (n-butyl cp2Fe) were studied using matrix isolation, UV-vis spectroscopy, and theoretical calculations. The codeposition of cp2Fe with O3 and of n-butyl cp2Fe with O3 into an argon matrix led to the production of 1:1 charge-transfer complexes with absorptions at 765 and 815 nm, respectively. These absorptions contribute to the green matrix color observed upon initial deposition. The charge-transfer complexes underwent photochemical reactions upon irradiation with red light (λ ≥ 600 nm). Theoretical UV-vis spectra of the charge-transfer complexes and photochemical products were calculated using TD-DFT at the B3LYP/6-311G++(d,2p) level of theory. The calculated UV-vis spectra were in good agreement with the experimental results. MO analysis of these long-wavelength transitions showed them to be n→ π* on the ozone subunit in the complex and indicated that the formation of the charge-transfer complex between ozone and cp2Fe or n-butyl cp2Fe affects how readily the π* orbital on O3 is populated when red light (λ ≥ 600 nm) is absorbed. 1:1 complexes of cp2Fe and n-butyl cp2Fe with O2 were also observed experimentally and calculated theoretically. These results support and enhance previous infrared studies of the mechanism of photooxidation of ferrocene by ozone, a reaction that has considerable significance for the formation of iron oxide thin films for a range of applications.

  4. Chemical Control of Charge Trapping and Charge Transfer Processes at the Organic-Inorganic Interface within Quantum Dot-Organic Complexes

    SciTech Connect

    Weiss, Emily A.

    2015-11-06

    Within the research program funded through the Early Career Research Award we designed complexes of colloidal semiconductor quantum dots (QDs) and organic molecules in which the interfacial chemistry controls the electronic structure and dynamics of the excitonic state of the QD. The program included two main projects; (1) investigation of the mechanisms by which organic surfactants control the quantum confinement of excitonic charge carriers; and (2) development of models for electron transfer between QDs and adsorbed molecules as a function of interfacial chemistry. This project was extremely successful in that our achievements in those two areas addressed the great majority of questions we outlined in the original proposal and answered questions I did not think to ask in that original proposal. Our work led to the discovery of “exciton delocalizing ligands”, which change the electronic structure of colloidal semiconductor nanocrystals by altering, with small synthetic modifications to their surfaces, their most defining characteristic – the quantum confinement of their excited states. It also led to detailed, quantitative descriptions of how the surface chemistry of a QD dictates, thermodynamically and kinetically, the probability of exchange of electrons between the QD and a small molecule. We used two of the three major techniques in the proposal (transient photoluminescence and transient absorption). Electrogenerated chemiluminescence was also proposed, but was too technically difficult with these systems to be useful. Instead, NMR spectroscopy emerged as a major analytical tool in our studies. With the fundamental advancements we made with this project, we believe that we can design QDs to be the next great class of visible-light photocatalysts.

  5. Synthesis of charge transfer complex of chloranilic acid as acceptor with p-nitroaniline as donor: Crystallographic, UV-visible spectrophotometric and antimicrobial studies

    NASA Astrophysics Data System (ADS)

    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.

  6. Synthesis of racemic and chiral BEDT-TTF derivatives possessing hydroxy groups and their achiral and chiral charge transfer complexes.

    PubMed

    Krivickas, Sara Jane; Hashimoto, Chiho; Yoshida, Junya; Ueda, Akira; Takahashi, Kazuyuki; Wallis, John D; Mori, Hatsumi

    2015-01-01

    arrangements, θ(21) and two kinds of α'-types, and their electrical conductivities of charge transfer complexes based upon the racemic and enantiopure (S,S)-2, and (R,R)-2 donors originates not only from the chirality, but also the introduced intermolecular hydrogen bonds involving the hydroxymethyl groups, perchlorate anion, and the included solvent H2O.

  7. Spectroscopic and thermodynamic study of charge transfer complex formation between cloxacillin sodium and riboflavin in aqueous ethanol media of varying composition

    NASA Astrophysics Data System (ADS)

    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.

  8. Direct visual evidence for chemical mechanism of SERRS of the S-complex of pyrimidine molecule adsorbed on silver nanoparticle via charge transfer

    NASA Astrophysics Data System (ADS)

    Zhang, Xin; Wang, Peijie; Sheng, Shaoxiang; Zhang, Lisheng; Fang, Yan

    2014-03-01

    In this paper, the S-complex of pyrimidine molecule absorbed on silver clusters was employed as a model molecule to study the enhancement mechanism in surface-enhanced resonance Raman scattering (SERRS). We described the chemical enhancement of SERRS through charge transfer (CT) from Ag20 to pyrimidine on resonance excitation, and electromagnetic enhancement through intracluster charge redistribution (CR) on the electronic intracluster collective oscillation excitation. It is shown that SERRS process of the pyrimidine molecule absorbed on silver clusters with different incident wavelength are dominated by different enhancement mechanisms. Both experimental and theoretical works have been performed to understand the CT process in SERRS.

  9. Solvent effects on the metal-to-ligand charge transfer transition of the complex [Ru(NH3)5(Pyrazine)]2+

    NASA Astrophysics Data System (ADS)

    Chagas, Marcelo A.; Rocha, Willian R.

    2014-09-01

    In this work the solvent effects on the structure and metal-to-ligand charge transfer (MLCT) transition of the complex [Ru(NH3)5(Pyrazine)]2+ was investigated in aqueous solution, using the hybrid Density Functional Theory/Effective Fragment Potential Hamiltonian (DFT/EFP/MD) approach. The MLCT transition causes a large charge separation in the complex and produces a dipole moment variation of 8.3 ± 1.1 Debye upon excitation in solution and causes a large red-shift of 0.55 ± 0.15 eV. The solvatochromic shift can be attributed to the large charge separation accompanying the MLCT transition in solution.

  10. A spectrophotometric and thermodynamic study of the charge-transfer complexes of iodine with 2-aminomethyl-15-crown-5 in chloroform and 1,2-dichloroethane solutions.

    PubMed

    Hasani, Masoumeh; Akbari, Sakineh

    2007-05-01

    Interaction of 2-aminomethyl-15-crown-5 (AM15C5) with iodine has been investigated spectrophotometrically in chloroform and 1,2-dichloroethane (1,2-DCE) solutions. The observed time dependence of the charge-transfer band and subsequent formation of I(3)(-) in solution were related to the slow transformation of the initially formed 1:1 AM15C5.I(2) outer complex to an inner electron donor-acceptor (EDA) complex, followed by fast reaction of the inner complex with iodine to form a triiodide ion. The pseudo-first-order rate constants were evaluated from the absorbance- and conductivity-time data. The stoichiometry and formation constants of the resulting EDA complexes have also been determined. Thermodynamic parameters, Delta H degrees and Delta S degrees , of the complexes have been determined from the temperature dependence of stability constants by Van't Hoff equation. The results indicate that iodine complexes of AM15C5 in both solvents are enthalpy stabilized but entropy destabilized. The influence of solvent properties on the kinetics and stability of the resulting charge-transfer complexes are discussed.

  11. Charge-transfer complexes of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone with amino molecules in polar solvents

    NASA Astrophysics Data System (ADS)

    Berto, Silvia; Chiavazza, Enrico; Ribotta, Valentina; Daniele, Pier Giuseppe; Barolo, Claudia; Giacomino, Agnese; Vione, Davide; Malandrino, Mery

    2015-10-01

    The charge-transfer complexes have scientific relevance because this type of molecular interaction is at the basis of the activity of pharmacological compounds and because the absorption bands of the complexes can be used for the quantification of electron donor molecules. This work aims to assess the stability of the charge-transfer complexes between the electron acceptor 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and two drugs, procaine and atenolol, in acetonitrile and ethanol. The stability of DDQ in solution and the time required to obtain the maximum complex formation were evaluated. The stoichiometry and the stability of the complexes were determined, respectively, by Job's plot method and by the elaboration of UV-vis titrations data. The latter task was carried out by using the non-linear global analysis approach to determine the equilibrium constants. This approach to data elaboration allowed us to overcome the disadvantages of the classical linear-regression method, to obtain reliable values of the association constants and to calculate the entire spectra of the complexes. NMR spectra were recorded to identify the portion of the donor molecule that was involved in the interaction. The data support the participation of the aliphatic amino groups in complex formation and exclude the involvement of the aromatic amine present in the procaine molecule.

  12. Single-molecule conductance of a chemically modified, π-extended tetrathiafulvalene and its charge-transfer complex with F4TCNQ.

    PubMed

    García, Raúl; Herranz, M Ángeles; Leary, Edmund; González, M Teresa; Bollinger, Gabino Rubio; Bürkle, Marius; Zotti, Linda A; Asai, Yoshihiro; Pauly, Fabian; Cuevas, Juan Carlos; Agraït, Nicolás; Martín, Nazario

    2015-01-01

    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.

  13. Electrochemical and spectral studies of auto-assembled arrays of calix[4]arenequinhydrone charge-transfer complex on indium-tin oxide (ITO) glass.

    PubMed

    Youchret-Zallez, Oumayma Ben; Besbes-Hentati, Salma; Bouvet, Marcel; Said, Hechmi

    2014-01-01

    A sensing materiel based on calix[4]arene molecules is electrochemically deposited on ITO electrode coated. A brown film was electrodeposited at a potential Eimp = -1.00 V versus SCE in acetonitrile solvent, however in dichloromethane solvent, a bluish film auto-assembled on the ITO electrode coated at a potential Eimp = -0.65 V versus SCE. Both films are subsequently analyzed by cyclic voltammetry and UV-Vis spectroscopy. This investigation shows that in acetonitrile solvent, the charge-transfer complex, calix[4]arenequinhydrone was formed in electrolytic solution and it was not self-assembled on the ITO electrode. The related UV-Vis spectrum shows a single absorption band towards a wavelength about 350 nm. The optical behaviour of the blue film shows two absorption bands: the first one appears on the first absorption band of the acceptor at 305 nm and the second one in the visible range at 502 nm. The band situated in the visible range correspond to a well-defined charge-transfer band indicating the presence of the charge-transfer complex, the calix[4]arenequinhydrone.

  14. Single-molecule conductance of a chemically modified, π-extended tetrathiafulvalene and its charge-transfer complex with F4TCNQ

    PubMed Central

    García, Raúl; Herranz, M Ángeles; González, M Teresa; Bollinger, Gabino Rubio; Bürkle, Marius; Zotti, Linda A; Asai, Yoshihiro; Pauly, Fabian; Cuevas, Juan Carlos; Agraït, Nicolás

    2015-01-01

    Summary 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. PMID:26199662

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

    NASA Astrophysics Data System (ADS)

    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.

  16. Microscopic solvation and femtochemistry of charge-transfer reactions: the problem of benzene(s)-iodine binary complexes and their solvent structures

    NASA Astrophysics Data System (ADS)

    Cheng, P. Y.; Zhong, D.; Zewail, A. H.

    1995-08-01

    Charge-transfer reactions are studied on the femtosecond and picosecond time scales and under controlled composition in a molecular beam. The system of interest is iodine in aromatic and non-aromatic solvents, which goes back to Hildebrand and Mulliken almost 50 years ago. For the first time, the isolated binary complex and its solvated structural dynamics are studied. The product iodine atoms are positively identified and the concept of harpoon mechanism introduced. The dynamics are related to the impact geometry of the transition state and the electronic structure. A global potential energy surface is described with molecular dynamics detailing the motion in the reaction coordinates.

  17. Surface charge-transfer complex formation of catechol on titanium(IV) oxide and the application to bio-sensing.

    PubMed

    Murata, Yusuke; Hori, Hiroshige; Taga, Atsushi; Tada, Hiroaki

    2015-11-15

    Adsorption properties of 2-hydroxyphenol (catechol) on TiO2 particles has been studied at 298K. The adsorption proceeds from the aqueous solution with the Langmuir type behavior. Diffuse reflectance infrared spectra of the catechol-adsorbed TiO2 suggested that catechol is adsorbed on TiO2 solution via the chelation to the surface Ti ions. The adsorption induces a strong absorption in the whole visible region, of which intensity increases with an increase in the adsorption amount. Photoelectrochemical experiments and molecular orbital calculations indicate that the absorption stems from the charge-transfer (CT) transition from the HOMO of catechol to the conduction band of TiO2. Time courses for the adsorption of catechol on mesoporous TiO2 nanocrystalline film-coated glass was traced by measuring the change in the absorbance of the CT band, and analyzed on the basis of the Langmuir model. This study would present a new simple technique for sensing of important biomolecules bearing the catechol moiety.

  18. Utility of positron annihilation lifetime technique for the assessment of spectroscopic data of some charge-transfer complexes derived from N-(1-Naphthyl)ethylenediamine dihydrochloride

    NASA Astrophysics Data System (ADS)

    Refat, Moamen S.; Adam, Abdel Majid A.; Sharshar, T.; Saad, Hosam A.; Eldaroti, Hala H.

    2014-03-01

    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.

  19. Sensitized emission of luminescent lanthanide complexes based on 4-naphthalen-1-yl-benzoic acid derivatives by a charge-transfer process.

    PubMed

    Kim, Yong Hee; Baek, Nam Seob; Kim, Hwan Kyu

    2006-01-16

    The photophysical properties of 4-naphthalen-1-yl-benzoic acid ligands and their Eu(III)-cored complexes were systematically investigated to elucidate the effective energy-transfer pathway in luminescent lanthanide complexes. A series of 4-naphthalen-1-yl-benzoic acid ligands, such as 4-naphthalen-1-yl-benzoic acid (NA-1), 4-[4-(4-methoxyphenyl)-naphthalen-1-yl]-benzoic acid (NA-2), and 4-{4-[4-(4-methoxyphenyl)-naphthalen-1-yl]-benzyloxy}-benzoic acid (NA-3), were synthesized and utilized for the synthesis of their Eu(III)-cored complexes, corresponding to NAC-1, NAC-2, and NAC-3. The fluorescence spectra of NA-1 and NA-2 show large Stokes shifts with increasing solvent polarity. These large Stokes shifts might be dominantly due to the formation of an intramolecular charge transfer (ICT) complex in the excited state. Also, the intensive luminescence of the Eu(III) ions by the photoexcitation of the ligand in NAC-1 and NAC-2 in polar solvents supports that the energy transfer from the ligand to the Eu(III) ion takes place efficiently. In the case of NA-3, which has a -CH2OPh- group that acts as a blocking group, there is no dependence of the fluorescence spectrum on the solvent nature and no luminescence of the Eu(III) ions by the photoexcitation of the ligand, indicating no formation of the ICT state. This can be due to the fact that the formation of the ICT state in NA-3 was prevented because the -OCH2- group acts as a blocking group by interrupting the pi-conjugation between the benzoic acid and the naphthalene unit. From these photophysical studies, we suggest that the ICT state plays a very important role in the energy-transfer pathway from the ligand to the Eu(III) ion. To our best knowledge, this is the first demonstration of sensitized emission of luminescent lanthanide complexes based on 4-naphthalen-1-yl-benzoic acid derivatives by the charge-transfer process.

  20. Complexes of acridine and 9-chloroacridine with I2: formation of unusual I6 chains through charge-transfer interactions involving amphoteric I2.

    PubMed

    Rimmer, E L; Bailey, R D; Hanks, T W; Pennington, W T

    2000-11-17

    Acridine and 9-chloroacridine form charge-transfer complexes with iodine in which the nitrogen-bound I2 molecule is amphoteric; one end serves as a Lewis acid to the heterocyclic donor, while the other end acts as a Lewis base to a second I2 molecule that bridges two acridine.I2 units. In the acridine derivative [(acridine.I2)2.I2, 1], the dimer has a "zigzag" conformation, while in the 9-chloroacridine derivative [(9-Cl-acridine.I2)2.I2, 2], the dimer is "C-shaped". The thermal decomposition of the two complexes is very different. Compound 1 loses one molecule of I2 to form an acridine.I2 intermediate, which has not been isolated. Further decomposition gives acridine as the form II polymorph, exclusively. Decomposition of 2 involves the loss of two molecules of I2 to form a relatively stable intermediate [(9-Cl-acridine)2.I2, 3]. Compound 3 consists of two 9-Cl-acridine molecules bridged through N...I charge-transfer interactions by a single I2 molecule. This compound represents the first known example, in which both ends of an I2 molecule form interactions in a complex that is not stabilized by the extended interactions of an infinite chain structure. The ability of the terminal iodine of an N-bound I2 to act either as an electron donor (complexes 1 and 2) or as an electron acceptor (complex 3) can be understood through a quantum mechanical analysis of the systems. Both electrostatic interactions and the overlap of frontier molecular orbitals contribute to the observed behavior.

  1. Synthesis, structures and charge-transfer complexations of 1,n-di-[3,6-di-(9-carbazolyl)-9-carbazolyl]alkanes with tetracyanoethylene and tetranitromethane

    NASA Astrophysics Data System (ADS)

    Özgün, Selin; Asker, Erol; Zeybek, Orhan

    2017-01-01

    Synthesis and charge-transfer (CT) complexations of amorphous 3,6-di-(9-carbazolyl)-9-ethylcarbazole, 3,6-di-(9-carbazolyl)-9-hexylcarbazole and a series of 1,n-di-[3,6-di-(9-carbazolyl)-9-carbazolyl]alkanes (n = 1-5) with electron acceptors tetracyanoethylene and tetranitromethane are reported. The molar extinction coefficients (ε), equilibrium constants (Keq), enthalpies (ΔH) and entropies (ΔS) of complexations have been determined. The low Keq values (1.83-3.82 M-1 for carbazole-TCNE and 0.28-0.45 M-1 for carbazole-TNM complexes) show weak donor-acceptor associations. The negative values of ΔH determined to be between -2.09 ± 0.08 and -3.10 ± 0.21 kcal mol-1 for carbazole-TCNE complexes and -0.91 ± 0.08 and -3.31 ± 0.28 kcal mol-1 for carbazole-TNM complexes indicate that complexations are driven by the exothermic enthalpies. Computational analysis using semi-empirical and DFT methods were applied to clarify the structures of the synthesized molecules and the nature of their CT complexations.

  2. Synthesis, characterization, spectrophotometric, structural and antimicrobial studies of the newly charge transfer complex of p-phenylenediamine with π acceptor picric acid

    NASA Astrophysics Data System (ADS)

    Khan, Ishaat M.; Ahmad, Afaq; Oves, M.

    2010-12-01

    Charge transfer complex (CTC) of donor, p-phenylenediamine (PPD) and acceptor, 2,4,6-trinitrophenol (picric acid) has been studied in methanol at room temperature. The CT complex was synthesized and characterized by elemental analysis, FTIR spectra, 1H NMR spectroscopy and electronic absorption spectra which indicate the CT interaction associated with proton migration from the acceptor to the donor followed by hydrogen bonding via N +-H⋯O -. The thermal stability of CT complex was studied using TGA and DTA analyses techniques. The CT complex was screened for its antifungal activity against Aspergillus niger (Laboratory isolate), Candida albicans (IQA-109) and Penicillium sp. (Laboratory isolate) and antibacterial activity against two Gram-positive bacteria Staphylococcus aureus (MSSA 22) and Bacillus subtilis (ATCC 6051) and two Gram-negative bacteria Escherichia coli (K 12) and Pseudomonas aeruginosa (MTCC 2488). It gives good antimicrobial activity. The stoichiometry of the CT complex was found to be 1:1. The physical parameters of CT complex were evaluated by the Benesi-Hildebrand equation. On the basis of the studies, the structure of CT complex is [(PPDH) +(PA) -], and a general mechanism for its formation is proposed.

  3. Quantitative studies of ground and excited state charge transfer complexes of fullerenes with N,N-dimethylaniline and N,N-diethylaniline

    SciTech Connect

    Sun, Y.P.; Bunker, C.E.; Ma, B. )

    1994-10-19

    A comprehensive spectroscopic study of ground state charge transfer complexes and exciplexes of C[sub 60] and C[sub 70] with N,N-diethylaniline (DEA) and N,N-dimethylaniline (DMA) is reported. The pure absorption spectra of ground state complexes and pure exciplex fluorescence spectra of C[sub 60]/C[sub 70]-DEA/DMA are determined by use of a chemometrics method principal component analysis - self modeling spectral resolution. The exciplex emissions are strongly solvent dependent. In room-temperature toluene, exciplex emissions are absent and the quenching of monomer fluorescence involves both dynamic and static processes. In room-temperature hexane, the quenching of monomer excited state is dominated by the formation of exciplexes. The observed dual fluorescence for C[sub 60]/C[sub 70]-DEA/DMA in hexane can be explained by a mechanism in which contributions from both prompt and delayed monomer emissions are considered. 36 refs., 12 figs.

  4. Determination of nicotine in tobacco with second-order spectra data of charge-transfer complex in ethanol-water binary solvents processed by parallel factor analysis.

    PubMed

    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.

  5. Determination of nicotine in tobacco with second-order spectra data of charge-transfer complex in ethanol-water binary solvents processed by parallel factor analysis

    NASA Astrophysics Data System (ADS)

    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.

  6. Sparfloxacin charge transfer complexes with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone and tetracyanoquinodimethane: Molecular structures, spectral, and DFT studies

    NASA Astrophysics Data System (ADS)

    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. Electronic, infrared, mass, 1H NMR spectral studies of the charge-transfer complexes of sulphonamide drugs with π-acceptors in acetonitrile

    NASA Astrophysics Data System (ADS)

    Frag, Eman Y.; Mohamed, Gehad G.

    2010-08-01

    The rapid interaction between sulphonamides (sulphamethoxazole (SMZ), sulphaguanidine (SGD), sulphaquinoxaline sodium (SQX) and sulphadimidine sodium (SDD)) as n-electron donors with the 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and 2,5-dichloro-3,6-dihydroxy-1,4-benzoquinone (chloranilic acid, p-CLA) as π-acceptors resulted in the formation of 1:1 charge-transfer complexes as the final products with the formula [(drug) (acceptor)]. The final products of the reactions have been isolated and characterized using FT-IR, 1H NMR, mass spectroscopy and elemental analyses as well as photometric measurements and thermogravimetric analysis (TG). The stoichiometry and apparent formation constants of the complexes formed were determined by applying the conventional spectrophotometric molar ratio method.

  8. Polymorphism in the organic charge-transfer complex dibenzotetrathiafulvalene-7,7,8,8-tetracyanoquinodimethane (DBTTF-TCNQ) and its effect on optical and electrical properties (Presentation Recording)

    NASA Astrophysics Data System (ADS)

    Goetz, Katelyn P.; Tsutsumi, Jun ya; Pookpanratana, Sujitra; Chen, Jihua; Hasegawa, Tatsuo; Jurchescu, Oana D.

    2015-10-01

    We present the structural, optical, and electronic properties of two polymorphs of the charge-transfer complex dibenzotetrathiafulvalene-7,7,8,8-tetracyanoquinodimethane (DBTTF-TCNQ). The structures were resolved using electron diffraction. One is a rectangular-shaped platelet and exhibits ambipolar transport with gold contacts in organic field-effect transistors (OFETs). The second polymorph grows as a thin, circular platelet and shows p-type transport within the same OFET structure. The difference in electrical characteristics originates from two factors. First, the position of the HOMO level of the rectangular polymorph lies 0.07 eV below that of the circular polymorph, as determined by ultraviolet photoelectron spectroscopy (UPS). Second, using X-Ray photoelectron and Raman spectroscopies we find that the degree of charge transfer between the donor DBTTF and acceptor TCNQ varies from 0.4e +/- 0.1e for the rectangular crystals to 0.1e +/- 0.1e for the circular crystals. Additional differences between the two polymorphs arise when measuring the absorbance of the crystals. First, the peak corresponding to intermolecular charge transfer is offset by 0.05 eV between the two polymorphs, in agreement with UPS measurements. Additionally, the polarization angle dependence of the intermolecular CT band for the rectangular crystal is shifted by 60deg with respect to the angle dependence of the intramolecular transition. In contrast, this shift was only 20deg for the circular polymorph. These angle dependences allowed us to couple the anisotropy of the electrical characteristics to the optical measurements. Our results demonstrate how slight modifications in crystal structure yield drastic differences in optical and electrical properties in organic semiconducting materials.

  9. Charge-Transfer Complexation at Carminic Acid-CdS Interface and Its Impact on the Efficiency of Dye-Sensitized Solar Cells

    NASA Astrophysics Data System (ADS)

    Shahzad, Naila; Shah, Syed Mujtaba; Munir, Shamsa; Hana, Amina; Jabeen, Uzma; Nosheen, Erum; Habib, Banafsha; Khan, Arif Ullah; Hassan, Zubair; Siddiq, Muhammad; Hussain, Hazrat

    2015-04-01

    We report for the first time charge-transfer complex formation at the interface of carminic acid and cadmium sulfide (CdS) nanoparticles. The complex formation was confirmed by ultraviolet-visible (UV-vis) and fluorescence emission spectroscopy. Cadmium sulfide nanoparticles were synthesized by the wet chemical method and characterized by UV-vis spectroscopy, x-ray diffraction and transmission electron microscopy. Carminic acid, in different concentrations, was chemisorbed on the surface of CdS nanoparticles. Grafting of carminic acid on CdS was confirmed by Fourier transform infrared spectroscopy. Energy levels of the highest occupied molecular orbitals and lowest unoccupied molecular orbitals (LUMO) of both carminic acid and CdS nanoparticles matched well for the injection of electron from LUMO of carminic acid to the conduction band of cadmium sulfide. The photoactive nanohybrid material was used in dye-sensitized solar cells. The efficiency of carminic acid functionalized CdS nanoparticles was found to be double the value obtained for the reference device and remained constant over a certain concentration range owing to the complex formation at the interface. However, raising the concentration of carminic acid beyond 2.5 × 10-5 M resulted in a decrease in efficiency. This was ascribed to charge recombination due to the presence of ungrafted carminic acid molecules.

  10. Neutral-Type One-Dimensional Mixed-Valence Halogen-Bridged Platinum Chain Complexes with Large Charge-Transfer Band Gaps.

    PubMed

    Otake, Ken-ichi; Otsubo, Kazuya; Sugimoto, Kunihisa; Fujiwara, Akihiko; Kitagawa, Hiroshi

    2016-03-07

    One-dimensional (1D) electronic systems have attracted significant attention for a long time because of their various physical properties. Among 1D electronic systems, 1D halogen-bridged mixed-valence transition-metal complexes (the so-called MX chains) have been thoroughly studied owing to designable structures and electronic states. Here, we report the syntheses, structures, and electronic properties of three kinds of novel neutral MX-chain complexes. The crystal structures consist of 1D chains of Pt-X repeating units with (1R,2R)-(-)-diaminocychlohexane and CN(-) in-plane ligands. Because of the absence of a counteranion, the neutral MX chains have short interchain distances, so that strong interchain electronic interaction is expected. Resonance Raman spectra and diffuse-reflectance UV-vis spectra indicate that their electronic states are mixed-valence states (charge-density-wave state: Pt(2+)···X-Pt(4+)-X···Pt(2+)···X-Pt(4+)-X···). In addition, the relationship between the intervalence charge-transfer (IVCT) band gap and the degree of distortion of the 1D chain shows that the neutral MX chains have a larger IVCT band gap than that of cationic MX-chain complexes. These results provide new insight into the physical and electronic properties of 1D chain compounds.

  11. Preparation, spectroscopic and thermal characterization of new charge-transfer complexes of ethidium bromide with π-acceptors. In vitro biological activity studies

    NASA Astrophysics Data System (ADS)

    Eldaroti, Hala H.; Gadir, Suad A.; Refat, Moamen S.; Adam, Abdel Majid A.

    2013-05-01

    Ethidium bromide (EtBr) is a strong DNA binder and has been widely used to probe DNA structure in drug-DNA and protein-DNA interaction. Four new charge-transfer (CT) complexes consisting of EtBr as donor and quinol (QL), picric acid (PA), tetracyanoquinodimethane (TCNQ) or dichlorodicyanobenzoquinone (DDQ) as acceptors, were synthesized and characterized by elemental analysis, electronic absorption, spectrophotometric titration, IR, Raman, 1H NMR and X-ray powder diffraction (XRD) techniques. The stoichiometry of these complexes was found to be 1:2 ratio and having the formula [(EtBr)(acceptor)]. The thermal stability of the synthesized CT complexes was investigated using thermogravimetric (TG) analyses, and the morphology and particle size of these complexes were obtained from scanning electron microscopy (SEM). The CT complexes were also tested for its antibacterial activity against two Gram-positive bacteria Staphylococcus aureus and Bacillus subtilis and two Gram-negative bacteria; Escherichia coli and Pseudomonas aeuroginosa strains by using Tetracycline as standard and antifungal property against Aspergillus flavus and Candida albicans by using amphotericin B as standard. The results were compared with the standard drugs and significant conclusions were obtained. The results indicated that the [(EtBr)(QL)2] complex had exerted excellent inhibitory activity against the growth of the tested bacterial strains.

  12. An unusual (H(2)O)(20) discrete water cluster in the supramolecular host of a charge transfer platinum(ii) complex: cytotoxicity and DNA cleavage activities.

    PubMed

    Mandal, Sutanuva; Castiñeiras, Alfonso; Mondal, Tapan K; Mondal, Arindam; Chattopadhyay, Dhrubajyoti; Goswami, Sreebrata

    2010-10-28

    The chemical reaction of Pt(II)(L(1))Cl(2) [L(1) = N-4-tolylpyridine-2-aldimine] with a bidentate N,S-donor atom ligand, 2-methylthioaniline, (HL(2)) in alkaline methanolic medium yielded a mixed ligand donor-acceptor complex, [Pt(II)(L(1))(L(2))]Cl, [1]Cl. The complex has been characterized by different spectroscopic and electrochemical techniques. The complex showed intense interligand charge transfer (ILCT) transition in the long wavelength region of UV-vis spectrum (>600 nm). The single-crystal X-ray structure of complex, [1]Cl·3.3H(2)O is reported. The cationic complex upon crystallization from aqueous methanol solvent produces an assembly of discrete, three dimensional (H(2)O)(20) guest moiety within the reference Pt-complex host lattice. The water assembly showed a unique type of aggregation of a distorted cube encapsulated by hydrogen bonded network of a twelve-water ring. The complex displayed one reversible cathodic response at -0.75 V and two irreversible anodic responses at 0.42 and 0.79 V versus Ag/AgCl reference electrode. The redox processes are characterized by EPR and spectroelectrochemistry. Density-functional theory calculations were employed to confirm the structural features and to support the spectral and redox properties of the complex. The square-planar complex has been found to intercalate DNA. Fluorescence spectroscopy, circular dichroism, cyclic voltammetry, viscosity measurements, together with DNA melting studies have been employed to characterize the binding of [1]Cl with calf thymus DNA. Agarose gel electrophoresis indicates that the complex cleaves supercoiled (SC) pUC19 plasmid DNA to its nicked circular (NC) form via singlet oxygen. As determined by a MTT assay, [1]Cl exhibits significant cytotoxicity with IC(50) value 58 μM.

  13. Study of interfacial charge-transfer complex on TiO{sub 2} particles in aqueous suspension by second-harmonic generation

    SciTech Connect

    Liu, Y.; Dadap, J.I.; Zimdars, D.; Eisenthal, K.B.

    1999-04-01

    Titanium dioxide (TiO{sub 2}) is a wide band-gap semiconductor having two common crystal forms: rutile and anatase. Due to its high physical and chemical stability, it is extensively studied as a photocatalyst for photolysis of water, and for oxidative photomineralization of organic pollutants in wastewater, aimed at harvesting solar energy. The authors report the first direct observation of an interfacial charge-transfer complex using second-harmonic spectroscopy. The second-harmonic spectrum of catechol adsorbed on 0.4 micron-sized TiO{sub 2} (anatase) colloidal particles in aqueous suspension reveals a charge-transfer band centered at 2.72 eV (456 nm). In addition, the adsorption isotherm of catechol on the colloidal TiO{sub 2} suspension was obtained and gave an excellent fit to the Langmuir adsorption model. From this, the authors infer the free energy of the adsorption to be {Delta}G{degree} = {minus}6.8 kcal/mol.

  14. Narrow-band irradiation of a homologous series of chlorophenols on TiO2: charge-transfer complex formation and reactivity.

    PubMed

    Agrios, Alexander G; Gray, Kimberly A; Weitz, Eric

    2004-07-06

    The goal of this research was to investigate the formation and reactivity of charge-transfer complexes (CTCs) among a homologous series of chlorophenols on TiO2. We previously showed that 2,4,5-trichlorophenol (245TCP) forms a CTC with Degussa P25, a commercial preparation of TiO2. Here, we probe how light energy influences reactivity and product formation. Slurries of P25 containing 245TCP were irradiated at 360, 400, 430, 480, and 550 nm. At each wavelength, the amount of transformation of 245TCP correlates to the diffuse-reflectance absorbance of a 245TCP/P25 system, supporting the CTC as the cause of reaction. In addition, polymeric products are formed only under wavelengths that excite the CTC, indicating a different reaction mechanism for the CTC than for bandgap excitation of TiO2. We also found a higher quantum efficiency for CTC reactivity than for bandgap activation of the catalyst, suggesting that the photocatalytic efficiency and selectivity can be improved for certain compounds by designing catalytic materials that form CTCs with them. Furthermore, to determine how chlorine substitution patterns affected adsorption and sub-bandgap reactivity, P25 slurries containing phenol, 4-chlorophenol, 2,4-dichlorophenol, or 2,4,6-trichlorophenol were probed following dark contact or irradiation at 360, 430, or 550 nm. With respect to the extent of adsorption, complexation, reaction, and polymerization on P25, the behavior of 245TCP far exceeded that of the other chlorophenols. Among these chlorophenols, only 2,4-dichlorophenol produced a polymeric product. 245TCP is unique among this family of chlorophenols, which we attribute to a chlorine arrangement that leads to a favorable orbital overlap with TiO2 and sterically permits coupling reactions. Our results demonstrate the critical role that charge-transfer complexation can play in determining the rates and products of photocatalytic reactions.

  15. Influence of fused aromatic ring on the stability of charge transfer complex between iodine and some five membered heterocyclic molecules through ultrasonic and spectral studies

    NASA Astrophysics Data System (ADS)

    Ulagendran, V.; Balu, P.; Kannappan, V.; Kumar, R.; Jayakumar, S.

    2017-08-01

    The charge transfer (CT) interaction between two fused heterocyclic compounds with basic pyrrole group as donors, viz., indole (IND) and carbazole (CAR), and iodine (acceptor) in DMSO medium is investigated by ultrasonic and UV-visible spectral methods at 303 K. The formation of CT complex in these systems is established from the trend in acoustical and excess thermo acoustical properties with molar concentration. The frequency acoustic spectra (FAS) is also carried out on these two systems for two fixed concentrations 0.002 M and 0.02 M, and in the frequency range 1 MHz-10 MHz to justify the frequency chosen for ultrasonic study. The absorption coefficient values in solution are computed and discussed. The formation constants of these complexes are determined using Kannappan equation in ultrasonic method. The formation of 1:1 complexes between iodine and IND, CAR was established by the theory of Benesi - Hildebrand in the UV-visible spectroscopic method. The stability constants of the CT complexes determined by spectroscopic and ultrasonic methods show a similar trend. These values also indicate that the presence of fused aromatic ring influences significantly when compared with K values of similar CT complexes of parent five membered heterocyclic compound (pyrrole) reported by us earlier.

  16. Photophysics of Re(I) and Ru(II) diimine complexes covalently linked to pyrene: contributions from intra-ligand charge transfer states.

    PubMed

    Del Guerzo, André; Leroy, Stéphanie; Fages, Frédéric; Schmehl, Russell H

    2002-01-28

    The photophysical properties of Ru(II) and Re(I) polypyridyl complexes including a bis-bipyridyl pyrene ligand are presented. The complexes ([(bpy)(2)Ru](2)bpb)(4+) and [(CO)(3)ReCl(bpb)] (bpy = 2,2'-bipyridine, bpb = 1,6-bis-(4-(2,2'-bipyrid-yl)-pyrene) were designed with the intent of examining intramolecular energy migration between MLCT states localized on the metal complexes and pyrene-localized (3)(pi-pi) states. Absorption spectroscopy of both complexes containing the bpb ligand reveals that in addition to the MLCT and the pyrene-centered (1)(pi-pi) transitions, a new absorption band is observed near 400 nm for both complexes. Absorption spectral data for the Re(I) complex strongly suggest the presence of a pyrene(pi) to bpy(pi) intraligand charge transfer (ILCT) transition. Emission spectra at room temperature and at 77 K are almost identical for the Ru(II) and Re(I) complexes containing the bpb ligand. The (3)MLCT emission of related bipyridyl compounds lacking the pyrene is observed at higher energy than for the pyrene-containing complexes, ([(bpy)(2)Ru](2)bpb)(4+) and [(CO(3)ReCl(bpb)]. The Ru(II) complex emits at room temperature with a remarkably long lifetime (130 micros in degassed DMSO). This emission is also strongly sensitive to oxygen and is almost entirely quenched in an aerated solution. In addition, excited-state absorption spectra exhibit features not consistent with (3)MLCT or (3)(pi-pi) states of the parent chromophores. The combined characteristics suggest the emission arises from either (3)(pi-pi) or (3)ILCT states or a state with mixed parentage.

  17. Coherence in metal-metal-to-ligand-charge-transfer excited states of a dimetallic complex investigated by ultrafast transient absorption anisotropy.

    PubMed

    Cho, Sung; Mara, Michael W; Wang, Xianghuai; Lockard, Jenny V; Rachford, Aaron A; Castellano, Felix N; Chen, Lin X

    2011-04-28

    Coherence in the metal-metal-to-ligand-charge transfer (MMLCT) excited state of diplatinum molecule [Pt(ppy)(μ-(t)Bu(2)pz)](2) has been investigated through the observed oscillatory features and their corresponding frequencies as well as polarization dependence in the single-wavelength transient absorption (TA) anisotropy signals. Anticorrelated parallel and perpendicular TA signals with respect to the excitation polarization direction were captured, while minimal oscillatory features were observed in the magic angle TA signal. The combined analysis of the experimental results coupled with those previous calculated in the literature maps out a plausible excited state trajectory on the potential energy surface, suggesting that (1) the two energetically close MMLCT excited states due to the symmetry of the molecule may be electronically and coherently coupled with the charge density shifting back and forth between the two phenylpyridine (ppy) ligands, (2) the electronic coupling strength in the (1)MMLCT and (3)MMLCT states may be extracted from the oscillation frequencies of the TA signals to be 160 and 55 cm(-1), respectively, (3) a stepwise intersystem crossing cascades follows (1)MMLCT → (3)MMLCT (T(1b)) → (3)MMLCT (T(1a)), and (4) a possible electronic coherence can be modulated via the Pt-Pt σ-interactions over a picosecond and survive the first step of intersystem crossing. Future experiments are in progress to further investigate the origin of the oscillatory features. These experimental observations may have general implications in design of multimetal center complexes for photoactivated reactions where coherence in the excited states may facilitate directional charge or energy transfer along a certain direction between different parts of a molecule.

  18. Spontaneous charged lipid transfer between lipid vesicles.

    PubMed

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

    2017-10-03

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

  19. Chemoselective Catalytic Oxidation of 1,2-Diols to α-Hydroxy Acids Controlled by TEMPO-ClO2 Charge-Transfer Complex.

    PubMed

    Furukawa, Keisuke; Shibuya, Masatoshi; Yamamoto, Yoshihiko

    2015-05-01

    Chemoselective catalytic oxidation from 1,2-diols to α-hydroxy acids in a cat. TEMPO/cat. NaOCl/NaClO2 system has been achieved. The use of a two-phase condition consisting of hydrophobic toluene and water suppresses the concomitant oxidative cleavage. A study of the mechanism suggests that the observed selectivity is derived from the precise solubility control of diols and hydroxy acids as well as the active species of TEMPO. Although the oxoammonium species TEMPO(+)Cl(-) is hydrophilic, the active species dissolves into the organic layer by the formation of the charge-transfer (CT) complex TEMPO-ClO2 under the reaction conditions.

  20. Utilization of charge-transfer complexation for the detection of carcinogenic substances in foods: Spectroscopic characterization of ethyl carbamate with some traditional π-acceptors

    NASA Astrophysics Data System (ADS)

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

    2013-04-01

    The study of toxic and carcinogenic substances in foods represents one of the most demanding areas in food safety, due to their repercussions for public health. One potentially toxic compound for humans is ethyl carbamate (EC). EC is a multi-site genotoxic carcinogen of widespread occurrence in fermented foods and alcoholic beverages. Structural and thermal stability of charge-transfer complexes formed between EC as a donor with quinol (QL), picric acid (PA), chloranilic acid (CLA), p-chloranil (p-CHL) and 1,3-dinitrobenzene (DNB) as acceptors were reported. Elemental analysis (CHN), electronic absorption spectra, photometric titration, IR, and 1H NMR spectra show that the interaction between EC and acceptors was stabilized by hydrogen bonding, via a 1:1 stoichiometry. Thermogravimetric (TG) analysis indicates that the formation of molecular CT complexes was stable, exothermic and spontaneous. Finally, the CT complexes were screened for their antibacterial and antifungal activities. The results indicated that the [(EC)(QL)] complex exhibited strong antimicrobial activities against various bacterial and fungal strains compared with standard drugs.

  1. Synthesis, spectroscopic characterization and structural investigations of a new charge transfer complex of 2,6-diaminopyridine with 3,5-dinitrobenzoic acid: DNA binding and antimicrobial studies

    NASA Astrophysics Data System (ADS)

    Khan, Ishaat M.; Ahmad, Afaq; Kumar, Sarvendra

    2013-03-01

    A new charge transfer (CT) complex [(DAPH)+(DNB)-] consisting of 2,6-diaminopyridine (DAP) as donor and 3,5-dinitrobenzoic acid (DNB-H) as acceptor, was synthesized and characterized by FTIR, 1H and 13C NMR, ESI mass spectroscopic and X-ray crystallographic techniques. The hydrogen bonding (N+-H⋯O-) plays an important role to consolidate the cation and anion together. CT complex shows a considerable interaction with Calf thymus DNA. The CT complex was also tested for its antibacterial activity against two Gram-positive bacteria Staphylococcus aureus and Bacillus subtilis and two Gram-negative bacteria Escherichia coli and Pseudomonas aeruginosa strains by using Tetracycline as standard, and antifungal property against Aspergillus niger, Candida albicans, and Penicillium sp. by using Nystatin as standard. The results were compared with standard drugs and significant conclusions were obtained. A polymeric net work through H-bonding interactions between neighboring moieties was observed. This has been attributed to the formation of 1:1 type CT complex.

  2. A new route for visible/near-infrared-light-driven H2 production over titania: Co-sensitization of surface charge transfer complex and zinc phthalocyanine

    NASA Astrophysics Data System (ADS)

    Zhang, Xiaohu; Peng, Bosi; Peng, Tianyou; Yu, Lijuan; Li, Renjie; Zhang, Jing

    2015-12-01

    This work introduces a new strategy for visible/near-infrared (NIR) light responsive H2 production over TiO2 nanoparticles co-sensitized with zinc phthalocyanine derivative (Zn-tri-PcNc) and surface ligand-to-metal charge transfer (LMCT) complex, which is in situ formed on the TiO2 nanoparticles' surfaces by using ascorbic acid (AA). The in situ formed surface LMCT complex (AA-TiO2) exhibits obvious visible-light-responsive photoactivity (126.2 μmol/h) for H2 production with a high apparent quantum yield (AQY) of 16.1% at 420 nm monochromatic light irradiation. Moreover, the co-sensitized TiO2 nanoparticles (Zn-tri-PcNc-TiO2-AA) shows a much higher photoactivity (162.2 μmol/h) for H2 production than the surface LMCT complex, and broader spectral responsive region (400-800 nm) with a relatively high AQY value (0.97%) at 700 nm monochromatic light irradiation. The present result reveals a possible substitute for the conventional Ru(II)-bipyridyl complexes or organic dyes as sensitizer of semiconductors in the field of solar fuel conversion.

  3. Syntheses, crystal structures, electronic spectra and magnetic properties of two ion-pair charge transfer complexes based on [Ni(mnt)2]-

    NASA Astrophysics Data System (ADS)

    Xu, Xiao-Yi; Chen, Xuan-Rong; Yang, Qing-Cheng; Xue, Chen; Tao, Jian-Qing; Liu, Jian-Lan; Ren, Xiao-Ming

    2017-01-01

    Two new bimetallic ion-pair complexes 1 and 2 with general formula [M(phen)3][Ni(mnt)2]2 (phen = 1, 10-phenanthroline, mnt2- = maleonitriledithiolate; M = Ni2+, Fe2+ for 1 and 2), have been prepared and characterized by IR, elemental analysis, single crystal X-ray diffraction, UV-vis-NIR spectra and magnetic measurements. The structural determination reveals that the crystals of two ion-pair complexes, with monoclinic space group C2/c, have similar cell parameters and the [M(phen)3]2+ cations and the [Ni(mnt)2]- anions are packed by forming alternate layers. Thermogravimetric (TG) analyses revealed that 1 and 2 are thermally stable up to ∼170 °C. UV-vis-NIR spectra discloses that two complexes exhibit sizable absorption in near-IR region because of ion-pair charge transfer (IPCT) transitions in 1 and 2. Investigation of the magnetic properties 1 shows Curie-Weiss-type paramagnetic behavior in the temperature range 2-400 K. For 2, the paramagnetic behavior above ∼40 K indicated the [Fe(phen)3]2+ ion has a low-spin state and the weak Curie-Weiss type tail below 40 K results from a trace amount of paramagnetic [Ni(mnt)2]- species.

  4. Charge-transfer complexations of 1, n-di(9-ethylcarbazol-3-yl)alkanes with tetracyanoethylene and tetranitromethane

    NASA Astrophysics Data System (ADS)

    Asker, Erol; Masnovi, John

    2009-01-01

    1, n-Di(9-ethylcarbazol-3-yl)alkanes, where n = 1-5, as the dichromophoric model compounds of poly-3-vinylcarbazoles were synthesized to examine their complexation behaviors with the electron acceptors tetracyanoethylene (TCNE) and tetranitromethane (TNM). 9,9'-Diethyl-3,3'-dicarbazolyl, di(3-ethylcarbazol-9-yl)methane, and three monomeric analogues were also included for comparison. In dichloromethane solution, the dicarbazoles formed stable 1:1 electron donor-acceptor complexes with TCNE having formation enthalpies around -3.5 kcal/mol. With TNM they formed more weakly bound complexes that showed little dependence on concentration and almost zero dependence on temperature changes having nearly 0 kcal/mol enthalpies of formation. The smaller gap between the two carbazole groups in 1, n-di(9-ethylcarbazol-3-yl)alkanes with n ≤ 2 affected complexation adversely, while such an effect was not observed in the dicarbazoles with n ≥ 3.

  5. Interfacial charge-transfer transitions and reorganization energies in sulfur-bridged TiO2-x-benzenedithiol complexes (x: o, m, p).

    PubMed

    Fujisawa, Jun-Ichi; Muroga, Ryuki; Hanaya, Minoru

    2016-08-10

    Surface complexes formed between TiO2 nanoparticles and enediol compounds such as 1,2-benzenediol (o-BDO) via Ti-O-C linkages show absorption of visible light due to interfacial charge-transfer (ICT) transitions. The ICT transitions take place from the π-conjugated systems to TiO2. Recently, we reported a surface complex formed between TiO2 and 1,2-benzenedithiol (o-BDT) via Ti-S-C linkages. This sulfur-bridged complex shows ICT transitions from the sulfur bridging atoms to TiO2. Interestingly, it was demonstrated that the ICT transitions in the sulfur-bridged TiO2-o-BDT complex induce photoelectric conversion more efficiently than those in the oxygen-bridged TiO2-o-BDO complex. This result suggests that carrier recombination is suppressed with the sulfur bridging atoms. In this paper, we examine ICT transitions and reorganization energies in the sulfur-bridged TiO2-x-BDT complexes (x: o, m, p) and compare them with those in the oxygen-bridged TiO2-x-BDO complexes. The estimated reorganization energies for the sulfur-bridged TiO2-x-BDT complexes (x: o, m, p) are much smaller than those for the oxygen-bridged TiO2-x-BDO ones. Based on the Marcus theory, the small reorganization energy calculated for the TiO2-o-BDT complex, which is less than half of that for the TiO2-o-BDO complex, increases the activation energy of carrier recombination. The small reorganization energy is attributed to the characteristic distribution of the highest occupied molecular orbital (HOMO) on the sulfur-bridging atoms in the TiO2-o-BDT complex, which inhibits structural changes in the benzene ring in the ICT excited state. Our work reveals the important role of the sulfur bridging atoms in the suppression of carrier recombination.

  6. Presence or absence of a novel charge-transfer complex in the base-catalyzed hydrolysis of N-ethylbenzamide or ethyl benzoate.

    PubMed

    Yamabe, Shinichi; Guan, Wei; Sakaki, Shigeyoshi

    2013-01-01

    Reaction paths of base-catalyzed hydrolyses of isoelectronic substrates, Ph-C(=O)-X-Et [X = O (ethyl benzoate) and X = NH (N-ethylbenzamide)], were traced by DFT calculations. To simulate bond interchanges accompanied by proton transfers, a cluster model of Ph-C(=O)-X-Et + OH(-)(H(2)O)(16) was employed. For X = O, three elementary processes and for X = NH four ones were obtained. The rate-determining step of X = O is the first TS (TS1, the OH(-) addition step), while that of X = NH is TS2. TS2 of X = NH leads to a novel Mulliken charge-transfer complex, Ph-(OH)(O=)C∙∙∙N(H(2))-Et. The superiority or inferiority between the direct nucleophilic process or the general base-catalyzed process for TS1 was examined with the model Ph-C(=O)-X-Et + OH(-)(H(2)O)(n), n = 3, 5, 8, 12, 16, 24 and 32. The latter process was calculated to be more favorable regardless of the number (n, except n = 3) of water molecules. The counter ion Na(+) works unfavorably on the ester hydrolysis, particularly on TS1. A minimal model of TS1 was proposed and was found to be insensitive to n.

  7. Absorption Spectrum of a Ru(II)-Aquo Complex in Vacuo: Resolving Individual Charge-Transfer Transitions.

    PubMed

    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.

  8. Cucurbit[8]uril-stabilized charge transfer complexes with diquat driven by pH: a SERS study.

    PubMed

    Roldán, María Lorena; Sanchez-Cortes, Santiago; García-Ramos, José Vicente; Domingo, Concepción

    2012-04-14

    In this work, we have studied the pH-dependence of the formation of DQCB[8] complexes by surface-enhanced Raman scattering (SERS) spectroscopy. The SERS spectra suggest that at acidic pH CB[8] can form a binary complex with the dication DQ(+2) while at higher pH ternary complexes with the radical cation dimer (DQ(+)˙)(2) and the radical cation-dication dimer (DQ(+)˙DQ(+2)) are formed. The pH-enhanced diquat (DQ) dimerization inside the cucurbit[8]uril cavity has not been reported until now. In addition, this study provides very valuable information regarding the use of CB[8] functionalized silver nanoparticles as SERS substrate for sensing applications.

  9. Spectral investigations of multiple charge transfer complex of p-nitrophenol as an electron acceptor with donor p-dimethylaminobenzaldehyde

    NASA Astrophysics Data System (ADS)

    Naeem, A.; Khan, I. M.; Ahmad, A.

    2011-10-01

    The convincing evidence have been given that both the interactions π-π and π-π* (between p-nitrophenol ( p-NTP) and p-dimethylaminobenzaldehyde ( p-DAB)) are simultaneously involved. This has been established by using IR spectrometry. Association constant K evaluated by the method of Foster under the condition [A]0 = [D]0 with apply in this equation, [A]0/ A = 1/ Kɛλ[D]0 + 2/ɛλ, where [A]0 is the initial concentration of acceptor equal to [D]0, A is the absorbance of the complex at λ, K is the association constant, and ɛλ is the molar absorptivity of the complex at λ. In the IR spectral studies of several related organic compounds, one comes to the conclusion that p-NTP shows a broad band centred at 1600 cm-1 and to nitro asymmetric stretching vibrations. In the complex while the 1500 cm-1 band remains without shift, the broad band localized at 1600 cm-1 shift to 1610 cm-1. A shift of 10 cm-1 shows weak interactions. Studies on molecular complexes of organ metallic donors and acceptors are of very recent origin. Though alkyl donors have been extensively studied, very few studies have appeared on aryl donors.

  10. Complex magnetic incommensurability and electronic charge transfer through the ferroelectric transition in multiferroic Co3TeO6.

    PubMed

    Lee, Chi-Hung; Wang, Chin-Wei; Zhao, Yang; Li, Wen-Hsien; Lynn, Jeffrey W; Harris, A Brooks; Rule, Kirrily; Yang, Hung-Duen; Berger, Helmuth

    2017-07-25

    Polarized and unpolarized neutron diffractions have been carried out to investigate the nature of the magnetic structures and transitions in monoclinic Co3TeO6. As the temperature is lowered below 26 K long range order develops, which is fully incommensurate (ICM) in all three crystallographic directions. Below 19.5 K additional commensurate magnetic peaks develop, consistent with the Γ4 irreducible representation, along with a splitting of the ICM peaks along the h direction which indicates that there are two separate sets of magnetic modulation vectors. Below 18 K, this small additional magnetic incommensurability disappears, ferroelectricity develops, an additional commensurate magnetic structure consistent with Γ3 irreducible representation appears, and the k component of the ICM wave vector disappears. Synchrotron x-ray diffraction measurements demonstrate that there is a significant shift of the electronic charge distribution from the Te ions at the crystallographic 8 f sites to the neighboring Co and O ions. These results, together with the unusually small electric polarization, its strong magnetic field dependence, and the negative thermal expansion in all three lattice parameters, suggest this material is an antiferroelectric. Below15 K the k component of the ICM structure reappears, along with second-order ICM Bragg peaks, which polarized neutron data demonstrate are magnetic in origin.

  11. Apparent Charge Transfer at Semiconductor Surfaces

    SciTech Connect

    Carpinelli, Joseph M.; Stumpf, Roland R.; Weitering, Hanno H.

    1999-05-11

    We investigate the apparent charge transfer between adatoms in the GeXPb[l.XjGe(lll) interface both experimentally and theoretically. Scanning tunneling microscopy and surface core level measurements suggest significant charge transfer from the Ge adatoms to the Pb adatoms. However, first-principles calculations unambiguously find that the total electronic displacement is negligibly small, and that the results of published experiments can be explained as a result of bond rearrangement.

  12. Opposites Attract: Organic Charge Transfer Salts

    ERIC Educational Resources Information Center

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

    2015-01-01

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

  13. Opposites Attract: Organic Charge Transfer Salts

    ERIC Educational Resources Information Center

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

    2015-01-01

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

  14. Interfacial charge-transfer absorption: semiclassical treatment.

    PubMed

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

    2005-05-26

    Optically induced charge transfer between adsorbed molecules and a metal electrode was predicted by Hush to lead to new electronic absorption features but has not been experimentally observed. However, Gerischer characterized photocurrents arising from such absorption between adsorbed metal atoms and semiconductor conduction bands. Interfacial charge-transfer absorption (IFCTA) provides information concerning the barriers to charge transfer between molecules and the metal/semiconductor and the magnitude of the electronic coupling and could thus provide a powerful tool for understanding interfacial charge-transfer kinetics. Here we provide a framework for modeling and predicting IFCTA spectra. The key feature of optical charge transfer to or from a band of electronic levels (taken to have a constant density of states and electronic coupling element) is that the absorption probability reaches half intensity at lambda + DeltaG(theta), where lambda and DeltaG(theta) are the reorganization energy and free-energy gap for the optical charge transfer, attains >90% intensity at lambda + DeltaG(theta) + 0.9 square root[4lambdak(B)T], and remains essentially constant until the top (bottom) level of the band is attained. However, when the electronic coupling and transition moment are assumed to be independent of photon energy (Mulliken-Hush model), a peaked, highly asymmetric absorption profile is predicted. We conclude that, in general, the electronic coupling between molecular adsorbates and the metal levels is so small that absorption is not detectable, whereas for semiconductors there may be intense features involving coupling to surface states.

  15. Validated spectroflurimetric determination of some H1 receptor antagonist drugs in pharmaceutical preparations through charge transfer complexation.

    PubMed

    el-Din, Mohie K Sharaf; Ibrahim, Fawzia; Eid, Manal I; Wahba, Mary E K

    2012-01-01

    A validated simple, rapid, and selective spectrofluorimetric method was developed for the determination of some antihistaminic H(1) receptor antagonist drugs namely ebastine (EBS), cetirizine dihydrochloride (CTZ), and fexofenadine hydrochloride (FXD). The method is based on the reaction of the cited drugs with some Π acceptors namely p-chloranilic acid (CLA), tetracyanoethylene (TCNE), and 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) to give highly fluorescent derivatives. The fluorescence intensity-concentration plots were rectilinear over the concentration ranges of 0.2-3.0, 0.2-2.5 and 0.15-2.0 μg/ml for EBS with CLA, DDQ, and TCNE respectively; 0.5-7.0, 0.5-6.0, and 0.2-4.0 μg/ml for CTZ with the previously mentioned reagents, and 0.2-3.5, 0.5-6.0, and 0.2-3.5 μg/ml for FXD. The factors affecting the formation of the reaction products were carefully studied and optimized. The method was applied for the determination of the studied drugs in their dosage forms. The results obtained were in good agreement with those obtained by the comparison methods. Reactions Stoichiometries of the complexes formed between the studied drugs and Π acceptors were defined by the Job's method of the continuous variation and found in 1:1 in all cases.

  16. Direct observation of metal-to-ligand charge-transfer (MLCT) excited states of pentaammineruthenium(II) complexes

    SciTech Connect

    Winkler, J.R.; Netzel, T.L.; Creutz, C.; Sutin, N.

    1987-04-15

    Excited-state difference spectra and lifetimes are reported for Ru(tpy)/sub 2//sup 2 +/ (tpy = 2,2',2''-terpyridine) and a series of pentaammineruthenium(II) complexes. The initially formed excited states (generated by approx. 25-ps excitation with 532-nm light) are well modeled by a Ru/sup III/(L/sup .-/) electronic configuration (L is an aromatic, N-heterocyclic ligand) since an excellent correspondence is found between their absorption features and those of (L/sup .-)H/sup +/ radicals. The transients are, therefore, assigned as MLCT states. The Ru(tpy)/sub 2//sup 2 +/ excited-state lifetime is 250 ps. The Ru(NH/sub 3/)/sub 5/L/sup 2 +/ excited-state lifetimes vary from less than or equal to 20 (L = protonated pyrazine, protonated 4,4'-bipyridine, and 4-acetylpyridine) to approx. 200 (L = pyrazine, isonicotinamide, 4,4'-bipyridine) ps in water at approx. 22/sup 0/C. Ammine aquation products, Ru(NH/sub 3/)/sub 4/(H/sub 2/O)L/sup 2 +/, are also observed and are shown to result from multiphoton absorption of the ps-excitation pulses. The MLCT states of Ru(NH/sub 3/)/sub 5/L/sup 2 +/ (L = pz or 4,4'-bpy) undergo protonation by solvent water and deactivation to Ru(NH/sub 3/)/sub 5/LH/sup 3 +/; rate constants for proton loss from the protonated species (Ru(NH/sub 3/)/sub 5/LH/sup 3 +/ + H/sub 2/O ..-->.. Ru(NH/sub 3/)/sub 5/L/sup 2 +/ + H/sub 3/O/sup +/) are (2-3) x 10/sup 7/ s/sup -1/ and 2 x 10/sup 5/ s/sup -1/ for L = pz and 4,4'-bpy, respectively. The Ru(NH/sub 3/)/sub 5/L/sup 2 +/ MLCT-excited-state lifetimes are discussed in terms of the lowest excited state tuning model of Ford and co-workers.

  17. 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.

    PubMed

    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

  18. Charge transfer in algebraic quantum field theory

    NASA Astrophysics Data System (ADS)

    Wright, Jill Dianne

    We discuss aspects of the algebraic structure of quantum field theory. We take the view that the superselection structure of a theory should be determinable from the vacuum representation of the observable algebra, and physical properties of the charge. Hence one determines the nature of the charge transfer operations: the automorphisms of the observable algebra corresponding to the movement of charge along space-time paths. New superselection sectors are obtained from the vacuum sector by an automorphism which is a limit of charge transfer operations along paths with an endpoint tending to spacelike infinity. Roberts has shown that for a gauge theory of the first kind, the charge transfer operations for a given charge form a certain kind of 1-cocycle over Minkowski space. The local 1-cohomology group of their equivalence classes corresponds to the superselection structure. The exact definition of the cohomology group depends on the properties of the charge. Using displaced Fock representations of free fields, we develop model field theories which illustrate this structure. The cohomological classification of displaced Fock representations has been elucidated by Araki. For more general representations, explicit determination of the cohomology group is a hard problem. Using our models, we can illustrate ways in which fields with reasonable physical properties depart fromthe abovementioned structure. In 1+1 dimensions, we use the Streater-Wilde model to illustrate explicitly the representation-dependence of the cohomology structure, and the direction-dependence of the limiting charge transfer operation. The cohomology structure may also be representation-dependent in higher-dimensional theories without strict localization of charge, for example the electromagnetic field. The algebraic structure of the electromagnetic field has many other special features, which we discuss in relation to the concept of charge transfer. We also give some indication of the modifications

  19. Characterization of low energy charge transfer transitions in (terpyridine)(bipyridine)ruthenium(II) complexes and their cyanide-bridged bi- and tri-metallic analogues.

    PubMed

    Tsai, Chia-Nung; Allard, Marco M; Lord, Richard L; Luo, Dao-Wen; Chen, Yuan-Jang; Schlegel, H Bernhard; Endicott, John F

    2011-12-05

    The lowest energy metal-to-ligand charge transfer (MLCT) absorption bands found in ambient solutions of a series of [Ru(tpy)(bpy)X](m+) complexes (tpy = 2,2':3',2''-terpyridine; bpy = 2,2'-bipyridine; and X = a monodentate ancillary ligand) feature one or two partly resolved weak absorptions (bands I and/or II) on the low energy side of their absorption envelopes. Similar features are found for the related cyanide-bridged bi- and trimetallic complexes. However, the weak absorption band I of [(bpy)(2)Ru{CNRu(tpy)(bpy)}(2)](4+) is missing in its [(bpy)(2)Ru{NCRu(tpy)(bpy)}(2)](4+) linkage isomer demonstrating that this feature arises from a Ru(II)/tpy MLCT absorption. The energies of the MLCT band I components of the [Ru(tpy)(bpy)X](m+) complexes are proportional to the differences between the potentials for the first oxidation and the first reduction waves of the complexes. Time-dependent density functional theory (TD-DFT) computational modeling indicates that these band I components correspond to the highest occupied molecular orbital (HOMO) to lowest unoccupied molecular orbital (LUMO) transition, with the HOMO being largely ruthenium-centered and the LUMO largely tpy-centered. The most intense contribution to a lowest energy MLCT absorption envelope (band III) of these complexes corresponds to the convolution of several orbitally different components, and its absorption maximum has an energy that is about 5000 cm(-1) higher than that of band I. The multimetallic complexes that contain Ru(II) centers linked by cyanide have mixed valence excited states in which more than 10% of electronic density is delocalized between the nearest neighbor ruthenium centers, and the corresponding stabilization energy contributions in the excited states are indistinguishable from those of the corresponding ground states. Single crystal X-ray structures and computational modeling indicate that the Ru-(C≡N)-Ru linkage is quite flexible and that there is not an appreciable variation

  20. The charge-transfer complex 1-amino­anthraquinone–7,7′,8,8′-tetra­cyano­quinodimethane (1/1)

    PubMed Central

    de Oliveira, Adriano Bof; Beck, Johannes; Daniels, Jörg; Santos, Jaciara Nascimento; Feitosa, Bárbara Regina Santos

    2013-01-01

    The reaction of 1-amino­anthraquinone with 7,7′,8,8′-tetra­cyano­quinodimethane yielded the title charge-transfer complex, C14H9NO2·C12H4N4. The mol­ecules have maximum deviations from the mean planes through the non-H atoms of 0.0769 (14) Å for an oxo O atom and 0.1175 (17) Å for a cyano N atom, respectively. The dihedral angle between the two planes is 3.55 (3)°. In the crystal, mol­ecules are stacked into columns along the a-axis direction. Pairs of N—H⋯N and N—H⋯O inter­actions connect the mol­ecules perpendicular to the stacking direction. Additionally, an intra­molecular N—H⋯O hydrogen-bond inter­action is observed for 1-amino­anthraquinone. PMID:23424566

  1. Preparation, spectroscopic and antibacterial studies on charge-transfer complexes of 2-hydroxypyridine with picric acid and 7,7‧,8,8‧-tetracyano-p-quinodimethane

    NASA Astrophysics Data System (ADS)

    Gaballa, Akmal S.; Amin, Alaa S.

    2015-06-01

    The reactions of electron acceptors such as picric acid (HPA) and 7,7‧,8,8‧-tetracyano-p-quinodimethane (TCNQ) with 2-hydroxypyridine (HPyO) have been investigated in EtOH at room temperature. Based on elemental analysis and IR spectra of the solid CT-complexes along with the photometric titration curves for the reactions, the data obtained indicate the formation of 1:1 charge transfer complexes [(H2PyO)(PA)] and [(PyO)(HTCNQ)], respectively. The infrared and 1H NMR spectroscopic data indicate a charge transfer interaction associated with a proton migration from the acceptor to the donor followed by intramolecular hydrogen bonding in [(H2PyO)(PA)] complex. Another charge transfer interaction was observed in [(PyO)(HTCNQ)] complex. The formation constants (KCT) for the CT-complexes are shown to be strongly dependent on the type and structure of the electron acceptors. Factors affecting the CT-processes and the kinetics of thermal decomposition of the complexes have been studied. The CT complexes were screened for their antibacterial activities against selected bacterial strains.

  2. Electronic structures of TiO2-TCNE, -TCNQ, and -2,6-TCNAQ surface complexes studied by ionization potential measurements and DFT calculations: Mechanism of the shift of interfacial charge-transfer bands

    NASA Astrophysics Data System (ADS)

    Fujisawa, Jun-ichi; Hanaya, Minoru

    2016-06-01

    Interfacial charge-transfer (ICT) transitions between inorganic semiconductors and π-conjugated molecules allow direct charge separation without loss of energy. This feature is potentially useful for efficient photovoltaic conversions. Charge-transferred complexes of TiO2 nanoparticles with 7,7,8,8-tetracyanoquinodimethane (TCNQ) and its analogues (TCNX) show strong ICT absorption in the visible region. The ICT band was reported to be significantly red-shifted with extension of the π-conjugated system of TCNX. In order to clarify the mechanism of the red-shift, in this work, we systematically study electronic structures of the TiO2-TCNX surface complexes (TCNX; TCNE, TCNQ, 2,6-TCNAQ) by ionization potential measurements and density functional theory (DFT) calculations.

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

    PubMed Central

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

    2015-01-01

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

  4. Charge transfer driven emergent phenomena in oxide heterostructures

    NASA Astrophysics Data System (ADS)

    Chen, Hanghui; Millis, Andrew

    2017-06-01

    Complex oxides exhibit many intriguing phenomena, including metal-insulator transition, ferroelectricity/multiferroicity, colossal magnetoresistance and high transition temperature superconductivity. Advances in epitaxial thin film growth techniques enable us to combine different complex oxides with atomic precision and form an oxide heterostructure. Recent theoretical and experimental work has shown that charge transfer across oxide interfaces generally occurs and leads to a great diversity of emergent interfacial properties which are not exhibited by bulk constituents. In this report, we review mechanisms and physical consequence of charge transfer across interfaces in oxide heterostructures. Both theoretical proposals and experimental measurements of various oxide heterostructures are discussed and compared. We also review the theoretical methods that are used to calculate charge transfer across oxide interfaces and discuss the success and challenges in theory. Finally, we present a summary and perspectives for future research.

  5. Charge transfer and charge transport on the double helix

    NASA Astrophysics Data System (ADS)

    Armitage, N. P.; Briman, M.; Grüner, G.

    2004-01-01

    We present a short review of various experiments that measure charge transfer and charge transport in DNA. Some general comments are made on the possible connection between various chemistry-style charge transfer experiments that probe fluorescence quenching and remote oxidative damage and physics-style measurements that measure transport properties as defined typically in the solid-state. We then describe measurements performed by our group on the millimeter wave response of DNA. By measuring over a wide range of humidity conditions and comparing the response of single strand DNA and double strand DNA, we show that the appreciable AC conductivity of DNA is not due to photon assisted hopping between localized states, but instead due to dissipation from dipole motion in the surrounding water helix.

  6. Charge transfer between fullerenes and highly charged noble gas ions

    NASA Astrophysics Data System (ADS)

    Narits, A. A.

    2008-07-01

    A semiclassical model for the description of charge-exchange processes in collisions between fullerenes and multiply charged ions is developed. It is based on the decay model combined with the impact-parameter representation for the heavy particles' relative motion. The charge-transfer process in our model is treated as a transition of the active electron over and under the quasistatic potential barrier formed by the electric fields of the target and projectile. Due to the high electron delocalization on the surface of fullerene we represent it as a perfectly conducting hard sphere, whose radius is determined by the dipole polarizability of C60. The energies of the active electrons are assumed to be equal to the corresponding ionization potentials including the Stark-shift effect. We have developed an efficient technique for the evaluation of the electron transmission coefficient through the asymmetric potential barrier. It is shown that our model provides a good agreement with the available experimental data on single-electron charge-exchange processes. Moreover, it allows us to get an adequate description of multi-electron transfer processes. The first theoretical results on charge exchange between the fullerene ions and highly charged ions have been obtained.

  7. 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.

    PubMed

    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

  8. 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

    NASA Astrophysics Data System (ADS)

    Bagchi (Chattaraj), Seema; Sharma, Kakali; Chakrabortty, Ashutosh; Lahiri, Sujit Chandra

    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 ΔG0, ΔH0 and ΔS0. The energies hνCT of the charge-transfer complexes were compared with the theoretical values of hνCT 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. hνCT (experimental) values of the transition energies of the complexes in acetonitrile differed

  9. Charge transfer in iridate-manganite superlattices

    DOE PAGES

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

    2017-03-03

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

  10. Charge Transfer in Iridate-Manganite Superlattices.

    PubMed

    Okamoto, Satoshi; Nichols, John; Sohn, Changhee; Kim, So Yeun; Noh, Tae Won; Lee, Ho Nyung

    2017-03-07

    Charge transfer in superlattices consisting of SrIrO3 and SrMnO3 is investigated using density functional theory. Despite the nearly identical work function and nonpolar interfaces between SrIrO3 and SrMnO3, rather large charge transfer was experimentally reported at the interface between them. Here, we report a microscopic model that captures the mechanism behind this phenomenon, providing a qualitative understanding of the experimental observation. This leads to unique strain dependence of such charge transfer in iridate-manganite superlattices. The predicted behavior is consistently verified by experiment with soft X-ray and optical spectroscopy. Our work thus demonstrates a new route to control electronic states in nonpolar oxide heterostructures.

  11. Ultrafast charge transfer and atomic orbital polarization

    SciTech Connect

    Deppe, M.; Foehlisch, A.; Hennies, F.; Nagasono, M.; Beye, M.; Sanchez-Portal, D.; Echenique, P. M.; Wurth, W.

    2007-11-07

    The role of orbital polarization for ultrafast charge transfer between an atomic adsorbate and a substrate is explored. Core hole clock spectroscopy with linearly polarized x-ray radiation allows to selectively excite adsorbate resonance states with defined spatial orientation relative to the substrate surface. For c(4x2)S/Ru(0001) the charge transfer times between the sulfur 2s{sup -1}3p*{sup +1} antibonding resonance and the ruthenium substrate have been studied, with the 2s electron excited into the 3p{sub perpendicular}* state along the surface normal and the 3p{sub parallel}* state in the surface plane. The charge transfer times are determined as 0.18{+-}0.07 and 0.84{+-}0.23 fs, respectively. This variation is the direct consequence of the different adsorbate-substrate orbital overlap.

  12. Correlating electronic and vibrational motions in charge transfer systems

    SciTech Connect

    Khalil, Munira

    2014-06-27

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

  13. Spacecraft Charging in Geostationary Transfer Orbit

    NASA Technical Reports Server (NTRS)

    Parker, Linda Neergaard; Minow, Joseph I.

    2014-01-01

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

  14. Spacecraft Charging in Geostationary Transfer Orbit

    NASA Astrophysics Data System (ADS)

    Parker, L. N.; Minow, J. I.

    2014-12-01

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

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

    PubMed Central

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

    2009-01-01

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

  16. Ligand(s)-to-metal charge transfer as a factor controlling the equilibrium constants of late first-row transition metal complexes: revealing the Irving-Williams thermodynamical series.

    PubMed

    Varadwaj, Pradeep R; Varadwaj, Arpita; Jin, Bih-Yaw

    2015-01-14

    A unified relationship between the experimental formation constants and the ligand(s)-to-metal charge transfer values of versatile ligand complexes of late transition series first-row bivalent metal ions is uncovered. The latter property not only explicates the Irving-Williams series but also rationalizes quantitatively Pearson's concept of hard and soft acids and bases by correlating the gas-phase to aqueous solution-phase chemistry in a broad sense.

  17. Biological charge transfer via flickering resonance

    PubMed Central

    Zhang, Yuqi; Liu, Chaoren; Balaeff, Alexander; Skourtis, Spiros S.; Beratan, David N.

    2014-01-01

    Biological electron-transfer (ET) reactions are typically described in the framework of coherent two-state electron tunneling or multistep hopping. However, these ET reactions may involve multiple redox cofactors in van der Waals contact with each other and with vibronic broadenings on the same scale as the energy gaps among the species. In this regime, fluctuations of the molecular structures and of the medium can produce transient energy level matching among multiple electronic states. This transient degeneracy, or flickering electronic resonance among states, is found to support coherent (ballistic) charge transfer. Importantly, ET rates arising from a flickering resonance (FR) mechanism will decay exponentially with distance because the probability of energy matching multiple states is multiplicative. The distance dependence of FR transport thus mimics the exponential decay that is usually associated with electron tunneling, although FR transport involves real carrier population on the bridge and is not a tunneling phenomenon. Likely candidates for FR transport are macromolecules with ET groups in van der Waals contact: DNA, bacterial nanowires, multiheme proteins, strongly coupled porphyrin arrays, and proteins with closely packed redox-active residues. The theory developed here is used to analyze DNA charge-transfer kinetics, and we find that charge-transfer distances up to three to four bases may be accounted for with this mechanism. Thus, the observed rapid (exponential) distance dependence of DNA ET rates over distances of ≲15 Å does not necessarily prove a tunneling mechanism. PMID:24965367

  18. Charge transfer states of the reaction center

    NASA Astrophysics Data System (ADS)

    Scherer, P. O. J.; Fischer, Sighart F.

    1998-08-01

    The energies of the low lying charge transfer states relevant for the photoinduced charge separation are analysed for Rps. viridis. The main prosthetic groups consisting of the special pair dimer P, the two adjacent monomers BL, and BM and the two pheophytines HL and HM are treated together with the surrounding residues quantum mechanically within a supermolecule approach on the basis of an INDO approximation. High order configuration interactions are incorporated to account for polarization effects and long range electrostatic effects of the protein are considered. The results are analyzed with regard to symmetry breaking effects between the L- and the M-branch. Internal reorganization effects within the dimer are also discussed.

  19. Enhancing SERS by Means of Supramolecular Charge Transfer

    NASA Technical Reports Server (NTRS)

    Wong, Eric; Flood, Amar; Morales, Alfredo

    2009-01-01

    In a proposed method of sensing small quantities of molecules of interest, surface enhanced Raman scattering (SERS) spectroscopy would be further enhanced by means of intermolecular or supramolecular charge transfer. There is a very large potential market for sensors based on this method for rapid detection of chemical and biological hazards. In SERS, the Raman signals (vibrational spectra) of target molecules become enhanced by factors of the order of 108 when those molecules are in the vicinities of nanostructured substrate surfaces that have been engineered to have plasmon resonances that enhance local electric fields. SERS, as reported in several prior NASA Tech Briefs articles and elsewhere, has remained a research tool and has not yet been developed into a practical technique for sensing of target molecules: this is because the short range (5 to 20 nm) of the field enhancement necessitates engineering of receptor molecules to attract target molecules to the nanostructured substrate surfaces and to enable reliable identification of the target molecules in the presence of interferants. Intermolecular charge-transfer complexes have been used in fluorescence-, photoluminescence-, and electrochemistry-based techniques for sensing target molecules, but, until now, have not been considered for use in SERS-based sensing. The basic idea of the proposed method is to engineer receptor molecules that would be attached to nanostructured SERS substrates and that would interact with the target molecules to form receptor-target supramolecular charge-transfer complexes wherein the charge transfer could be photoexcited.

  20. [Spectrophotometric determination of codeine through charge-transfer reaction].

    PubMed

    Du, Li-ming; Li, Li; Wu, Hao

    2007-02-01

    The charge-transfer reaction of 7,7,8,8-tetracyano-quinodimethane (TCNQ) as a pi-electron acceptor with codeine as electron donors was investigated by spectrophotometry. TCNQ was found to react with codeine to produce stable charge-transfer complexes in acetone. Meanwhile, the studied drugs suffer a considerable bathochromic shift (from 216 to 843 nm). The influential factor of charge-transfer reaction and the optimum conditions for the determination of codeine were investigated in detail. Therefore a simple, rapid and accurate method with a good selectivity for the determination of codeine has been developed. The results show that Beer's law is obeyed in the ranges 0.1-1.6 microg x mL(-1) for codeine. The apparent molar absorptivity of the complex at 843 nm is 1.7 x 10(4) L x mol(-1) x cm(-1). Furthermore, the association constants and standard free energy changes were studied, and the mechanism of charge-transfer reaction was explored elementarily. The proposed method has been applied successfully to the determination of codeine in pharmaceutical preparations. The recoveries are from (98.94+/-0.96)% to (99.12+/-1.21)%.

  1. Calculations on the electronic structure and nonlinear second-order optical susceptibility of the C{sub 60} aniline charge-transfer complex

    SciTech Connect

    Li, J.; Feng, J.; Sun, C.

    1994-09-01

    Using both INDO/2 and INDO/CI methods, we have calculated the structure and UV-visible spectra of C{sub 60}/ aniline (AN), a model of the experimentally studied C{sub 60}/N,N-diethylaniline (DEA). The aniline fragment is bound directly to a carbon atom of C{sub 60}, and the charge transfer from aniline to C{sub 60} takes place. The calculated UV-visible spectra show new charge-transfer bands at 635-819 nm, which are comparable with experiment. On the basis of correct electronic spectra, calculations of the nonlinear second-order optical susceptibility {beta}{sub ijk} and {beta}{sub mu} have been performed using the INDO/CI method combined with a sum-over-states expression. The calculated {beta}{sub mu}, value is 3.217 x 10{sup -29} esu ({omega} = 1.91 {mu}m), which is in excellent agreement with observation. 27 refs., 3 figs., 3 tabs.

  2. Charge transfer complexes of quinones in aqueous medium: spectroscopic and theoretical studies on interaction of cimetidine with novel substituted 1,4-benzoquinones and its application in colorimetric sensing of anions.

    PubMed

    Balraj, C; Satheshkumar, A; Ganesh, K; Elango, Kuppanagounder P

    2013-10-01

    For the first time, the charge transfer (CT) complexes of quinones in aqueous medium have been reported. A series of novel water soluble 1,4-benzoquinones possessing variable number of chloro and methoxy substituents has been employed as electron acceptors (MQ1-4) in the CT complexation with cimetidine (CTD) drug. The mechanism of the interaction has been investigated using various spectral techniques such as UV-Vis, (1)H NMR and FT-IR spectra. The rate of the CT interaction was observed to decrease with progressive replacement of chloro by methoxy substituent in the quinone and this variation is well supported by the formation constant and enthalpy of activation values. Ab initio DFT calculations predicted that the variation in the bond lengths of the carbonyl moieties and the charge densities on the carbonyl oxygen atoms depend largely on the nature of the substituent present in the quinone ring. Also, the HOMO(Donor)-LUMO(Acceptor) energy gaps correlate linearly with the formation constants of the CT complex. The equilibrium, kinetic, electrochemical and theoretical investigations of the CT interaction of these quinones indicated that progressive replacement of electron withdrawing chlorine atom (-I effect) by an electron releasing methoxy group (+M effect) makes these acceptors progressively weaker. The charge-transfer complex, formed between CTD and monomethoxy quinone derivative, has been employed as a new class of chromogenic sensor for the colorimetric sensing of fluoride and acetate ions.

  3. Noncovalent functionalization and charge transfer in antimonene.

    PubMed

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

    2017-09-25

    Antimonene, a novel group-15 2D material, is functionalized with a tailor-made perylene bisimide through strong van-der-Waals interactions. The functionalization process leads to a dramatic quenching of the perylene fluorescence, which surpasses that observed for graphene or black phosphorus, allowing a 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, 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 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Applications of Charge Transfer Devices in Spectroscopy.

    DTIC Science & Technology

    1988-02-04

    and the decrease in cost of computer memory necessary for processing large image data arrays. The sensitivity, spatial resolution, wide spectral...mately one microsecond per transfer for most CCDs. Because the clocking of the parallel phases of the CCD is under computer control, linear and non-linear...destructive readout of charge allows the computer system to choose the optimum integration period for each spectral line. Intense lines are digitized early in

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

    NASA Astrophysics Data System (ADS)

    Babb, James F.; McLaughlin, B. M.

    2017-02-01

    Radiative charge exchange collisions between a carbon atom {{C}}({}3P) and a helium ion {{He}}+({}2S), 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 interstellar photon dominated regions and in x-ray dominated regions, where the abundance of {{He}}+ affects the abundance of {CO}.

  6. Charge transfer in the living matrix.

    PubMed

    Oschman, James L

    2009-07-01

    The living matrix is defined as the continuous molecular fabric of the organism, consisting of fascia, the other connective tissues, extracellular matrices, integrins, cytoskeletons, nuclear matrices and DNA. The extracellular, cellular and nuclear biopolymers or ground substances constitute a body-wide reservoir of charge that can maintain electrical homeostasis and "inflammatory preparedness" throughout the organism. Recent research has emphasized the significance of charge transfer in relation to the scavenging or neutralization of free radicals delivered to sites of injury during and after the oxidative burst. Evidence comes from studies of the role of electrons in mitigating the consequences of inflammation when living systems are connected to the earth (earthing). The phenomenon helps explain how bodywork and movement therapies can facilitate the resolution of acute or chronic injuries, and how patients with inflammatory conditions may "deplete" a therapist during hands-on treatments. It is suggested that barefoot contact with the earth as well as hands-on and hands-off therapies facilitate healing by stimulating the migration of charges into sites of acute or chronic inflammation. One hypothesis to explain the effects of earthing is that charges from the ground substance reservoir prevent "collateral damage" to healthy tissues in the vicinity of an injury. A second hypothesis is that earthing allows electrons to replenish charge in the ground substance reservoirs, making electrons available throughout the body.

  7. Synthesis, spectroscopic characterization and structural investigation of a new charge transfer complex of 2,6-diaminopyridine with 4-nitrophenylacetic acid: Antimicrobial, DNA binding/cleavage and antioxidant studies

    NASA Astrophysics Data System (ADS)

    Murugesan, Venkatesan; Saravanabhavan, Munusamy; Sekar, Marimuthu

    2015-08-01

    A new hydrogen-bonded charge-transfer complex (CT) formed by the reaction between donor, 2,6-diaminopyridine and acceptor, 4-nitrophenylacetic acid in methanol at room temperature. The crystal was characterized by elemental analysis, IR, NMR spectroscopic studies and thermal studies. The elemental analysis of CT complex, obtained data revealed that the formation of 1:1 ratio CT complex was proposed. Infrared and NMR studies confirm the chemical constituents and molecular structure of the synthesized complex crystal. The high thermal stability is due to the molecular frame work through H-bonding interactions. Structural investigation indicates that cation and anion are linked through strong N+-H⋯O- type of hydrogen bond. The hydrogen bonded charge transfer crystal was screened for its pharmacology, such as antimicrobial, DNA binding/cleavage and antioxidant studies. The CT complex was screened for its antibacterial and antifungal activity against various bacterial and fungal species, which shows good antimicrobial activity. The DNA binding results indicated that the compound could interact with DNA through intercalation. It should have weak to moderate capacity of scavenging with DPPH.

  8. Halogen contacts-induced unusual coloring in Bi(III) bromide complex: anion-to-cation charge transfer via Br···Br interactions.

    PubMed

    Adonin, Sergey A; Gorokh, Igor D; Novikov, Alexander S; Abramov, Pavel A; Sokolov, Maxim N; Fedin, Vladimir P

    2017-09-21

    A yellow bromobismuthate {(2-BrPy)2H}[BiBr4] (1) transforms into unusually deeply colored cherry-red (2-BrPyH)2[BiBr5] (2). Combination of structural studies and theoretical calculations confirms that appearance of short non-covalent Br···Br interactions (≈ 3.3 Å) in 2 is responsible for the anion-to-cation charge transfer (LP(Brligand) → σ*(Br-C)), yielding in dramatic changes in optical behavior. This effect opens the way towards novel halogen bonding-templated halometalate-based hybrid materials with enhanced optical properties. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Shedding light on the photostability of two intermolecular charge-transfer complexes between highly fluorescent bis-1,8-naphthalimide dyes and some π-acceptors: A spectroscopic study in solution and solid states

    NASA Astrophysics Data System (ADS)

    Refat, Moamen S.; Ismail, Lamia A.; Adam, Abdel Majid A.

    2015-01-01

    Given the great importance of the various uses of 1,8-naphthalimides in the trends of biology, medicine and industry, the current study focused on extending the scope of these dyes by introducing some of their charge-transfer (CT) complexes. For this purpose, two highly fluorescent bis-1,8-naphthalimide dyes and their complexes with some π-acceptors have been synthesized and characterized spectroscopically. The π-acceptors include picric acid (PA), chloranilic acid (CLA), tetracyanoquinodimethane (TCNQ) and dichlorodicyanobenzoquinone (DDQ). The molecular structure, spectroscopic and fluorescence properties as well as the binding modes were deduced from IR, UV-vis and 1H NMR spectral studies. The binding ratio of complexation was determined to be 1:1 according to the elemental analyses and photometric titrations. It has been found that the order of acceptance ability for the different acceptors is TCNQ > DDQ > CLA > PA. The photostability of 1,8-naphthalimide dye as a donor and its charge-transfer complex doped in polymethyl methacrylate/PMMA were exposed to UV-Vis radiation and the change in the absorption spectra was achieved at different times during irradiation period.

  10. Pattern classification using charge transfer devices

    NASA Technical Reports Server (NTRS)

    1980-01-01

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

  11. Saturn-like charge-transfer complexes Li₄&B₃₆, Li₅&B₃₆⁺, and Li₆&B₃₆²⁺: exohedral metalloborospherenes with a perfect cage-like B₃₆⁴⁻ core.

    PubMed

    Tian, Wen-Juan; Chen, Qiang; Li, Hai-Ru; Yan, Miao; Mu, Yue-Wen; Lu, Hai-Gang; Zhai, Hua-Jin; Li, Si-Dian

    2016-04-21

    Based on extensive first-principles theory calculations, we present the possibility of construction of the Saturn-like charge-transfer complexes Li4&B36 (2), Li5&B36(+) (3), and Li6&B36(2+) (4) all of which contain a perfect cage-like B36(4-) (1) core composed of twelve interwoven boron double chains with a σ + π double delocalization bonding pattern, extending the Bn(q) borospherene family from n = 38-42 to n = 36 with the highest symmetry of T(h).

  12. 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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2017-01-01

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

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

    PubMed Central

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

    2017-01-01

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

  15. Electron delocalization in the S1 and T1 metal-to-ligand charge transfer states of trans-substituted metal quadruply bonded complexes

    PubMed Central

    Alberding, Brian G.; Chisholm, Malcolm H.; Gallucci, Judith C.; Ghosh, Yagnaseni; Gustafson, Terry L.

    2011-01-01

    The singlet S1 and triplet T1 photoexcited states of the compounds containing MM quadruple bonds trans-M2(TiPB)2(O2CC6H4-4-CN)2, where TiPB = 2,4,6-triisopropylbenzoate and M = Mo (I) or M = W (I′), and trans-M2(O2CMe)2((N[i Pr ])2CC ≡ CC6H5)2, where M = Mo (II) and M = W (II′), have been investigated by a variety of spectroscopic techniques including femtosecond time-resolved infrared spectroscopy. The singlet states are shown to be delocalized metal-to-ligand charge transfer (MLCT) states for I and I′ but localized for II and II′ involving the cyanobenzoate or amidinate ligands, respectively. The triplet states are MoMoδδ* for both I and II but delocalized 3MLCT for I′ and localized 3MLCT for II′. These differences arise from consideration of the relative orbital energies of the M2δ or M2δ* and the ligand π∗ as well as the magnitudes of orbital overlap. PMID:21525414

  16. Charge transfer initiated nitroxyl chemistry on free silver clusters Ag{sub 2-5}{sup-} : size effects and magic complexes.

    SciTech Connect

    Hagen, J.; Socaciu-Sieberg, L. D.; LeRoux, J.; Popolan, D.; Vajda, S.; Bernhardt, T. M.; Woste, L.; Chemistry; Freie Univ.; Univ. Ulm

    2007-01-01

    The reactivity of small silver cluster anions Ag{sub 2--5}- toward nitric oxide and mixtures of nitric oxide with carbon monoxide is investigated under multi-collision conditions in a radio frequency octopole ion trap at temperatures of 100 and 300 K. A strongly cluster size dependent reaction behavior is observed, where reactive fragmentation dominates for clusters with four or fewer atoms and only Ag{sub 5}- is able to form reaction products without dissociation of the metal cluster. The decisive role of charge transfer in the NO bond breakage, NO oxidation, and the formation of free NO{sub 2}{sup -} and N{sub 2}O{sub 4}{sup -} ions, as well as NxO(y>x)-ligands on the silver clusters is discussed. The mass spectrometric data reveal the particular stability of the reaction products AgN{sub 2}O{sub 4}{sup -} and Ag{sub 3}NO{sup -}. The reaction product mass spectra obtained for Ag{sub 5}{sup -} in the presence of NO and CO show the depletion of the NxO(y>x)-ligands on the metal cluster possibly involving the oxidation of CO to CO2.

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

    PubMed

    Zhang, Chaoyang; Ma, Yu; Jiang, Daojian

    2012-11-01

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

  18. Enhancement of IR and VCD intensities due to charge transfer.

    PubMed

    Nicu, Valentin Paul; Autschbach, Jochen; Baerends, Evert Jan

    2009-03-14

    Donor-acceptor interactions such as the one between the Cl(-) base and the N-H sigma* acceptor orbitals encountered in the complexation of Cl(-) counterions to the [Co(en)(3)](3+) transition metal complex, have been shown to cause huge enhancement (between 1 and 2 orders of magnitude) of the VCD intensities of N-H stretching modes. This effect has been fully analyzed, and could be attributed to increased charge flow from the Cl(-) donors when the N-H bonds become stretched. The transfer of charge counteracts the movement of negative electronic charge that happens along with the motion of the H nuclei, effectively reversing the electronic part of the electric dipole transition moment (EDTM) in the direction of the charge flow (z, say), and of the magnetic transition dipole moment (MDTM) in the perpendicular direction. The consequences for the IR and VCD intensity follow: IR intensity is strongly increased if the EDTM is polarized in the z direction, e.g. in A(2) modes, but not so much if it is polarized in the xy plane (E modes), the VCD is strongly enhanced if the EDTM and MTDM are polarized in the xy plane (in E modes), but less so when they are polarized in the z direction (in A(2) modes). The explanation holds generally for complexation phenomena of this sort, including the donor-acceptor part of hydrogen bonding interactions, e.g. with solvent molecules.

  19. Optical and positron annihilation spectroscopic studies on PMMA polymer doped by rhodamine B/chloranilic acid charge transfer complex: Special relevance to the effect of γ-ray irradiation

    NASA Astrophysics Data System (ADS)

    Hassan, H. E.; Refat, Moamen S.; Sharshar, T.

    2016-04-01

    Polymeric sheets of poly (methylmethaclyerate) (PMMA) containing charge transfer (CT) complex of rhodamine B/chloranilic acid (Rho B/CHA) were synthesized in methanol solvent at room temperature. The systematic analysis done on the Rho B and its CT complex in the form of powder or polymeric sheets confirmed their structure and thermal stability. The IR spectra interpreted the charge transfer mode of interaction between the CHA central positions and the terminal carboxylic group. The polymer sheets were irradiated with 70 kGy of γ radiation using 60Co source to study the enhanced changes in the structure and optical parameters. The microstructure changes of the PMMA sheets caused by γ-ray irradiation were analyzed using positron annihilation lifetime (PAL) and positron annihilation Doppler broadening (PADB) techniques. The positron life time components (τi) and their corresponding intensities (Ii) as well as PADB line-shape parameters (S and W) were found to be highly sensitive to the enhanced disorder occurred in the organic chains of the polymeric sheets due to γ-irradiation.

  20. Optical and positron annihilation spectroscopic studies on PMMA polymer doped by rhodamine B/chloranilic acid charge transfer complex: Special relevance to the effect of γ-ray irradiation.

    PubMed

    Hassan, H E; Refat, Moamen S; Sharshar, T

    2016-04-15

    Polymeric sheets of poly (methylmethaclyerate) (PMMA) containing charge transfer (CT) complex of rhodamine B/chloranilic acid (Rho B/CHA) were synthesized in methanol solvent at room temperature. The systematic analysis done on the Rho B and its CT complex in the form of powder or polymeric sheets confirmed their structure and thermal stability. The IR spectra interpreted the charge transfer mode of interaction between the CHA central positions and the terminal carboxylic group. The polymer sheets were irradiated with 70 kGy of γ radiation using (60)Co source to study the enhanced changes in the structure and optical parameters. The microstructure changes of the PMMA sheets caused by γ-ray irradiation were analyzed using positron annihilation lifetime (PAL) and positron annihilation Doppler broadening (PADB) techniques. The positron life time components (τ(i)) and their corresponding intensities (I(i)) as well as PADB line-shape parameters (S and W) were found to be highly sensitive to the enhanced disorder occurred in the organic chains of the polymeric sheets due to γ-irradiation.

  1. Flavin Charge Transfer Transitions Assist DNA Photolyase Electron Transfer

    NASA Astrophysics Data System (ADS)

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

    2007-12-01

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

  2. Complexation behavior of oppositely charged polyelectrolytes: Effect of charge distribution

    NASA Astrophysics Data System (ADS)

    Zhao, Mingtian; Zhou, Jihan; Su, Cuicui; Niu, Lin; Liang, Dehai; Li, Baohui

    2015-05-01

    Complexation behavior of oppositely charged polyelectrolytes in a solution is investigated using a combination of computer simulations and experiments, focusing on the influence of polyelectrolyte charge distributions along the chains on the structure of the polyelectrolyte complexes. The simulations are performed using Monte Carlo with the replica-exchange algorithm for three model systems where each system is composed of a mixture of two types of oppositely charged model polyelectrolyte chains (EGEG)5/(KGKG)5, (EEGG)5/(KKGG)5, and (EEGG)5/(KGKG)5, in a solution including explicit solvent molecules. Among the three model systems, only the charge distributions along the chains are not identical. Thermodynamic quantities are calculated as a function of temperature (or ionic strength), and the microscopic structures of complexes are examined. It is found that the three systems have different transition temperatures, and form complexes with different sizes, structures, and densities at a given temperature. Complex microscopic structures with an alternating arrangement of one monolayer of E/K monomers and one monolayer of G monomers, with one bilayer of E and K monomers and one bilayer of G monomers, and with a mixture of monolayer and bilayer of E/K monomers in a box shape and a trilayer of G monomers inside the box are obtained for the three mixture systems, respectively. The experiments are carried out for three systems where each is composed of a mixture of two types of oppositely charged peptide chains. Each peptide chain is composed of Lysine (K) and glycine (G) or glutamate (E) and G, in solution, and the chain length and amino acid sequences, and hence the charge distribution, are precisely controlled, and all of them are identical with those for the corresponding model chain. The complexation behavior and complex structures are characterized through laser light scattering and atomic force microscopy measurements. The order of the apparent weight-averaged molar

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

    PubMed

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

    2013-12-07

    We investigate the electron ionization of clusters generated in mixed Ar-water expansions. The electron energy dependent ion yields reveal the neutral cluster composition and structure: water clusters fully covered with the Ar solvation shell are formed under certain expansion conditions. The argon atoms shield the embedded (H2O)n clusters resulting in the ionization threshold above ≈15 eV for all fragments. The argon atoms also mediate more complex reactions in the clusters: e.g., the charge transfer between Ar(+) and water occurs above the threshold; at higher electron energies above ~28 eV, an excitonic transfer process between Ar(+)* and water opens leading to new products Ar(n)H(+) and (H2O)(n)H(+). On the other hand, the excitonic transfer from the neutral Ar* state at lower energies is not observed although this resonant process was demonstrated previously in a photoionization experiment. Doubly charged fragments (H2O)(n)H2(2+) and (H2O)(n)(2+) ions are observed and Intermolecular Coulomb decay (ICD) processes are invoked to explain their thresholds. The Coulomb explosion of the doubly charged cluster formed within the ICD process is prevented by the stabilization effect of the argon solvent.

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

    SciTech Connect

    Kočišek, J. E-mail: michal.farnik@jh-inst.cas.cz Lengyel, J.; Fárník, M. E-mail: michal.farnik@jh-inst.cas.cz; Slavíček, P. E-mail: michal.farnik@jh-inst.cas.cz

    2013-12-07

    We investigate the electron ionization of clusters generated in mixed Ar-water expansions. The electron energy dependent ion yields reveal the neutral cluster composition and structure: water clusters fully covered with the Ar solvation shell are formed under certain expansion conditions. The argon atoms shield the embedded (H{sub 2}O){sub n} clusters resulting in the ionization threshold above ≈15 eV for all fragments. The argon atoms also mediate more complex reactions in the clusters: e.g., the charge transfer between Ar{sup +} and water occurs above the threshold; at higher electron energies above ∼28 eV, an excitonic transfer process between Ar{sup +}* and water opens leading to new products Ar{sub n}H{sup +} and (H{sub 2}O){sub n}H{sup +}. On the other hand, the excitonic transfer from the neutral Ar* state at lower energies is not observed although this resonant process was demonstrated previously in a photoionization experiment. Doubly charged fragments (H{sub 2}O){sub n}H{sub 2}{sup 2+} and (H{sub 2}O){sub n}{sup 2+} ions are observed and Intermolecular Coulomb decay (ICD) processes are invoked to explain their thresholds. The Coulomb explosion of the doubly charged cluster formed within the ICD process is prevented by the stabilization effect of the argon solvent.

  5. Charge Transfer Calculations and Database for Astrophysics

    NASA Technical Reports Server (NTRS)

    Wang, J. G.; Stancil, P. C.; Rakovic, M.; Schultz, D. R.; Zygelman, B.

    2002-01-01

    A variety of theoretical approaches, having different but overlapping energy ranges of applicability, are applied to investigate charge transfer processes for collisions of atomic ions with atoms and molecules. The methods include quantal molecular-orbital close-coupling, classical trajectory Monte Carlo, and continuum distorted wave methods. Recent collision systems studied include S(+4) + H, S(+4) + He, N(+7) + He, H2O, CO, and CO2, O(+q)(q = 1 - 8) + H, H2, and S(+q)(q = 1 - 16) + H2. The database effort is concentrating on astrophysically important reactions of atomic ions X(+q)(X=H-Zn, q=1-4, and selected higher charges) with H, He, various metal atoms, H2, and other selected molecular targets. Existing data, much of it produced by us, has been compiled and critically evaluated. Data for many reactions missing in the literature are estimated using the multichannel Landau-Zener approximation. Fits to cross sections and rate coefficients using standard functions are provided as well as tabulations of the raw data. The database is available on the World Wide Web at cfadc.phy.ornl.gov/astro/ps/data.

  6. Synthesis, spectral investigations, antimicrobial activity and DNA-binding studies of novel charge transfer complex of 1,10-phenanthroline as an electron donor with π-acceptor p-Nitrophenol

    NASA Astrophysics Data System (ADS)

    Khan, Ishaat M.; Ahmad, Afaq

    2010-08-01

    Proton or charge transfer (CT) complex of donor, 1,10-phenanthroline (Phen) with π-acceptor, p-Nitrophenol (PNP) has been studied spectrophotometrically in methanol at room temperature. The binding of the CT complex with calf thymus (ct) DNA has been investigated by fluorescence spectrum, to establish the ability of the CT complex of its interaction with DNA. Stern-Volmer quenching constant ( Ksv) has also been calculated. The formation constant ( KCT), molar extinction coefficient ( ɛCT), free energy (Δ Go) and stoichiometric ratio of the CT complex have been determined by Benesi-Hildebrand equation. The stoichiometry was found to be 1:1. The CT complex was screened for its pharmacology as antibacterial and antifungal activity against various bacterial and fungal strains, showing excellent antibacterial and antifungal activity. The newly synthesized CT complex has been characterized by FTIR spectra, elemental analysis, 1H NMR, electronic absorption spectra. TGA-DTA studies were also carried out to check the stability of CT complex.

  7. Dynamical Treatment of Charge Transfer through Duplex Nucleic Acids Containing Modified Adenines

    PubMed Central

    Brancolini, Giorgia; Migliore, Agostino; Corni, Stefano; Fuentes-Cabrera, Miguel; Luque, F. Javier; Di Felice, Rosa

    2014-01-01

    We address the issue of whether chemical alterations of nucleobases are an effective tool to modulate charge transfer through DNA molecules. Our investigation uses a multi-level computational approach based on classical molecular dynamics and quantum chemistry. We find yet another evidence that structural fluctuations are a key factor to determine the electronic structure of double-stranded DNA. We argue that the electronic structure and charge transfer ability of flexible polymers is the result of a complex intertwining of various structural, dynamical and chemical factors. Chemical intuition may be used to design molecular wires, but this is not the sole component in the complex charge transfer mechanism through DNA. PMID:24060008

  8. A new TPE-based tetrapodal ligand and its Ln(iii) complexes: multi-stimuli responsive AIE (aggregation-induced emission)/ILCT(intraligand charge transfer)-bifunctional photoluminescence and NIR emission sensitization.

    PubMed

    Zhu, Yi-Xuan; Wei, Zhang-Wen; Pan, Mei; Wang, Hai-Ping; Zhang, Jian-Yong; Su, Cheng-Yong

    2016-01-21

    A tetrapodal zwitterionic-type ligand featuring both AIE (aggregation-induced emission) and ILCT (intraligand charge transfer) properties, namely 1,1',1'',1'''-(4,4',4'',4'''-(ethene-1,1,2,2-tetrayl)tetrakis(benzene-4,1-diyl))tetrakis(methylene)tetrapyridin-4(1H)-one (TPE-4PO) has been designed and applied to the assembly of lanthanide complexes LIFM-21(Ln) (Ln = Sm, Eu, Gd, Tb and Dy). Apart from sensitization of NIR emission of Sm(3+) and Dy(3+), the resulting ligand and lanthanide complexes show both AIE and ILCT-related photoluminescence behaviors. The photo-response of this system to different aggregation states, solvents' polarity and mechanical grinding was demonstrated by distinguishable emission intensities and colours.

  9. Effects of the Distributions of Energy or Charge Transfer Rates on Spectral Hole Burning in Pigment-Protein Complexes at Low Temperatures

    SciTech Connect

    Herascu, N.; Ahmouda, S.; Picorel, R.; Seibert, M.; Jankowiak, R.; Zazubovich, V.

    2011-12-22

    Effects of the distributions of excitation energy transfer (EET) rates (homogeneous line widths) on the nonphotochemical (resonant) spectral hole burning (SHB) processes in photosynthetic chlorophyll-protein complexes (reaction center [RC] and CP43 antenna of Photosystem II from spinach) are considered. It is demonstrated that inclusion of such a distribution results in somewhat more dispersive hole burning kinetics. More importantly, however, inclusion of the EET rate distributions strongly affects the dependence of the hole width on the fractional hole depth. Different types of line width distributions have been explored, including those resulting from Foerster type EET between weakly interacting pigments as well as Gaussian ones, which may be a reasonable approximation for those resulting, for instance, from so-called extended Foerster models. For Gaussian line width distributions, it is possible to determine the parameters of both line width and tunneling parameter distributions from SHB data without a priori knowledge of any of them. Concerning more realistic asymmetric distributions, we demonstrate, using the simple example of CP43 antenna, that one can use SHB modeling to estimate electrostatic couplings between pigments and support or exclude assignment of certain pigment(s) to a particular state.

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

    SciTech Connect

    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.

  11. Modeling noncovalent radical-molecule interactions using conventional density-functional theory: beware erroneous charge transfer.

    PubMed

    Johnson, Erin R; Salamone, Michela; Bietti, Massimo; DiLabio, Gino A

    2013-02-07

    Conventional density-functional theory (DFT) has the potential to overbind radical-molecule complexes because of erroneous charge transfer. We examined this behavior by exploring the ability of various DFT approximations to predict fractional charge transfer and by quantifying the overbinding in a series of complexes. It is demonstrated that too much charge is transferred from molecules to radicals when the radical singly unoccupied molecular orbitals are predicted to be erroneously too low in energy relative to the molecule highest occupied molecular orbitals, leading to excessive Coulombic attraction. In this respect, DFT methods formulated with little or no Hartree-Fock exchange perform most poorly. The present results illustrate that the charge-transfer problem is much broader than may have been previously expected and is not limited to conventional (i.e., molecule-molecule) donor-acceptor complexes.

  12. Charge transfer complexes of fullerenes containing C₆₀˙⁻ and C₇₀˙⁻ radical anions with paramagnetic Co(II)(dppe)₂Cl⁺ cations (dppe: 1,2-bis(diphenylphosphino)ethane).

    PubMed

    Konarev, Dmitri V; Troyanov, Sergey I; Otsuka, Akihiro; Yamochi, Hideki; Saito, Gunzi; Lyubovskaya, Rimma N

    2016-04-21

    The reduction of Co(II)(dppe)Cl2 with sodium fluorenone ketyl produces a red solution containing the Co(I) species. The dissolution of C60 in the obtained solution followed by the precipitation of crystals with hexane yields a salt {Co(I)(dppe)2(+)}(C60˙(-))·2C6H4Cl2 and a novel complex {Co(dppe)2Cl}(C60) (). With C70, only the crystals of {Co(dppe)2Cl}(C70)·0.5C6H4Cl2 () are formed. Complex contains zig-zag fullerene chains whereas closely packed double chains are formed from fullerenes in . According to the optical spectra and magnetic data charge transfer occurs in both and with the formation of the Co(II)(dppe)2Cl(+) cations and the C60˙(-) or C70˙(-) radical anions. In spite of the close packing in crystals, C60˙(-) or C70˙(-) retain their monomeric form at least down to 100 K. The effective magnetic moments of and of 1.98 and 2.27μB at 300 K, respectively, do not attain the value of 2.45μB expected for the system with two non-interacting S = 1/2 spins at full charge transfer to fullerenes. Most probably diamagnetic {Co(I)(dppe)2Cl}(0) and neutral fullerenes are partially preserved in the samples which can explain the weak magnetic coupling of spins and the absence of fullerene dimerization in both complexes. The EPR spectra of and show asymmetric signals approximated by several lines with g-factors ranging from 2.0009 to 2.3325. These signals originate from the exchange interaction between the paramagnetic Co(II)(dppe)2Cl(+) cations and the fullerene˙(-) radical anions.

  13. Melatonin charge transfer complex with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone: Molecular structure, DFT studies, thermal analyses, evaluation of biological activity and utility for determination of melatonin in pure and dosage forms

    NASA Astrophysics Data System (ADS)

    Mohamed, Gehad G.; Hamed, Maher M.; Zaki, Nadia G.; Abdou, Mohamed M.; Mohamed, Marwa El-Badry; Abdallah, Abanoub Mosaad

    2017-07-01

    A simple, accurate and fast spectrophotometric method for the quantitative determination of melatonin (ML) drug in its pure and pharmaceutical forms was developed based on the formation of its charge transfer complex with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) as an electron acceptor. The different conditions for this method were optimized accurately. The Lambert-Beer's law was found to be valid over the concentration range of 4-100 μg mL- 1 ML. The solid form of the CT complex was structurally characterized by means of different spectral methods. Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations were carried out. The different quantum chemical parameters of the CT complex were calculated. Thermal properties of the CT complex and its kinetic thermodynamic parameters were studied, as well as its antimicrobial and antifungal activities were investigated. Molecular docking studies were performed to predict the binding modes of the CT complex components towards E. coli bacterial RNA and the receptor of breast cancer mutant oxidoreductase.

  14. Ion momentum and energy transfer rates for charge exchange collisions

    NASA Technical Reports Server (NTRS)

    Horwitz, J.; Banks, P. M.

    1973-01-01

    The rates of momentum and energy transfer have been obtained for charge exchange collisions between ion and neutral gases having arbitrary Maxwellian temperatures and bulk transport velocities. The results are directly applicable to the F-region of the ionosphere where 0+ - 0 charge is the dominant mechanism affecting ion momentum and energy transfer.

  15. DNA charge transfer: Hot holes break the speed limit

    NASA Astrophysics Data System (ADS)

    Beratan, D. N.; Waldeck, D. H.

    2016-11-01

    Charge transfer through DNA has been well studied over recent decades from both a biological and electronics perspective. It has now been shown that charge transfer can be accelerated one hundredfold by using highly energetic 'hot holes', revealing a new mechanism that could help to create useful electronic biomaterials.

  16. Photoinduced Charge and Energy Transfer Processes in Molecular Aggregates

    SciTech Connect

    John F. Endicott

    2009-10-20

    This project involved the experimental probing of the electronic excited states generated by photoinduced (center-to-center) electron and energy transfer processes in several classes of transition metal donor/acceptor (D/A) complexes. Some of the general properties inferred from these studies should be useful in the design of new systems for energy conversion applications. Pursuit of the project goals has involved the determination of electron transfer efficiencies and the detailed study of variations in the electronic spectra of D/A complexes. This has resulted in the study of some very fundamental issues of photoinduced charge transfer and the identification of some of the constraints on its efficiency. The experimental studies of the competition between the degradative non-radiative unimolecular relaxation of transition metal excited states and their transfer of charge from these excited states to external acceptors have involved a range of techniques such as transient decay kinetics, photoacoustic calorimetry and transient or stationary state spectroscopy. The substrates synthesized for these studies were selected to provide model systems, or series of model systems to probe the validity of models of electronic excited states and their reactivity. The work during the last few years has focused largely, but not exclusively, on the use of emission spectral band shapes to probe the properties of charge transfer (CT) excited states. Bandshape variations are one of the very few approaches for systematically probing electronic excited states and good band shape resolution is necessary in order to gain information about the structural variations that correlate with excited state reactivity. Differences in molecular structure correlate with differences in chemical reactivity, and the variations in emission bandshapes are well known to relate to variations in the molecular structural differences between the excited and ground electronic states. However, it is has been

  17. Estimating and modeling charge transfer from the SAPT induction energy.

    PubMed

    Deng, Shi; Wang, Qiantao; Ren, Pengyu

    2017-10-05

    Recent studies using quantum mechanics energy decomposition methods, for example, SAPT and ALMO, have revealed that the charge transfer energy may play an important role in short ranged inter-molecular interactions, and have a different distance dependence comparing with the polarization energy. However, the charge transfer energy component has been ignored in most current polarizable or non-polarizable force fields. In this work, first, we proposed an empirical decomposition of SAPT induction energy into charge transfer and polarization energy that mimics the regularized SAPT method (ED-SAPT). This empirical decomposition is free of the divergence issue, hence providing a good reference for force field development. Then, we further extended this concept in the context of AMOEBA polarizable force field, proposed a consistent approach to treat the charge transfer phenomenon. Current results show a promising application of this charge transfer model in future force field development. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

  18. Constrained photophysics of partially and fully encapsulated charge transfer probe (E)-3-(4-Methylaminophenyl) acrylic acid methyl ester inside cyclodextrin nano-cavities: Evidence of cyclodextrins cavity dependent complex stoichiometry

    NASA Astrophysics Data System (ADS)

    Ghosh, Shalini; Jana, Sankar; Guchhait, Nikhil

    2011-12-01

    The polarity sensitive intra-molecular charge transfer (ICT) emission from (E)-3-(4-Methylaminophenyl) acrylic acid methyl ester (MAPAME) is found to show distinct changes once introduced into the nano-cavities of cyclodextrins in aqueous environment. Movement of the molecule from the more polar aqueous environment to the less polar, hydrophobic cyclodextrin interior is marked by the blue shift of the CT emission band with simultaneous fluorescence intensity enhancement. The emission spectral changes on complexation with the α- and β-CD show different stoichiometries as observed from the Benesi-Hildebrand plots. Fluorescence anisotropy and lifetime measurements were performed to probe the different behaviors of MAPAME in aqueous α- and β-CD solutions.

  19. Constrained photophysics of partially and fully encapsulated charge transfer probe (E)-3-(4-Methylaminophenyl) acrylic acid methyl ester inside cyclodextrin nano-cavities: evidence of cyclodextrins cavity dependent complex stoichiometry.

    PubMed

    Ghosh, Shalini; Jana, Sankar; Guchhait, Nikhil

    2011-12-15

    The polarity sensitive intra-molecular charge transfer (ICT) emission from (E)-3-(4-Methylaminophenyl) acrylic acid methyl ester (MAPAME) is found to show distinct changes once introduced into the nano-cavities of cyclodextrins in aqueous environment. Movement of the molecule from the more polar aqueous environment to the less polar, hydrophobic cyclodextrin interior is marked by the blue shift of the CT emission band with simultaneous fluorescence intensity enhancement. The emission spectral changes on complexation with the α- and β-CD show different stoichiometries as observed from the Benesi-Hildebrand plots. Fluorescence anisotropy and lifetime measurements were performed to probe the different behaviors of MAPAME in aqueous α- and β-CD solutions. Copyright © 2011 Elsevier B.V. All rights reserved.

  20. Charge-transfer reactions, energy gaps, and electron-transfer diabatic surfaces

    NASA Astrophysics Data System (ADS)

    Marzari, Nicola; Sit, P. H.-L.

    2007-03-01

    Density-functional theory in the LDA or GGA approximation has become the widely-used standard model of condensed matter theory. I will discuss shortcomings and solutions to some of the problems that arise when addressing complex chemical reactions. These challenges include the correct description of electron-transfer processes, where electrons become delocalized and shared between ions that should be in different oxidation states. An effective solution can be obtained by introducing a penalty functional that imposes the correct charge state on the ions involved in the reaction [1]. This approach is validated in a model system, showing that the ground state and the charge-transfer excited state can be calculated with negligible errors, and then applied to the determination of the diabatic free-energy surfaces for ferrous and ferric ions in solution. [1] P. H.-L. Sit, Matteo Cococcioni and Nicola Marzari, Phys. Rev. Lett. 97, 028303 (2006).

  1. Spectroscopic and molecular docking studies on the charge transfer complex of bovine serum albumin with quinone in aqueous medium and its influence on the ligand binding property of the protein

    NASA Astrophysics Data System (ADS)

    Satheshkumar, Angupillai; Elango, Kuppanagounder P.

    2014-09-01

    The spectral techniques such as UV-Vis, 1H NMR and fluorescence and electrochemical experiments have been employed to investigate the interaction between 2-methoxy-3,5,6-trichloro-1,4-benzoquinone (MQ; a water soluble quinone) and bovine serum albumin (BSA) in aqueous medium. The fluorescence of BSA was quenched by MQ via formation of a 1:1 BSA-MQ charge transfer adduct with a formation constant of 3.3 × 108 L mol-1. Based on the Forster’s theory the binding distance between them is calculated as 2.65 nm indicating high probability of binding. For the first time, influence of quinone on the binding property of various types of ligands such as aspirin, ascorbic acid, nicotinimide and sodium stearate has also been investigated. The results indicated that the strong and spontaneous binding existing between BSA and MQ, decreased the intensity of binding of these ligands with BSA. Since Tryptophan (Trp) is the basic residue present in BSA, a comparison between binding property of Trp-MQ adduct with that of BSA-MQ with these ligands has also been attempted. 1H NMR titration study indicated that the Trp forms a charge transfer complex with MQ, which reduces the interaction of Trp with the ligands. Molecular docking study supported the fact that the quinone interacts with the Trp212 unit of the BSA and the free energy change of binding (ΔG) for the BSA-MQ complex was found to be -46 kJ mol-1, which is comparable to our experimental free energy of binding (-49 kJ mol-1) obtained from fluorescence study.

  2. Properties of Manganese(III) Ferrocenyl-β-Diketonato Complexes Revealed by Charge Transfer and Multiplet Splitting in the Mn 2p and Fe 2p X-Ray Photoelectron Envelopes.

    PubMed

    Buitendach, Blenerhassitt E; Erasmus, Elizabeth; Niemantsverdriet, J W Hans; Swarts, Jannie C

    2016-10-26

    A series of ferrocenyl-functionalized β-diketonato manganese(III) complexes, [Mn(FcCOCHCOR)₃] with R = CF₃, CH₃, Ph (phenyl) and Fc (ferrocenyl) was subjected to a systematic XPS study of the Mn 2p3/2 and Fe 2p3/2 core-level photoelectron lines and their satellite structures. A charge-transfer process from the β-diketonato ligand to the Mn(III) metal center is responsible for the prominent shake-up satellite peaks of the Mn 2p photoelectron lines and the shake-down satellite peaks of the Fe 2p photoelectron lines. Multiplet splitting simulations of the photoelectron lines of the Mn(III) center of [Mn(FcCOCHCOR)₃] resemble the calculated Mn 2p3/2 envelope of Mn(3+) ions well, indicating the Mn(III) centers are in the high spin state. XPS spectra of complexes with unsymmetrical β-diketonato ligands (i.e., R not Fc) were described with two sets of multiplet splitting peaks representing fac and the more stable mer isomers respectively. Stronger electron-donating ligands stabilize fac more than mer isomers. The sum of group electronegativities, ΣχR, of the β-diketonato pendant side groups influences the binding energies of the multiplet splitting and charge transfer peaks in both Mn and Fe 2p3/2 photoelectron lines, the ratio of satellite to main peak intensities, and the degree of covalence of the Mn-O bond.

  3. Spectroscopic and molecular docking studies on the charge transfer complex of bovine serum albumin with quinone in aqueous medium and its influence on the ligand binding property of the protein.

    PubMed

    Satheshkumar, Angupillai; Elango, Kuppanagounder P

    2014-09-15

    The spectral techniques such as UV-Vis, (1)H NMR and fluorescence and electrochemical experiments have been employed to investigate the interaction between 2-methoxy-3,5,6-trichloro-1,4-benzoquinone (MQ; a water soluble quinone) and bovine serum albumin (BSA) in aqueous medium. The fluorescence of BSA was quenched by MQ via formation of a 1:1 BSA-MQ charge transfer adduct with a formation constant of 3.3×10(8) L mol(-1). Based on the Forster's theory the binding distance between them is calculated as 2.65 nm indicating high probability of binding. For the first time, influence of quinone on the binding property of various types of ligands such as aspirin, ascorbic acid, nicotinimide and sodium stearate has also been investigated. The results indicated that the strong and spontaneous binding existing between BSA and MQ, decreased the intensity of binding of these ligands with BSA. Since Tryptophan (Trp) is the basic residue present in BSA, a comparison between binding property of Trp-MQ adduct with that of BSA-MQ with these ligands has also been attempted. 1H NMR titration study indicated that the Trp forms a charge transfer complex with MQ, which reduces the interaction of Trp with the ligands. Molecular docking study supported the fact that the quinone interacts with the Trp212 unit of the BSA and the free energy change of binding (ΔG) for the BSA-MQ complex was found to be -46 kJ mol(-1), which is comparable to our experimental free energy of binding (-49 kJ mol(-1)) obtained from fluorescence study.

  4. Evidence of Ultrafast Charge Transfer Driven by Coherent Lattice Vibrations.

    PubMed

    Rury, Aaron S; Sorenson, Shayne A; Dawlaty, Jahan M

    2017-01-05

    We report evidence that intermolecular vibrations coherently drive charge transfer between the sites of a material on ultrafast time scales. Following a nonresonant stimulated Raman pump pulse that excites the organic material quinhydrone, we observe the initial appearance of oscillations due to intermolecular lattice vibrations and then the delayed appearance of a higher-frequency oscillation that we assign to a totally symmetric intramolecular vibration. We use the coherent dynamics of the transient reflectivity signal to propose that coherence transfer drives excitation of this intramolecular vibration. Furthermore, we conclude that the dynamical frequency shift of the intramolecular vibration reports the formation of a quasi-stable charge-separated state on ultrafast time scales. We calculate model dynamics using the extended Hubbard Hamiltonian to explain coherence transfer due to vibrationally driven charge transfer. These results demonstrate that the coherent excitation of low-frequency vibrations can drive charge transfer in the solid state and control material properties.

  5. The Pushkin—Varshney—Kamoonpuri equation for the evaluation of association constants for the charge transfer complexes of sparingly soluble acceptors

    NASA Astrophysics Data System (ADS)

    Qureshi, Pushkin M.; Varshney, Rishi K.; Kamoonpuri, S. Iqbal M.

    The proposed Pushkin—Varshney—Kamoonpuri equation proposes a simple way in which the association constants of complexes of sparingly soluble acceptors may be evaluated. The method can be used where the concentration of the acceptor is not known.

  6. Charge Transfer and Catalysis at the Metal Support Interface

    SciTech Connect

    Baker, Lawrence Robert

    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.

  7. Synthesis and Photophysical and Electrochemical Properties of Functionalized Mono-, Bis-, and Trisanthracenyl Bridged Ru(II) Bis(2,2′:6′,2″-terpyridine) Charge Transfer Complexes

    PubMed Central

    Adeloye, Adewale O.; Ajibade, Peter A.

    2014-01-01

    With the aim of developing new molecular devices having long-range electron transfer in artificial systems and as photosensitizers, a series of homoleptic ruthenium(II) bisterpyridine complexes bearing one to three anthracenyl units sandwiched between terpyridine and 2-methyl-2-butenoic acid group are synthesized and characterized. The complexes formulated as bis-4′-(9-monoanthracenyl-10-(2-methyl-2-butenoic acid) terpyridyl) ruthenium(II) bis(hexafluorophosphate) (RBT1), bis-4′-(9-dianthracenyl-10-(2-methyl-2-butenoic acid) terpyridyl) ruthenium(II) bis(hexafluorophosphate) (RBT2), and bis-4′-(9-trianthracenyl-10-(2-methyl-2-butenoic acid) terpyridyl) ruthenium(II) bis(hexafluorophosphate) (RBT3) were characterized by elemental analysis, FT-IR, UV-Vis, photoluminescence, 1H and 13C NMR spectroscopy, and electrochemical techniques by elemental analysis, FT-IR, UV-Vis, photoluminescence, 1H and 13C NMR spectroscopy, and electrochemical techniques. The cyclic voltammograms (CVs) of (RBT1), (RBT2), and (RBT3) display reversible one-electron oxidation processes at E1/2 = 1.13 V, 0.71 V, and 0.99 V, respectively (versus Ag/AgCl). Based on a general linear correlation between increase in the length of π-conjugation bond and the molar extinction coefficients, the Ru(II) bisterpyridyl complexes show characteristic broad and intense metal-to-ligand charge transfer (MLCT) band absorption transitions between 480–600 nm, ε = 9.45 × 103 M−1 cm−1, and appreciable photoluminescence spanning the visible region. PMID:24883408

  8. Improved Charge-Transfer Fluorescent Dyes

    NASA Technical Reports Server (NTRS)

    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 < 400 nm) and emit photons in the long-wavelength ultraviolet, visible, and, when dissolved in some solvents, near-infrared regions. In addition, these dyes can be excited by two-photon absorption at near-infrared wavelengths (600 to 800 nm) to produce 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

  9. Charge transfer interactions in oligomer coated gold nanoclusters

    NASA Astrophysics Data System (ADS)

    Newmai, M. Boazbou; Kumar, Pandian Senthil

    2016-05-01

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

  10. Charge transfer interactions in oligomer coated gold nanoclusters

    SciTech Connect

    Newmai, M. Boazbou; Kumar, Pandian Senthil

    2016-05-23

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

  11. Experimental study of charge vertical transfer in surface air layer

    NASA Astrophysics Data System (ADS)

    Panchishkina, I. N.; Petrova, G. G.; Petrov, A. I.

    2017-05-01

    The variability of air-earth electric currents in the lower 3-m air layer is analyzed in a complex with measurement data on the physical parameters that affect charge transfer in the atmosphere. Three types of air-earth current density profiles have been revealed during experimental observations in summer in Rostov region: (1) the current density decreases with an increase in the distance from the Earth's surface and then stabilizes (nighttime conditions); (2) the current density increases with altitude up to 1 m and then decreases as altitude increases (day hours); (3) transient between types 1 and 2 that are observed in the morning and evening hours. The intensity of charge transfer in the surface air layer under the action of mechanical forces under different stratifications is estimated on the basis of data on altitude variations in the air-earth current density in view of the stationarity of electric processes and the constancy in the altitude of the total air-earth current density. Thermodynamic conditions are estimated with the use of wind velocity measurements and calculations of the turbulence factor and vertical component of the air temperature gradient.

  12. Energy Transfer of a Shaped Charge.

    SciTech Connect

    Milinazzo, Jared Joseph

    2016-11-01

    A cylinder of explosive with a hollow cavity on one and a detonator at the other is considered a hollow charge. When the explosive is detonated the detonation products form a localized intense force. If the hollow charge is placed near or in contact with a steel plate then the damage to the plate is greater than a solid cylinder of explosive even though there is a greater amount of explosive in the latter charge. The hollow cavity can take almost any geometrical shape with differing amounts of damage associated with each shape. This phenomenon is known in the United States as the Munroe effect.

  13. Charge transfer in time-dependent density functional theory

    NASA Astrophysics Data System (ADS)

    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.

  14. Spectral, thermal and kinetic studies of charge-transfer complexes formed between the highly effective antibiotic drug metronidazole and two types of acceptors: σ- and π-acceptors

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

    Understanding the interaction between drugs and small inorganic or organic molecules is critical in being able to interpret the drug-receptor interactions and acting mechanism of these drugs. A combined solution and solid state study was performed to describe the complexation chemistry of drug metronidazole (MZ) which has a broad-spectrum antibacterial activity with two types of acceptors. The acceptors include, σ-acceptor (i.e., iodine) and π-acceptors (i.e., dichlorodicyanobenzoquinone (DDQ), chloranil (CHL) and picric acid (PA)). The molecular structure, spectroscopic characteristics, the binding modes as well as the thermal stability were deduced from IR, UV-vis, 1H NMR and thermal studies. The binding ratio of complexation (MZ: acceptor) was determined to be 1:2 for the iodine acceptor and 1:1 for the DDQ, CHL or PA acceptor, according to the CHN elemental analyses and spectrophotometric titrations. It has been found that the complexation with CHL and PA acceptors increases the values of enthalpy and entropy, while the complexation with DDQ and iodine acceptors decreases the values of these parameters compared with the free MZ donor.

  15. Spectral, thermal and kinetic studies of charge-transfer complexes formed between the highly effective antibiotic drug metronidazole and two types of acceptors: σ- and π-acceptors.

    PubMed

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

    2015-04-15

    Understanding the interaction between drugs and small inorganic or organic molecules is critical in being able to interpret the drug-receptor interactions and acting mechanism of these drugs. A combined solution and solid state study was performed to describe the complexation chemistry of drug metronidazole (MZ) which has a broad-spectrum antibacterial activity with two types of acceptors. The acceptors include, σ-acceptor (i.e., iodine) and π-acceptors (i.e., dichlorodicyanobenzoquinone (DDQ), chloranil (CHL) and picric acid (PA)). The molecular structure, spectroscopic characteristics, the binding modes as well as the thermal stability were deduced from IR, UV-vis, (1)H NMR and thermal studies. The binding ratio of complexation (MZ: acceptor) was determined to be 1:2 for the iodine acceptor and 1:1 for the DDQ, CHL or PA acceptor, according to the CHN elemental analyses and spectrophotometric titrations. It has been found that the complexation with CHL and PA acceptors increases the values of enthalpy and entropy, while the complexation with DDQ and iodine acceptors decreases the values of these parameters compared with the free MZ donor.

  16. Charge prediction machine: tool for inferring precursor charge states of electron transfer dissociation tandem mass spectra.

    PubMed

    Carvalho, Paulo C; Cociorva, Daniel; Wong, Catherine C L; Carvalho, Maria da Gloria da C; Barbosa, Valmir C; Yates, John R

    2009-03-01

    Electron transfer dissociation (ETD) can dissociate highly charged ions. Efficient analysis of ions dissociated with ETD requires accurate determination of charge states for calculation of molecular weight. We created an algorithm to assign the charge state of ions often used for ETD. The program, Charge Prediction Machine (CPM), uses Bayesian decision theory to account for different charge reduction processes encountered in ETD and can also handle multiplex spectra. CPM correctly assigned charge states to 98% of the 13,097 MS2 spectra from a combined data set of four experiments. In a comparison between CPM and a competing program, Charger (ThermoFisher), CPM produced half the mistakes.

  17. Charge transfer reactions in nematic liquid crystals

    SciTech Connect

    Wiederrecht, G.P.; Wasielewski, M.R. |; Galili, T.; Levanon, H.

    1998-07-01

    Ultrafast transient absorption studies of intramolecular photoinduced charge separation and thermal charge recombination were carried out on a molecule consisting of a 4-(N-pyrrolidino)naphthalene-1,8-imide donor (PNI) covalently attached to a pyromellitimide acceptor (PI) dissolved in the liquid crystal 4{prime}-(n-pentyl)-4-cyanobiphenyl (5CB). The temperature dependencies of the charge separation and recombination rates were obtained at temperatures above the nematic-isotropic phase transition of 5CB, where ordered microdomains exist and scattering of visible light by these domains is absent. The authors show that excited state charge separation is dominated by molecular reorientation of 5CB perpendicular to the director within the liquid crystal microdomains. They also show that charge recombination is adiabatic and is controlled by the comparatively slow collective reorientation of the liquid crystal microdomains relative to the orientation of PNI{sup +}-PI{sup {minus}}. They also report the results of time resolved electron paramagnetic resonance (TREPR) studies of photoinduced charge separation in a series of supramolecular compounds dissolved in oriented liquid crystal solvents. These studies permit the determination of the radical pair energy levels as the solvent reorganization energy increases from the low temperature crystalline phase, through the soft glass phase, to the nematic phase of the liquid crystal.

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

    NASA Astrophysics Data System (ADS)

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

    2006-05-01

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

  19. Laser photolysis studies on Cu I complexes of thia-calix[3]pyridine. Phosphorescence from the intramolecular charge-transfer excited state

    NASA Astrophysics Data System (ADS)

    Kinoshita, Isamu; Hamazawa, Akihisa; Nishioka, Takanori; Adachi, Haruna; Suzuki, Hiroyuki; Miyazaki, Yoshio; Tsuboyama, Akira; Okada, Shinjiro; Hoshino, Mikio

    2003-04-01

    Copper(I) complexes of thia-calix[3]pyridine in dichloromethane exhibit phosphorescence from the MLCT triplet states at room temperature. The phosphorescence spectrum shifts to red on going from 300 to 180 K. The laser photolysis study carried out in the temperature range 300-180 K reveals that phosphorescence originates from the two triplet states, TH and TL, which are in thermal equilibrium with the energy difference of ca. 5 kcal mol -1.

  20. Photoconductivity and photovoltaic effect of charge-transfer complex of poly[4-phenyl-2,6--(p-phenoxy) quinoline] and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone

    SciTech Connect

    Donghoon Choi; Eun Ju Lee; Kyeongah Kim; Soo Young Park; Nakjoong Kim . Polymer Chemistry Lab.)

    1993-11-20

    A new polymer containing a heterocyclic quinoline unit in the main chain,poly[4-phenyl-2,6-(p-phenoxy) quinoline] (PQ), was synthesized by an acid-catalyzed self-condensation reaction. The authors have found that PQ, which is generally a good insulator itself, can show photoconductivity when doped with an electron acceptor. From the UV-VIS absorption spectra, they found that PQ can form a charge-transfer (CT) complex with an electron acceptor, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ). The CT complex of the PQ-DDQ mixture showed distinct photoconductivity. Employing the DDQ composition ranging from 5 to 10 wt %, the ratio of dark and photoconductivity was calculated to be about 1: 100 at an applied electric field of 10[sup 5] V/cm. Additionally,the bilayer sample of PQ/DDQ exhibited a significant photovoltaic current increased with increasing photointensity. The open-circuit voltage was measured ranging from 0.4 to 0.7 V and the photovoltaic conversion efficiency was calculated to be [sup [minus]3]--10[sup [minus]2]%. The PQ film treated with DDQ vapor showed a relatively higher photovoltaic effect than that of the sample treated with DDQ solution.

  1. Spectrophotometric and fluorescence quenching studies of the charge transfer complexation of (4-dimethylamino-benzylidene)-(4,6-dimethyl-pyrimidin-2-yl)-amine with some organic acceptors

    NASA Astrophysics Data System (ADS)

    El-Sayed, Yusif S.

    2011-04-01

    The interaction of organic acceptors such as tetrafluoro-1,4-benzoquinone (p-TFQ), tetrachloro-1,4-benzoquinone (p-TCQ), tetrachloro-1,2-benzoquinone (o-TCQ), tetrabromo-1,4-benzoquinone (p-TBQ), tetrabromo-1,2-benzoquinone (o-TBQ) and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) with (4-dimethylamino-benzylidene)-(4,6-dimethyl-pyrimidin-2-yl)-amine (SB) as donor is studied spectrophotometrically and fluoremetrically in dichloromethane and trichloromethane. The association constant ( K), thermodynamic parameters (Δ G°, Δ H° and Δ S°), oscillator strength ( f), transition dipole moment ( μ) and stoichiometric ratio are calculated using Benezi-Hildbrand's, Job and straight-line methods, respectively. The results reveal that the interaction between the donor and acceptors is due to π-π* transitions by the formation of radical ion pairs. The fluorescence quenching of SB with different organic acceptors is investigated. The results reveal that the fluorescence quenching obeys the static type mechanism via charge transfer complex formation in the ground state. The effect of temperature on the equilibrium constants of the CT complexes is also studied.

  2. Spectrophotometric and fluorescence quenching studies of the charge transfer complexation of (4-dimethylamino-benzylidene)-(4,6-dimethyl-pyrimidin-2-yl)-amine with some organic acceptors.

    PubMed

    El-Sayed, Yusif S

    2011-04-01

    The interaction of organic acceptors such as tetrafluoro-1,4-benzoquinone (p-TFQ), tetrachloro-1,4-benzoquinone (p-TCQ), tetrachloro-1,2-benzoquinone (o-TCQ), tetrabromo-1,4-benzoquinone (p-TBQ), tetrabromo-1,2-benzoquinone (o-TBQ) and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) with (4-dimethylamino-benzylidene)-(4,6-dimethyl-pyrimidin-2-yl)-amine (SB) as donor is studied spectrophotometrically and fluoremetrically in dichloromethane and trichloromethane. The association constant (K), thermodynamic parameters (ΔG°, ΔH° and ΔS°), oscillator strength (f), transition dipole moment (μ) and stoichiometric ratio are calculated using Benezi-Hildbrand's, Job and straight-line methods, respectively. The results reveal that the interaction between the donor and acceptors is due to π-π* transitions by the formation of radical ion pairs. The fluorescence quenching of SB with different organic acceptors is investigated. The results reveal that the fluorescence quenching obeys the static type mechanism via charge transfer complex formation in the ground state. The effect of temperature on the equilibrium constants of the CT complexes is also studied.

  3. Screen charge transfer by grounded tip on ferroelectric surfaces.

    SciTech Connect

    Kim, Y.; Kim, J.; Buhlmann, S.; Hong, S.; Kim, Y. K.; Kim, S.-H.; No, K.; Materials Science Division; Korea Advanced Inst. of Science and Technology; Samsung Advanced Inst. of Technology; Inostek Inc.

    2008-03-01

    We have investigated polarization reversal and charge transfer effects by a grounded tip on 50 nm thick ferroelectric thin films using piezoelectric force microscopy and Kelvin force microscopy. We observed the polarization reversal in the center of written domains, and also identified another mechanism, which is the transfer of screen charges toward the grounded tip. In order to overcome these phenomena, we successfully applied a modified read/write scheme featuring a bias voltage.

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

    SciTech Connect

    Douhal, Abderrazzak; Sanz, Mikel; Carranza, Maria Angeles; Organero, Juan Angel; Tormo, Laura

    2005-03-17

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

  5. Modelling Charge Transfer Reactions and Excitations with Subsystem DFT

    NASA Astrophysics Data System (ADS)

    Pavanello, Michele; Neugebauer, Johannes

    2012-02-01

    The subsystem formulation of DFT known as Frozen Density Embedding (FDE) offers an excellent platform for studying charge transfer reactions in solvated systems, such as biosystems. We present the necessary theory developments for the calculation of the electronic couplings as well as the charge transfer excitations from FDE derived densities. We present preliminary calculations on DNA oligomers radical cations that include donor-bridge, donor-bridge-acceptor, and fully solvated systems.

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

    NASA Technical Reports Server (NTRS)

    Avila, Eldo E.; Caranti, Giorgio M.

    1991-01-01

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

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

    SciTech Connect

    Mirkin, Noemi G.; Krimm, Samuel

    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.

  8. Discrete electrostatic charge transfer by the electrophoresis of a charged droplet in a dielectric liquid.

    PubMed

    Im, Do Jin; Ahn, Myung Mo; Yoo, Byeong Sun; Moon, Dustin; Lee, Dong Woog; Kang, In Seok

    2012-08-14

    We have experimentally investigated the electrostatic charging of a water droplet on an electrified electrode surface to explain the detailed inductive charging processes and use them for the detection of droplet position in a lab-on-a-chip system. The periodic bouncing motion of a droplet between two planar electrodes has been examined by using a high-resolution electrometer and an image analysis method. We have found that this charging process consists of three steps. The first step is inductive charge accumulation on the opposite electrode by the charge of a droplet. This induction process occurs while the droplet approaches the electrode, and it produces an induction current signal at the electrometer. The second step is the discharging of the droplet by the accumulated induced charge at the moment of contact. For this second step, there is no charge-transfer detection at the electrometer. The third step is the charging of the neutralized droplet to a certain charged state while the droplet is in contact with the electrode. The charge transfer of the third step is detected as the pulse-type signal of an electrometer. The second and third steps occur simultaneously and rapidly. We have found that the induction current by the movement of a charged droplet can be accurately used to measure the charge of the droplet and can also be used to monitor the position of a droplet under actuation. The implications of the current findings for understanding and measuring the charging process are discussed.

  9. Charge transfer reactions in multiply charged ion-atom collisions. [in interstellar clouds

    NASA Technical Reports Server (NTRS)

    Steigman, G.

    1975-01-01

    Charge-transfer reactions in collisions between highly charged ions and neutral atoms of hydrogen and/or helium may be rapid at thermal energies. If these reactions are rapid, they will suppress highly charged ions in H I regions and guarantee that the observed absorption features from such ions cannot originate in the interstellar gas. A discussion of such charge-transfer reactions is presented and compared with the available experimental data. The possible implications of these reactions for observations of the interstellar medium, H II regions, and planetary nebulae are outlined.

  10. SEMICONDUCTOR DEVICES: Simulation for signal charge transfer of charge coupled devices

    NASA Astrophysics Data System (ADS)

    Zujun, Wang; Yinong, Liu; Wei, Chen; Benqi, Tang; Zhigang, Xiao; Shaoyan, Huang; Minbo, Liu; Yong, Zhang

    2009-12-01

    Physical device models and numerical processing methods are presented to simulate a linear buried channel charge coupled devices (CCDs). The dynamic transfer process of CCD is carried out by a three-phase clock pulse driver. By using the semiconductor device simulation software MEDICI, dynamic transfer pictures of signal charges cells, electron concentration and electrostatic potential are presented. The key parameters of CCD such as charge transfer efficiency (CTE) and dark electrons are numerically simulated. The simulation results agree with the theoretic and experimental results.

  11. Charge transfer in strongly correlated systems: An exact diagonalization approach to model Hamiltonians

    SciTech Connect

    Schöppach, Andreas; Gnandt, David; Koslowski, Thorsten

    2014-04-07

    We study charge transfer in bridged di- and triruthenium complexes from a theoretical and computational point of view. Ab initio computations are interpreted from the perspective of a simple empirical Hamiltonian, a chemically specific Mott-Hubbard model of the complexes' π electron systems. This Hamiltonian is coupled to classical harmonic oscillators mimicking a polarizable dielectric environment. The model can be solved without further approximations in a valence bond picture using the method of exact diagonalization and permits the computation of charge transfer reaction rates in the framework of Marcus' theory. In comparison to the exact solution, the Hartree-Fock mean field theory overestimates both the activation barrier and the magnitude of charge-transfer excitations significantly. For triruthenium complexes, we are able to directly access the interruthenium antiferromagnetic coupling strengths.

  12. Charge transfer in strongly correlated systems: an exact diagonalization approach to model Hamiltonians.

    PubMed

    Schöppach, Andreas; Gnandt, David; Koslowski, Thorsten

    2014-04-07

    We study charge transfer in bridged di- and triruthenium complexes from a theoretical and computational point of view. Ab initio computations are interpreted from the perspective of a simple empirical Hamiltonian, a chemically specific Mott-Hubbard model of the complexes' π electron systems. This Hamiltonian is coupled to classical harmonic oscillators mimicking a polarizable dielectric environment. The model can be solved without further approximations in a valence bond picture using the method of exact diagonalization and permits the computation of charge transfer reaction rates in the framework of Marcus' theory. In comparison to the exact solution, the Hartree-Fock mean field theory overestimates both the activation barrier and the magnitude of charge-transfer excitations significantly. For triruthenium complexes, we are able to directly access the interruthenium antiferromagnetic coupling strengths.

  13. INTRAMOLECULAR CHARGE AND ENERGY TRANSFER IN MULTICHROMOPHORIC AROMATIC SYSTEMS

    SciTech Connect

    Edward C. Lim

    2008-09-09

    A concerted experimental and computational study of energy transfer in nucleic acid bases and charge transfer in dialkylaminobenzonitriles, and related electron donor-acceptor molecules, indicate that the ultrafast photoprocesses occur through three-state conical interactions involving an intermediate state of biradical character.

  14. Real-time simulations of photoinduced coherent charge transfer and proton-coupled electron transfer.

    PubMed

    Eisenmayer, Thomas J; Buda, Francesco

    2014-10-20

    Photoinduced electron transfer (ET) and proton-coupled electron transfer (PCET) are fundamental processes in natural phenomena, most noticeably in photosynthesis. Time-resolved spectroscopic evidence of coherent oscillatory behavior associated with these processes has been reported both in complex biological environments, as well as in biomimetic models for artificial photosynthesis. Here, we consider a few biomimetic models to investigate these processes in real-time simulations based on ab initio molecular dynamics and Ehrenfest dynamics. This allows for a detailed analysis on how photon-to-charge conversion is promoted by a coupling of the electronic excitation with specific vibrational modes and with proton displacements. The ET process shows a characteristic coherence that is linked to the nuclear motion at the interface between donor and acceptor. We also show real-time evidence of PCET in a benzimidazole-phenol redox relay. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Noether charge, black hole volume, and complexity

    NASA Astrophysics Data System (ADS)

    Couch, Josiah; Fischler, Willy; Nguyen, Phuc H.

    2017-03-01

    In this paper, we study the physical significance of the thermodynamic volumes of AdS black holes using the Noether charge formalism of Iyer and Wald. After applying this formalism to study the extended thermodynamics of a few examples, we discuss how the extended thermodynamics interacts with the recent complexity = action proposal of Brown et al. (CA-duality). We, in particular, discover that their proposal for the late time rate of change of complexity has a nice decomposition in terms of thermodynamic quantities reminiscent of the Smarr relation. This decomposition strongly suggests a geometric, and via CA-duality holographic, interpretation for the thermodynamic volume of an AdS black hole. We go on to discuss the role of thermodynamics in complexity = action for a number of black hole solutions, and then point out the possibility of an alternate proposal, which we dub "complexity = volume 2.0". In this alternate proposal the complexity would be thought of as the spacetime volume of the Wheeler-DeWitt patch. Finally, we provide evidence that, in certain cases, our proposal for complexity is consistent with the Lloyd bound whereas CA-duality is not.

  16. Experimental and theoretical studies of charge transfer and deuterium ion transfer between D2O+ and C2H4

    NASA Astrophysics Data System (ADS)

    Liu, Li; Cai, Xiaohui; Li, Yue; Richards O'Grady, Elizabeth; Farrar, James M.

    2004-08-01

    The charge transfer and deuterium ion transfer reactions between D2O+ and C2H4 have been studied using the crossed beam technique at relative collision energies below one electron volt and by density functional theory (DFT) calculations. Both direct and rearrangement charge transfer processes are observed, forming C2H4+ and C2H3D+, respectively. Independent of collision energy, deuterium ion transfer accounts for approximately 20% of the reactive collisions. Between 22 and 36 % of charge transfer collisions occur with rearrangement. In both charge transfer processes, comparison of the internal energy distributions of products with the photoelectron spectrum of C2H4 shows that Franck-Condon factors determine energy disposal in these channels. DFT calculations provide evidence for transient intermediates that undergo H/D migration with rearrangement, but with minimal modification of the product energy distributions determined by long range electron transfer. The cross section for charge transfer with rearrangement is approximately 103 larger than predicted from the Rice-Ramsperger-Kassel-Marcus isomerization rate in transient complexes, suggesting a nonstatistical mechanism for H/D exchange. DFT calculations suggest that reactive trajectories for deuterium ion transfer follow a pathway in which a deuterium atom from D2O+ approaches the π-cloud of ethylene along the perpendicular bisector of the C-C bond. The product kinetic energy distributions exhibit structure consistent with vibrational motion of the D-atom in the bridged C2H4D+ product perpendicular to the C-C bond. The reaction quantitatively transforms the reaction exothermicity into internal excitation of the products, consistent with mixed energy release in which the deuterium ion is transferred in a configuration in which both the breaking and the forming bonds are extended.

  17. Heat Transfer in Complex Fluids

    SciTech Connect

    Mehrdad Massoudi

    2012-01-01

    Amongst the most important constitutive relations in Mechanics, when characterizing the behavior of complex materials, one can identify the stress tensor T, the heat flux vector q (related to heat conduction) and the radiant heating (related to the radiation term in the energy equation). Of course, the expression 'complex materials' is not new. In fact, at least since the publication of the paper by Rivlin & Ericksen (1955), who discussed fluids of complexity (Truesdell & Noll, 1992), to the recently published books (Deshpande et al., 2010), the term complex fluids refers in general to fluid-like materials whose response, namely the stress tensor, is 'non-linear' in some fashion. This non-linearity can manifest itself in variety of forms such as memory effects, yield stress, creep or relaxation, normal-stress differences, etc. The emphasis in this chapter, while focusing on the constitutive modeling of complex fluids, is on granular materials (such as coal) and non-linear fluids (such as coal-slurries). One of the main areas of interest in energy related processes, such as power plants, atomization, alternative fuels, etc., is the use of slurries, specifically coal-water or coal-oil slurries, as the primary fuel. Some studies indicate that the viscosity of coal-water mixtures depends not only on the volume fraction of solids, and the mean size and the size distribution of the coal, but also on the shear rate, since the slurry behaves as shear-rate dependent fluid. There are also studies which indicate that preheating the fuel results in better performance, and as a result of such heating, the viscosity changes. Constitutive modeling of these non-linear fluids, commonly referred to as non-Newtonian fluids, has received much attention. Most of the naturally occurring and synthetic fluids are non-linear fluids, for example, polymer melts, suspensions, blood, coal-water slurries, drilling fluids, mud, etc. It should be noted that sometimes these fluids show Newtonian

  18. The study of surface acoustic wave charge transfer device

    NASA Technical Reports Server (NTRS)

    Papanicolaou, N.; Lin, H. C.

    1978-01-01

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

  19. Coherent ultrafast charge transfer in an organic photovoltaic blend.

    PubMed

    Falke, Sarah Maria; Rozzi, Carlo Andrea; Brida, Daniele; Maiuri, Margherita; Amato, Michele; Sommer, Ephraim; De Sio, Antonietta; Rubio, Angel; Cerullo, Giulio; Molinari, Elisa; Lienau, Christoph

    2014-05-30

    Blends of conjugated polymers and fullerene derivatives are prototype systems for organic photovoltaic devices. The primary charge-generation mechanism involves a light-induced ultrafast electron transfer from the light-absorbing and electron-donating polymer to the fullerene electron acceptor. Here, we elucidate the initial quantum dynamics of this process. Experimentally, we observed coherent vibrational motion of the fullerene moiety after impulsive optical excitation of the polymer donor. Comparison with first-principle theoretical simulations evidences coherent electron transfer between donor and acceptor and oscillations of the transferred charge with a 25-femtosecond period matching that of the observed vibrational modes. Our results show that coherent vibronic coupling between electronic and nuclear degrees of freedom is of key importance in triggering charge delocalization and transfer in a noncovalently bound reference system. Copyright © 2014, American Association for the Advancement of Science.

  20. Luminescent charge-transfer platinum(II) metallacycle.

    PubMed

    Hua, Fei; Kinayyigit, Solen; Rachford, Aaron A; Shikhova, Elena A; Goeb, Sébastien; Cable, John R; Adams, Christopher J; Kirschbaum, Kristin; Pinkerton, A Alan; Castellano, Felix N

    2007-10-15

    The photophysical and electrochemical properties of a platinum(II) diimine complex bearing the bidentate diacetylide ligand tolan-2,2'-diacetylide (tda), Pt(dbbpy)(tda) [dbbpy = 4,4'-di-tert-butyl-2,2'-bipyridine] (1), are compared with two reference compounds, Pt(dbbpy)(C[triple bond]CPh)(2) (2) and Pt(dppp)tda [dppp = 1,3-bis(diphenylphosphino)propane] (3), respectively. The X-ray crystal structure of 1 is reported, which illustrates the nearly perfect square planarity exhibited by this metallacycle. Chromophore 2 possesses low-lying charge-transfer excited states analogous to 1, whereas structure 3 lacks such excited states but features a low-lying platinum-perturbed tda intraligand triplet manifold. In CH(2)Cl(2), 1 exhibits a broad emission centered at 562 nm at ambient temperature, similar to 2, but with a higher photoluminescence quantum yield and longer excited-state lifetime. In both instances, the photoluminescence is consistent with triplet-charge-transfer excited-state parentage. The rigidity imposed by the cyclic diacetylide ligand in 1 leads to a reduction in nonradiative decay, which enhances its room-temperature photophysical properties. By comparison, 3 radiates highly structured tda-localized triplet-state phosphorescence at room temperature. The 77 K emission spectrum of 1 in 4:1 EtOH/MeOH becomes structured and is quantitatively similar to that measured for 3 under the same conditions. Because the 77 K spectra are nearly identical, the emissions are assigned as (3)tda in nature, implying that the charge-transfer states are raised in energy, relative to the (3)tda levels in 1 in the low-temperature glass. Nanosecond transient absorption spectrometry and ultrafast difference spectra were determined for 1-3 in CH(2)Cl(2) and DMF at ambient temperature. In 1 and 2, the major absorption transients are consistent with the one-electron reduced complexes, corroborated by reductive spectroelectrochemical measurements performed at room temperature. As 3

  1. The role of charge-transfer states in energy transfer and dissipation within natural and artificial bacteriochlorophyll proteins.

    PubMed

    Wahadoszamen, Md; Margalit, Iris; Ara, Anjue Mane; van Grondelle, Rienk; Noy, Dror

    2014-10-24

    Understanding how specific protein environments affect the mechanisms of non-radiative energy dissipation within densely assembled chlorophylls in photosynthetic protein complexes is of great interest to the construction of bioinspired solar energy conversion devices. Mixing of charge-transfer and excitonic states in excitonically interacting chlorophylls was implicated in shortening excited states' lifetimes, but its relevance to active control of energy dissipation in natural systems is under considerable debate. Here we show that the degree of fluorescence quenching in two similar pairs of excitonically interacting bacteriochlorophyll derivatives is directly associated with increasing charge-transfer character in the excited state, and that the protein environment may control non-radiative dissipation by affecting the mixing of charge-transfer and excitonic states. The capability of local protein environments to determine the fate of excited states, and thereby to confer different functionalities to excitonically coupled dimers substantiates the dimer as the basic functional element of photosynthetic enzymes.

  2. Intramolecular energy transfer reactions in polymetallic complexes.. Progress report, 1991--1992

    SciTech Connect

    Petersen, J.

    1992-12-01

    (1) Excited-state energy transfer: The major effort was an attempt to sensitize the photoelimination of H{sub 2} from a bimetallic, metal-dihydride complex. These complexes have involved Fe, Ru, and Co complexes. (2) Excited-state electron transfer (charge separation): A series of diad and triad complexes were prepared in order to sustain charge separation in an artificial photosynthetic system.

  3. Criticality and Connectivity in Macromolecular Charge Complexation

    SciTech Connect

    Qin, Jian; de Pablo, Juan J.

    2016-11-04

    We examine the role of molecular connectivity and architecture on the complexation of ionic macromolecules (polyelectrolytes) of finite size. A unified framework is developed and applied to evaluate the electrostatic correlation free energy for point-like, rod-like, and coil-like molecules. That framework is generalized to molecules of variable fractal dimensions, including dendrimers. Analytical expressions for the free energy, correlation length, and osmotic pressure are derived, thereby enabling consideration of the effects of charge connectivity, fractal dimension, and backbone stiffness on the complexation behavior of a wide range of polyelectrolytes. Results are presented for regions in the immediate vicinity of the critical region and far from it. A transparent and explicit expression for the coexistence curve is derived in order to facilitate analysis of experimentally observed phase diagrams.

  4. Charge Transfer in Multiple Site Chemical Systems.

    DTIC Science & Technology

    2014-09-26

    transfer, II1 7 III 3+* 111 III o (dte)2ClRu (L)Ru Cllkpy) 2 -(dpte) 2 ClRu (L)Rul( py) (bpy) , and is ompetitive with excited state nonradiative ...energy, mixed-valence iscmer to the ground state, (dpte) 2ClRu II(L)Ru IICl- * Cpy)2 3+-+(pte 2 ClRuI (L)Ru ICl(tpy)2 3+, folowing nonradiative decay

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

    PubMed

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

    2016-09-14

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

  6. Nigericin-induced charge transfer across membranes.

    PubMed

    Markin, V S; Sokolov, V S; Bogulavsky, L I; Jaguzhinsky, L S

    1975-12-04

    The electric properties of the bilayer lecithin membranes have been studied in the presence of the antibiotic nigericin. When the antibiotic concentration is about 10(-7) ohm-1 cm-2. The potassium ion concentration gradient gives rise to a transmembrane potential of the order of 40 mV per 10-fold concentration gradient with the side of the higher potassium concentration negative. The transmembrane potential produced by the hydrogen ion concentration gradient is a function of the potassium ion concentration which is equal on both sides of the membrane. For low potassium ion concentrations the hydrogen potential has the expected polarity with the solution having higher concentration of protons negative. For potassium ion concentrations exceeding 0.03 M the hydrogen potential has the reverse polarity. This unexpected result cannot be accounted for in terms of the available simple hypotheses about the charge transport mechanism for nigericin in BLM. In order to account for the experimental results obtained, a theoretical approach has been developed based on the assumption that charge is transported across the membrane by nigericin dimers. The theoretical predicitons are in satisfactory agreement with the experimental results. The model also yields some predictions which may be verified in future experiments.

  7. Intramolecular Charge Transfer States in the Condensed Phase

    NASA Astrophysics Data System (ADS)

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

    2009-06-01

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

  8. Charge Transfer in Multiple Site Chemical Systems

    DTIC Science & Technology

    1992-03-01

    electrochemical reduction of films of poly- Fe(vbpy)2(CN)2 ,poly-Rh(vbpy)(COD)CI and the catalytic properties of Rh particles in the dicyano films are under...coefficient (for the substrate) within the polymeric film was made. The mechanism of catalytic oxidation of benzyl alcohol in solution and and in the polymeric...pH-Induced Intramolecular Quenching. Ligand-Bridged Complexes Containing Osmium and Ruthenium 5 In the ligand-bridged complex [( tpy )(bpy)Os(4,4’-bpy

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

    SciTech Connect

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

    2015-06-24

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

  10. Charge transfer in helium-rich supernova plasma

    NASA Technical Reports Server (NTRS)

    Swartz, Douglas A.

    1994-01-01

    Charge transfer rate coefficients are estimated using Landau-Zener and modified Demkov approximations. The coefficients, augmented by those available from the literature, are used in statistical equilibrium equations describing the state of helium-rich supernova plasma. Such a plasma may describe both Type Ib and Type Ic supernova ejecta. The hypothesis that extensive mixing of metals with helium in Type Ic supernovae may provide a catalyst for rapid charge transfer that weakens the helium line emission by altering the excitation balance is tested. It is shown that charge transfer as a mechanism for suppressing helium line emission is ineffective unless the metal abundance is comparable to or larger than the helium abundance. This result supports an earlier conclusion that Type Ic supernovae must be helium poor relative to Type Ib events.

  11. Intramolecular charge transfer effects on 3-aminobenzoic acid

    NASA Astrophysics Data System (ADS)

    Stalin, T.; Rajendiran, N.

    2006-03-01

    Effect of solvents, buffer solutions of different pH and β-cyclodextrin on the absorption and fluorescence spectra of 3-aminobenzoic acid (3ABA) have been investigated. The solid inclusion complex of 3ABA with β-CD is discussed by UV-Vis, fluorimetry, semiempirical quantum calculations (AM1), FT-IR, 1H NMR and Scanning Electron Microscope (SEM). The thermodynamic parameters (Δ H, Δ G and Δ 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 1 state. Solvent, β-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 0 and S 1 states are calculated. β-Cyclodextrin studies shows that 3ABA forms a 1:1 inclusion complex with β-CD. β-CD studies suggest COOH group present in non-polar part and amino group present in hydrophilic part of the β-CD cavity. A mechanism is proposed to explain the inclusion process.

  12. Multiple-charge transfer and trapping in DNA dimers

    NASA Astrophysics Data System (ADS)

    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.

  13. Ab initio Determination of Formation Energies and Charge Transfer Levels of Charged Ions in Water

    NASA Astrophysics Data System (ADS)

    Vatti, Anoop Kishore; Todorova, Mira; Neugebauer, Joerg

    The ability to describe the complex atomic and electronic structure of liquid water and hydrated ions on a microscopic level is a key requirement to understand and simulate electro-chemical and biological processes. Identifying theoretical concepts which enable us to achieve an accurate description in a computationally efficient way is thereby of central importance. Aiming to unravel the importance and influence of different contributions on the hydration energy of ions we perform extensive ab-initio molecular dynamics simulations for charged and neutral cations (Zn, Mg) and anions (Cl, Br, I) in water. The structural correlations and electronic properties of the studied ions are analysed and compared to experimental observations. Following an approach inspired by the defect chemistry in semiconductors and aligning the water band edges on an absolute scale allows us to benchmark the calculated formation energies, identify transition states and compare the results to experiment. Based on these results we discuss the performance of various DFT xc-functionals to predict charge transfer levels and photo-emission experiments.

  14. Charge transfer to a semi-esterified bifunctional phenol

    NASA Astrophysics Data System (ADS)

    Brede, O.; Hermann, R.; Orthner, H.

    1996-03-01

    The charge transfer from solvent radical cations of n-butyl chloride and cyclohexane to 2-butyl-6(3'-t-butyl-2'-hydroxy-5'-methylbenzyl)-4-methyl-phenylacrylate (GM) yields in the first step phenoxyl radicals as well as acrylate radical cations of this semi-acrylated bifunctional phenol. Subsequently an intramolecular charge transfer from the acrylate radical cation to the phenol group takes place. Because of the instability of phenol radical cations, under our experimental conditions (nanosecond pulse radiolysis, non-polar solvents, room temperature) phenoxyl radicals are the only observable products of phenol ionization.

  15. Transfer ionization in collisions with a fast highly charged ion.

    PubMed

    Voitkiv, A B

    2013-07-26

    Transfer ionization in fast collisions between a bare ion and an atom, in which one of the atomic electrons is captured by the ion whereas another one is emitted, crucially depends on dynamic electron-electron correlations. We show that in collisions with a highly charged ion a strong field of the ion has a very profound effect on the correlated channels of transfer ionization. In particular, this field weakens (strongly suppresses) electron emission into the direction opposite (perpendicular) to the motion of the ion. Instead, electron emission is redirected into those parts of the momentum space which are very weakly populated in fast collisions with low charged ions.

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

    NASA Astrophysics Data System (ADS)

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

    2017-02-01

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

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

    PubMed Central

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

    2017-01-01

    We investigated the mechanism of intramolecular charge transfer and the following radiationless dynamics of the excited states of 1-aminoanthraquinone using steady state and time-resolved absorption spectroscopy combined with quantum chemical calculations. Following photoexcitation with 460 nm, conformational relaxation via twisting of the amino group, charge transfer and the intersystem crossing (ISC) processes have been established to be the major relaxation pathways responsible for the ultrafast nonradiative of the excited S1 state. Intramolecular proton transfer, which could be induced by intramolecular hydrogen bonding is inspected and excluded. Time-dependent density functional theory (TDDFT) calculations reveal the change of the dipole moments of the S0 and S1 states along the twisted coordinate of the amino group, indicating the mechanism of twisted intra-molecular charge transfer (TICT). The timescale of TICT is measured to be 5 ps due to the conformational relaxation and a barrier on the S1 potential surface. The ISC from the S1 state to the triplet manifold is a main deactivation pathway with the decay time of 28 ps. Our results observed here have yield a physically intuitive and complete picture of the photoinduced charge transfer and radiationless dynamics in anthraquinone pharmaceutial products. PMID:28233835

  18. [Dynamics of charge transfer along an oligonucleotide at finite temperature].

    PubMed

    Lakhno, V D; Fialko, N S

    2004-01-01

    The quantum-statistical approach was used to describe the charge transfer in nucleotide sequences. The results of numerical modeling for hole transfer in the GTTGGG sequence with background temperature noise are given. It was shown that, since guanine has an oxidation potential lower than thymine, the hole created at the G donor in this sequence passes through the thymine barrier into the guanine triplet (acceptor) at a time of approximately 10 ps at a temperature of 37 degrees C.

  19. Introduction to charge transfer device discrete time processing

    NASA Technical Reports Server (NTRS)

    Brodersen, R. W.

    1976-01-01

    This tutorial paper reviews some of the advantages and disadvantages of a discrete time representation of a signal. Also reviewed are some of the recent theoretical advances in digital signal processing which can be implemented by the use of charge transfer signal processing devices. In particular, the design and implementation of transversal filters and spectrum analyzers will be discussed.

  20. Charge transfer devices. Citations from the NTIS data base

    NASA Astrophysics Data System (ADS)

    Reed, W. E.

    1980-04-01

    The technology, design, fabrication, and applications of charge transfer devices are presented in the cited research reports. Applications include imaging, signal processing, detectors, filters, amplifiers, and memory devices. This updated bibliography contains 107 abstracts, all of which are new entries to the previous edition.

  1. Charge-Transfer Interactions in Organic Functional Materials

    PubMed Central

    Lin, Hsin-Chieh; Jin, Bih-Yaw

    2010-01-01

    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. PMID:28883326

  2. Extending transfer-matrix studies of charge transport in dsDNA: diagonal ladder model

    NASA Astrophysics Data System (ADS)

    Wells, Stephen; Roemer, Rudoph

    2008-03-01

    The π-stacking of aromatic bases along the axis of the DNA double helix suggests that DNA should be capable of supporting electron transport. This possibility has been investigated by a variety of experimental methods, including charge-transfer between intercalated dye molecules and direct measurement of conductivity in DNA molecules bridging two electrodes. In order to explore either the biological or nanotechnological significance of charge transport in DNA, we need theoretical models capable of predicting the influence of DNA sequence and structure on its charge transport properties. Transfer matrix methods have been used in conjunction with a ladder model of dsDNA (incorporating charge transfer between adjacent bases along a strand, and between hydrogen-bonded base pairs) to predict different transport properties for random, repetitive, or coding DNA sequences. It has been suggested that DNA charge transport may be involved in cellular mechanisms to detect and repair damage to DNA strands. We present extensions to the ladder model to allow for, firstly, charge transfer ``diagonally'' (from a base on a 5' strand to an adjacent base on a 3' strand, for example), and secondly, variations in hopping amplitudes due to bending of the helix (for example, in wrapping round a histone complex). Hence we take into account the extent of the electronic states and the geometry of the DNA strand in our modeling.

  3. Long-lived photoinduced charge separation for solar cell applications in supramolecular complexes of multi-metalloporphyrins and fullerenes.

    PubMed

    Fukuzumi, Shunichi; Ohkubo, Kei

    2013-12-07

    Monomers, dimers, trimers, dendrimers and oligomers of metalloporphyrins form supramolecular complexes with fullerene derivatives via electrostatic interactions, π-π interactions and coordination bonds. Photoexcitation of the supramolecular complexes resulted in photoinduced electron transfer from the porphyrin moiety to the fullerene moiety to produce the charge-separated states as revealed by laser flash photolysis measurements. The rate constants of photoinduced charge separation and charge recombination in supramolecular complexes of multi-metalloporphyrins and fullerenes were also determined by laser flash photolysis measurements and the results depending on the number of porphyrins in the supramolecular complexes are discussed in terms of efficiency of photoinduced energy transfer and charge separation as well as the lifetimes of charge-separated states. The photoelectrochemical performances of solar cells composed of supramolecular complexes of monomers, dimers, dendrimers and oligomers of metalloporphyrins with fullerenes are compared in relation to the rate constants of photoinduced charge separation and charge recombination.

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

    DOE PAGES

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

    2016-12-19

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

  5. Effect of Aperiodicity on the Charge Transfer Through DNA Molecules

    NASA Astrophysics Data System (ADS)

    Ghosh, Angsula; Chaudhuri, Puspitapallab

    The effect of aperiodicity on the charge transfer process through DNA molecules is investigated using a tight-binding model. Single-stranded aperiodic Fibonacci polyGC and polyAT sequences along with aperiodic Rudin-Shapiro poly(GCAT) sequences are used in the study. Based on the tight-binding model, molecular orbital calculations of the DNA chains are performed and ionization potentials compared, as this might be relevant to understanding the charge transfer process. Charges migrate through the sequences in a multistep hopping process. Results for current conduction through aperiodic sequences are compared with those for the corresponding periodic sequences. We find that dinucleotide aperiodic Fibonacci sequences decrease the current while tetranucleotide aperiodic Rudin-Shapiro sequences increase the current when compared with the corresponding periodic sequences. The conductance in all cases decays exponentially as the sequence length increases.

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

    PubMed Central

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

    2017-01-01

    The detection of furfural in transformer oil through surface enhanced Raman spectroscopy (SERS) is one of the most promising online monitoring techniques in the process of transformer aging. In this work, the Raman of individual furfural molecules and SERS of furfural-Mx (M = Ag, Au, Cu) complexes are investigated through density functional theory (DFT). In the Raman spectrum of individual furfural molecules, the vibration mode of each Raman peak is figured out, and the deviation from experimental data is analyzed by surface charge distribution. In the SERS of furfural-Mx complexes, the influence of atom number and species on SERS chemical enhancement factors (EFs) are studied, and are further analyzed by charge transfer effect. Our studies strengthen the understanding of charge transfer effect in the SERS of furfural molecules, which is important in the online monitoring of the transformer aging process through SERS. PMID:28767053

  7. Graphene nonvolatile memory prototype based on charge-transfer mechanism

    NASA Astrophysics Data System (ADS)

    Lv, Hongming; Wu, Huaqiang; Huang, Can; Wang, Yuda; Qian, He

    2014-04-01

    A graphene nonvolatile memory (GNVM) prototype based on charge transfer between the graphene layer and the NH2(CH2)3Si(OEt)3 (APTES) self-assembled monolayer (SAM) is demonstrated. Graphene was transferred to an APTES-SAM-engineered SiO2 substrate and patterned into bottom-gate transistors. Owing to the charge trapping/detrapping property of the nitrogen atoms in APTES, a significant and reproducible transfer curve hysteresis is observed. Memory performance metrics, including retention and endurance, are reported. Comparisons between vacuum and ambient environment test results indicate air absorbates’ detrimental effect. Loss of nonvolatile storage is explained on the basis of a two-layer tunneling junction model, which sheds light on further device improvement through aminosilane molecule structure optimization.

  8. Active pixel sensor with intra-pixel charge transfer

    NASA Technical Reports Server (NTRS)

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

    2004-01-01

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

  9. Active pixel sensor with intra-pixel charge transfer

    NASA Technical Reports Server (NTRS)

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

    1995-01-01

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

  10. Active pixel sensor with intra-pixel charge transfer

    NASA Technical Reports Server (NTRS)

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

    2003-01-01

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

  11. WEST (FRONT) OF FURNACE COMPLEX, INCLUDING STACKS, WITH CHARGING BRIDGE ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    WEST (FRONT) OF FURNACE COMPLEX, INCLUDING STACKS, WITH CHARGING BRIDGE AND TRESSLE, LOOKING SOUTHEAST. - Tannehill Furnace, 12632 Confederate Parkway, Tannehill Historical State Park, Bucksville, Tuscaloosa County, AL

  12. Charge-transfer crystallites as molecular electrical dopants

    PubMed Central

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

    2015-01-01

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

  13. Theoretical Evidence for Multiple Charge Transfer Pathways in Bacteriorhodopsin.

    PubMed

    Lee, Choongkeun; Mertz, Blake

    2016-04-12

    The development of molecular-scale junctions utilizing biomolecules is a challenging field that requires intimate knowledge of the relationship between molecular structure and conductance characteristics. One of the key parameters to understanding conductance efficiency is the charge mobility, which strongly influences the response time of electronic devices. The charge mobility of bacteriorhodopsin (bR), a membrane protein that has been studied experimentally in detail, was theoretically investigated using extended Marcus-Hush theory. Charge mobilities of 1.3 × 10(-2) and 9.7 × 10(-4) cm(2)/(V s) for hole and electron transfer, respectively, were determined. The computed electron mobility is comparable to experimentally measured values (9 × 10(-4) cm(2)/(V s)). Interestingly, the pathways for hole and electron hopping were very distinct from each other, utilizing different transmembrane helices to traverse the protein. In particular, only the electron transfer pathway involved the retinal chromophore, indicating that the efficiency of charge transfer is directly affected by the tertiary arrangement of proteins. Our results provide a template for obtaining the molecular and electronic-level details that can reveal fundamental insights into experimental studies on protein electron transport and inform efficient design of biomolecular-based junctions on the nanoscale.

  14. Spectrophotometric, Fourier transform infrared spectroscopic and theoretical studies of the charge-transfer complexes between methyldopa [(S)-2 amino-3-(3,4-dihydroxyphenyl)-2-methyl propanoic acid] and the acceptors (chloranilic acid, o-chloranil and dichlorodicyanobenzoquinone) in acetonitrile and their thermodynamic properties

    NASA Astrophysics Data System (ADS)

    Sharma, K.; Sharma, S. P.; Lahiri, S. C.

    Methyldopa is a much used antihypertensive drug. It is the subject matter of study mostly for the determination and estimation of methyldopa in pharmaceutical properties. These considerations led us to study the charge-transfer interactions between methyldopa, a centrally acting antihypertensive agent of limited use with the known acceptors like o-chloranil (o-ClN), chloranilic acid (ClA) and dichlorodicyanobenzoquinone (DDQ). Methyldopa (MDP) formed beautifully colored complexes (having absorption maxima at 581 nm and 368 nm; 519 nm; 583.5 nm, 547 nm and 346 nm, respectively) with the acceptors mentioned before. The physico-chemical properties of the complexes were studied using UV-visible spectrophotometry and FTIR measurements. The composition, the accurate association constants and thermodynamics of the complexes were determined spectrophotometrically. Attempts were made to interpret the thermodynamics of complexes in terms of IDV, EAV and hνCT. Solid CT complexes between MDP + o-ClN, MDP + ClA and MDP + DDQ were prepared and FTIR spectra of the complexes were studied. The energies hνCT of the charge-transfer complexes and vertical ionization potential IDV of methyldopa were compared with the theoretical values of hνCT obtained from HOMO and LUMO of the donors and acceptors calculated using Density Function Theory utilizing different basis sets. The agreement between the results can be regarded to be reasonable. Oscillator strengths and dipole strengths of the complexes were determined theoretically and experimentally and the limitations of the calculations were outlined.

  15. Multistep hopping and extracellular charge transfer in microbial redox chains.

    PubMed

    Pirbadian, Sahand; El-Naggar, Mohamed Y

    2012-10-28

    Dissimilatory metal-reducing bacteria are microorganisms that gain energy by transferring respiratory electrons to extracellular solid-phase electron acceptors. In addition to its importance for physiology and natural environmental processes, this form of metabolism is being investigated for energy conversion and fuel production in bioelectrochemical systems, where microbes are used as biocatalysts at electrodes. One proposed strategy to accomplish this extracellular charge transfer involves forming a conductive pathway to electrodes by incorporating redox components on outer cell membranes and along extracellular appendages known as microbial nanowires within biofilms. To describe extracellular charge transfer in microbial redox chains, we employed a model based on incoherent hopping between sites in the chain and an interfacial treatment of electrochemical interactions with the surrounding electrodes. Based on this model, we calculated the current-voltage (I-V) characteristics and found the results to be in good agreement with I-V measurements across and along individual microbial nanowires produced by the bacterium Shewanella oneidensis MR-1. Based on our analysis, we propose that multistep hopping in redox chains constitutes a viable strategy for extracellular charge transfer in microbial biofilms.

  16. Charge transfer induced polarity switching in carbon nanotube transistors.

    PubMed

    Klinke, Christian; Chen, Jia; Afzali, Ali; Avouris, Phaedon

    2005-03-01

    We probed the charge transfer interaction between the amine-containing molecules hydrazine, polyaniline, and aminobutyl phosphonic acid and carbon nanotube field effect transistors (CNTFETs). We successfully converted p-type CNTFETs to n-type and drastically improved the device performance in both the ON- and OFF-transistor states, utilizing hydrazine as dopant. We effectively switched the transistor polarity between p- and n- type by accessing different oxidation states of polyaniline. We also demonstrated the flexibility of modulating the threshold voltage (Vth) of a CNTFET by engineering various charge-accepting and -donating groups in the same molecule.

  17. What is the "best" atomic charge model to describe through-space charge-transfer excitations?

    PubMed

    Jacquemin, Denis; Le Bahers, Tangui; Adamo, Carlo; Ciofini, Ilaria

    2012-04-28

    We investigate the efficiency of several partial atomic charge models (Mulliken, Hirshfeld, Bader, Natural, Merz-Kollman and ChelpG) for investigating the through-space charge-transfer in push-pull organic compounds with Time-Dependent Density Functional Theory approaches. The results of these models are compared to benchmark values obtained by determining the difference of total densities between the ground and excited states. Both model push-pull oligomers and two classes of "real-life" organic dyes (indoline and diketopyrrolopyrrole) used as sensitisers in solar cell applications have been considered. Though the difference of dipole moments between the ground and excited states is reproduced by most approaches, no atomic charge model is fully satisfactory for reproducing the distance and amount of charge transferred that are provided by the density picture. Overall, the partitioning schemes fitting the electrostatic potential (e.g. Merz-Kollman) stand as the most consistent compromises in the framework of simulating through-space charge-transfer, whereas the other models tend to yield qualitatively inconsistent values.

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

    NASA Technical Reports Server (NTRS)

    Kwong, Victor H. S.

    2003-01-01

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

  19. Modelling flavoenzymatic charge transfer events: development of catalytic indole deuteration strategies.

    PubMed

    Murray, Alexander T; Challinor, Jonathan D; Gulácsy, Christina E; Lujan, Cristina; Hatcher, Lauren E; Pudney, Christopher R; Raithby, Paul R; John, Matthew P; Carbery, David R

    2016-04-12

    The formation and chemistry of flavin-indole charge transfer (CT) complexes has been studied using a model cationic flavin. The ability to form a CT complex is sensitive to indole structure as gauged by spectroscopic, kinetics and crystallographic studies. Single crystals of sufficient quality of a flavin-indole CT complex, suitable for X-ray diffraction, have been grown, allowing solid-state structural analysis. When CT complex formation is conducted in d4-methanol, an efficient and synthetically useful C-3 indole deuteration is observed.

  20. Raman Spectroscopy of Charge Transfer Interactions Between Single Wall Carbon Nanotubes and [FeFe] Hydrogenase

    SciTech Connect

    Blackburn, J. L. Svedruzic, D.; McDonald, T. J.; Kim, Y. H.; King, P. W.; Heben, M. J.

    2008-01-01

    We report a Raman spectroscopy study of charge transfer interactions in complexes formed by single-walled carbon nanotubes (SWNTs) and [FeFe] hydrogenase I (CaHydI) from Clostridium acetobutylicum. The choice of Raman excitation wavelength and sample preparation conditions allows differences to be observed for complexes involving metallic (m) and semiconducting (s) species. Adsorbed CaHydI can reversibly inject electronic charge into the LUMOs of s-SWNTs, while charge can be injected and removed from m-SWNTs at lower potentials just above the Fermi energy. Time-dependent enzymatic assays demonstrated that the reduced and oxidized forms of CaHydI are deactivated by oxygen, but at rates that varied by an order of magnitude. The time evolution of the oxidative decay of the CaHydI activity reveals different time constants when complexed with m-SWNTs and s-SWNTs. The correlation of enzymatic assays with time-dependent Raman spectroscopy provides a novel method by which the charge transfer interactions may be investigated in the various SWNT-CaHydI complexes. Surprisingly, an oxidized form of CaHydI is apparently more resistant to oxygen deactivation when complexed to m-SWNTs rather than s-SWNTs.

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

    NASA Astrophysics Data System (ADS)

    Bohr, Henrik G.; Malik, F. Bary

    2013-11-01

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

  2. Charge transfer and interface properties in inorganic superstructures and composites

    NASA Astrophysics Data System (ADS)

    Flyagina, I. S.; Petrov, A. A.; Pervov, V. S.

    2016-06-01

    The processes of charge transfer and electronic reconstruction at interfaces of inorganic superstructures and composites have not yet been adequately investigated. This review integrates and analyzes the results of theoretical and experimental studies of structural and electronic effects at interfaces of metal oxide or chalcogenide superstructures and composites. Charge transfer and, hence, change in interface properties compared to the properties of substructures are shown to be determined by the preparation method of composites and chemical nature of the superstructures, incommensurability of structural parameters and valence states of the constituent metals. The changes are maximal for nanoheterostructures, and the degree of change is related to electronic conductivity of substructures. The macroscopic properties of the composite materials depend on the amount of interfaces in their bulk. The bibliography includes 66 references.

  3. Charge transfer magnetoexciton formation at vertically coupled quantum dots

    PubMed Central

    2012-01-01

    A theoretical investigation is presented on the properties of charge transfer excitons at vertically coupled semiconductor quantum dots in the presence of electric and magnetic fields directed along the growth axis. Such excitons should have two interesting characteristics: an extremely long lifetime and a permanent dipole moment. We show that wave functions and the low-lying energies of charge transfer exciton can be found exactly for a special morphology of quantum dots that provides a parabolic confinement inside the layers. To take into account a difference between confinement potentials of an actual structure and of our exactly solvable model, we use the Galerkin method. The density of energy states is calculated for different InAs/GaAs quantum dots’ dimensions, the separation between layers, and the strength of the electric and magnetic fields. A possibility of a formation of a giant dipolar momentum under external electric field is predicted. PMID:23092373

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

    PubMed

    Pavanello, Michele; Neugebauer, Johannes

    2011-12-21

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

  5. Raman scattering from molecular conduction junctions: Charge transfer mechanism

    NASA Astrophysics Data System (ADS)

    Oren, Michal; Galperin, Michael; Nitzan, Abraham

    2012-03-01

    We present a model for the charge transfer contribution to surface-enhanced Raman spectroscopy (SERS) in a molecular junction. The model is a generalization of the equilibrium scheme for SERS of a molecule adsorbed on a metal surface [B. N. J. Persson. Chem. Phys. Lett.CHPLBC0009-261410.1016/0009-2614(81)85441-3 82, 561 (1981)]. We extend the same physical consideration to a nonequilibrium situation in a biased molecular junction and to nonzero temperatures. Two approaches are considered and compared: a semiclassical approach appropriate for nonresonance Raman scattering, and a quantum approach based on the nonequilibrium Green's function method. Nonequilibrium effects on this contribution to SERS are demonstrated with numerical examples. It is shown that the semiclassical approach provides an excellent approximation to the full quantum calculation as long as the molecular electronic state is outside the Fermi window, that is, as long as the field-induced charge transfer is small.

  6. Exciton strings in an organic charge-transfer crystal

    NASA Astrophysics Data System (ADS)

    Kuwata-Gonokami, M.; Peyghambarian, N.; Meissner, K.; Fluegel, B.; Sato, Y.; Ema, K.; Shimano, R.; Mazumdar, S.; Guo, F.; Tokihiro, T.; Ezaki, H.; Hanamura, E.

    1994-01-01

    COLLECTIVE excitations resulting from many-body Coulomb interactions have been studied extensively in the solid state1: for example, the exchange interaction between the electrons in two excitons (bound electron-hole pairs) can bind the excitons together, forming a biexciton. At the other extreme, if the number of excitons is sufficiently large (~106), they can condense into a degenerate 'liquid' phase known as an electron-hole drop. But in conventional semiconductors, intermediate bound states, consisting of more than two excitons, are not formed. We show here, both theoretically and experimentally, that bound states of multiple excitons can form in the organic charge-transfer solid anthracene-(pyromellitic acid dianhydride). Coulomb interactions along the one-dimensional stacks of this material can stabilize trains of several charge-transfer excitons, and we refer to the resulting collective excitations as exciton strings.

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

    NASA Astrophysics Data System (ADS)

    Pavanello, Michele; Neugebauer, Johannes

    2011-12-01

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

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

    SciTech Connect

    Pavanello, Michele; Neugebauer, Johannes

    2011-12-21

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

  9. Charge transfer transitions within the octahedral uranate group

    NASA Astrophysics Data System (ADS)

    Bleijenberg, K. C.

    1980-07-01

    In this paper the excitation spectra of the luminescence of the octahedral uranate group (UO6-6) are presented for various uranium-doped compounds. The excitation bands have been assigned using the results of theoretical and experimental investigations into the spectroscopic properties of uranium hexafluoride which is isoelectronic with the octahedral uranate group. Charge transfer transitions from orbitals having mainly oxygen 2p character to orbitals having mainly uranium 5f charcter have been observed in the region 2.24-˜4 eV. Charge transfer transitions to orbitals having mainly uranium 6d character have been observed at 4.4 eV and at 5.4 eV.

  10. Negative ion-uranium hexafluoride charge transfer reactions

    NASA Astrophysics Data System (ADS)

    Streit, Gerald E.; Newton, T. W.

    1980-10-01

    The flowing afterglow technique has been used to study the process of charge transfer from selected negative ions (F-, Cl-, Br-, I-, SF6-) to UF6. The sole ionic product in all cases was observed to be UF6-. Data analysis was complicated by an unexpected coupling of chemical and diffusive ion loss processes when UF6- product ions were present. The rate coefficients for the charge transfer processes are (k in 10-9 cm3 molecule-1 s-1) F-, 1.3; Cl-, 1.1; Br-, 0.93; I-, 0.77; and SF6-, 0.69. The rate constants agree quite well with the classical Langevin predictions.

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

    PubMed

    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.

  12. Charge-assisted halogen bonding: donor-acceptor complexes with variable ionicity.

    PubMed

    Lieffrig, Julien; Jeannin, Olivier; Frąckowiak, Arkadiusz; Olejniczak, Iwona; Świetlik, Roman; Dahaoui, Slimane; Aubert, Emmanuel; Espinosa, Enrique; Auban-Senzier, Pascale; Fourmigué, Marc

    2013-10-25

    Charge-assisted halogen bonding is unambiguously revealed from structural and electronic investigations of a series of isostructural charge-transfer complexes derived from iodinated tetrathiafulvalene and tetracyanoquinodimethane derivatives, (EDT-TTFI2)2(TCNQF(n)), n=0-2, which exhibit variable degrees of ionicity. The iodinated tetrathiafulvalene derivative, EDT-TTFI2, associates with tetracyanoquinodimethane (TCNQ) and its derivatives of increasing reduction potential (TCNQF, TCNQF2) through highly directional C-I⋅⋅⋅N≡C halogen-bond interactions. With the less oxidizing TCNQ acceptor, a neutral and insulating charge-transfer complex is isolated whereas with the more oxidizing TCNQF2 acceptor, an ionic, highly conducting charge-transfer salt is found, both of 2:1 stoichiometry and isostructural with the intermediate TCNQF complex, in which a neutral-ionic conversion takes place upon cooling. A correlation between the degree of charge transfer and the C-I⋅⋅⋅N≡C halogen-bond strength is established from the comparison of the structures of the three isostructural complexes at temperatures from 300 to 20 K, thus demonstrating the importance of electrostatics in the halogen-bonding interaction. The neutral-ionic conversion in (EDT-TTFI2)2(TCNQF) is further investigated through the temperature dependence of its magnetic susceptibility and the stretching modes of the C≡N groups. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. The Dynamics of Resonant Charge Transfer in Hyperthermal Energy Ion-Surface Collisions

    NASA Astrophysics Data System (ADS)

    Behringer, Ernest Robert

    I have studied the dynamics of resonant charge transfer in hyperthermal energy collisions of positively charged alkali ions with clean and alkali-covered Cu(001) surfaces. Li^+ ions incident on these surfaces may scatter into a variety of directions with different energies and in different charge states. To characterize the scattering from these surfaces, I have measured the in-plane energy and angular distributions of Li^+ scattered from the clean Cu(001) surface for incident energies of 400 and 100 eV and have reproduced these distributions with classical trajectory simulations which make use of a model ion-surface potential constructed from a sum of Hartree-Fock pair potentials and a long-ranged attractive potential. It is found that the scattering of lithium is more complex than for the other alkalis due to its small size, and that inelastic losses are appreciable for this system at the incident energies studies. The measurements of the scattering distractions provide useful information for the analysis of the charge transfer experiments. I have studied the dynamics of charge transfer by measuring the work function dependence of the absolute yields of different charge states and of the relative yields of excited states in the scattered flux that results when hyperthermal energy Li^+ ions impinge on clean and alkali-covered Cu(001). The data are compared to the predictions of a many-body charge transfer theory and it is found that all of the qualitative trends in the data are reproduced. Examination of the theoretical predictions shows that the dynamics of the charge transfer are complex and depend on the energies and lifetimes of all of the atomic states, even if these states are not found in the scattered flux. The theory also indicates that the dynamics depends on the relationship between the time scales set by the atomic state lifetimes and the velocity of the scattered particle, and predicts that most of the charge transferred from the mental to the atom is

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

    NASA Technical Reports Server (NTRS)

    Townsend, L. W.; Wilson, J. W.; Khan, F.; Khandelwal, G. S.

    1991-01-01

    Relativistic heavy ion charge-exchange reactions yield fragments (Delta-Z = + 1) whose longitudinal momentum distributions are downshifted by larger values than those associated with the remaining fragments (Delta-Z = 1, -2,...). Kinematics alone cannot account for the observed downshifts; therefore, an additional contribution from collision dynamics must be included. In this work, an optical model description of collision momentum transfer is used to estimate the additional dynamical momentum downshift. Good agreement between theoretical estimates and experimental data is obtained.

  15. Charge-Transfer Interactions between Transition Metal Hexafluorides and Xenon

    DTIC Science & Technology

    1977-10-01

    HEXAFLUORIDES AND XENON’. by J. D./Webb M E. R./Bernstein\\ Prepared for Publication in the Journal of the American Chemical Society DTIE Department of...Metal Hexafluorides ar. Xenon" " 6. PERFORMIKG ORG REPk)RT NUMODE . CONTRACT OR GNANT NUMBLR(e) J. D. Webb and E. R. Bernstein N00014-75-C-1179 9...neceoswy and Idenifil by block numbet) charge transfer electron affinities Transitio Metal Hexafluorides Xencn electronegativities 4,AGSTRACT Coninue an

  16. Interfacial Charge Transfer States in Condensed Phase Systems

    NASA Astrophysics Data System (ADS)

    Vandewal, Koen

    2016-05-01

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

  17. Crystal structure of the charge-transfer complex 2-(1,2,3,4-tetra-hydro-naph-thal-en-1-yl-idene)hydrazinecarbo-thio-amide-pyrazine-2,3,5,6-tetra-carbo-nitrile (2/1).

    PubMed

    Beck, Johannes; Daniels, Jörg; Krieger-Beck, Petra; Dittmann, Gertrud; de Oliveira, Adriano Bof

    2014-10-01

    The reaction of 2-(1,2,3,4-tetra-hydro-napthalen-1-yl-idene)hydrazinecarbo-thio-amide (TTSC) with pyrazine-2,3,5,6-tetra-carbo-nitrile (tetra-cyano-pyrazine, TCNP) yields the title 2:1 charge-transfer adduct, 2C11H12N3S·C6N8. The complete TCNP mol-ecule is generated by a crystallographic inversion centre and the non-aromatic ring in the TTSC mol-ecule adopts an envelope conformation with a methyl-ene C atom as the flap. In the crystal, the thio-semicarbazone mol-ecules are connected through inversion-related pairs of N-H⋯S inter-actions, building a polymeric chain along the b-axis direction. The TCNP mol-ecules are embedded in the structure, forming TTSC-TCNP-TTSC stacks with the aromatic rings of TTSC and the mol-ecular plane of TCNP in a parallel arrangement [centroid-centroid distance = 3.5558 (14) Å]. Charge-transfer (CT) via π-stacking is indicated by a CT band around 550 cm(-1) in the single-crystal absorption spectrum.

  18. Charge transfer plasmons: Recent theoretical and experimental developments

    NASA Astrophysics Data System (ADS)

    Koya, Alemayehu Nana; Lin, Jingquan

    2017-06-01

    The unique property of a charge transfer plasmon (CTP) that emerges in conductively bridged plasmonic nanoparticles makes linked nanosystems suitable candidates for building artificial molecules, nanomotors, sensors, and other optoelectronic devices. In this focused review, we present recent theoretical and experimental developments in fundamentals and applications of CTPs in conductively coupled metallic nanoparticles of various sizes and shapes. The underlying physics of charge transfer in linked nanoparticles with nanometer- and atomic-scale inter-particle gap is described from both classical and quantum mechanical perspectives. In addition, we present a detailed discussion of mechanisms of controlling charge transfer and tuning the corresponding CTP spectra in bridged nanoparticles as functions of junction conductance and nanoparticle parameters. Furthermore, the active control of reversible switching between capacitive and conductive coupling in plasmonic nanoshell particles and dynamic evolution of related plasmon modes are emphasized. Finally, after highlighting the implication of the CTP resonance shift for surface-based sensing applications, we end up with the current challenges and future outlooks of the topic that need to be addressed.

  19. Accumulative electron transfer: multiple charge separation in artificial photosynthesis.

    PubMed

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

    2012-01-01

    To achieve artificial photosynthesis it is necessary to couple the single-electron event of photoinduced charge separation with the multi-electron reactions of fuel formation and water splitting. Therefore, several rounds of light-induced charge separation are required to accumulate enough redox equivalents at the catalytic sites for the target chemistry to occur, without any sacrificial donors or acceptors other than the catalytic substrates. Herein, we discuss the challenges of such accumulative electron transfer in molecular systems. We present a series of closely related systems base on a Ru(II)-polypyridine photosensitizer with appended triaryl-amine or oligo-triaryl-amine donors, linked to nanoporous TiO2 as the acceptor. One of the systems, based on dye 4, shows efficient accumulative electron transfer in high overall yield resulting in the formation of a two-electron charge-separated state upon successive excitation by two photons. In contrast, the other systems do not show accumulative electron transfer because of different competing reactions. This illustrates the difficulties in designing successful systems for this still largely unexplored type of reaction scheme.

  20. Energy and charge transfer in nanoscale hybrid materials.

    PubMed

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

    2015-06-01

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

  1. Ultrafast Charge Recombination Dynamics in Ternary Electron Donor-Acceptor Complexes: (Benzene)2-Tetracyanoethylene Complexes.

    PubMed

    Chiu, Chih-Chung; Hung, Chih-Chang; Cheng, Po-Yuan

    2016-12-08

    The charge-transfer (CT) state relaxation dynamics of the binary (1:1) and ternary (2:1) benzene/tetracyanoethylene (BZ/TCNE) complexes are reported. Steady-state and ultrafast time-resolved broadband fluorescence (TRFL) spectra of TCNE dissolved in a series of BZ/CCl4 mixed solvents are measured to elucidate the spectroscopic properties of the BZ/TCNE complexes and their CT-state relaxation dynamics. Both steady-state and TRFL spectra exhibit marked BZ concentration dependences, which can be attributed to the formation of two types of 2:1 complexes in the ground and excited states. By combining with the density functional theory (DFT) calculations, it was concluded that the BZ concentration dependence of the absorption spectra is mainly due to the formation and excitation of the sandwich-type 2:1 ternary complexes, whereas the changes in fluorescence spectra at high BZ concentrations are due to the formation of the asymmetric-type 2:1 ternary complex CT1 state. A unified mechanism involving both direct excitation and secondary formation of the 2:1 complexes CT states are proposed to account for the observations. The equilibrium charge recombination (CR) time constant of the 1:1 CT1 state is determined to be ∼150 ps in CCl4, whereas that of the 2:1 DDA-type CT1 state becomes ∼70 ps in 10% BZ/CCl4 and ∼34 ps in pure BZ. The CR rates and the CT1-S0 energy gap of these complexes in different solvents exhibit a correlation conforming to the Marcus inverted region. It is concluded that partial charge resonance occurring between the two adjacent BZs in the asymmetric-type 2:1 CT1-state reduces the CR reaction exothermicity and increases the CR rate.

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

    NASA Astrophysics Data System (ADS)

    Vandewal, Koen; Albrecht, Steve; Hoke, Eric T.; Graham, Kenneth R.; Widmer, Johannes; Douglas, Jessica D.; Schubert, Marcel; Mateker, William R.; Bloking, Jason T.; Burkhard, George F.; Sellinger, Alan; Fréchet, Jean M. J.; Amassian, Aram; Riede, Moritz K.; McGehee, Michael D.; Neher, Dieter; Salleo, Alberto

    2014-01-01

    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.

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

    PubMed

    Vandewal, Koen; Albrecht, Steve; Hoke, Eric T; Graham, Kenneth R; Widmer, Johannes; Douglas, Jessica D; Schubert, Marcel; Mateker, William R; Bloking, Jason T; Burkhard, George F; Sellinger, Alan; Fréchet, Jean M J; Amassian, Aram; Riede, Moritz K; McGehee, Michael D; Neher, Dieter; Salleo, Alberto

    2014-01-01

    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.

  4. Ground and excited state intramolecular proton transfer controlled intramolecular charge separation and recombination: A new type of charge and proton transfer reaction

    NASA Astrophysics Data System (ADS)

    Nie, Daobo; Bian, Zuqiang; Yu, Anchi; Chen, Zhuqi; Liu, Zhiwei; Huang, Chunhui

    2008-06-01

    A novel β-diketone 1-(4-(9-carbazol)phenyl)-3-phenyl-1,3-propanedione (CDBM) has been synthesized. When excited at 380 nm, this molecule shows single fluorescence. However, when excited at 338 nm, it shows dual fluorescence. A Al 3+ complex Al(CDBM) 3 has been synthesized to investigate the dual fluorescence of CDBM. It is found that this complex shows single fluorescence under all excitation. This result indicated that the dual fluorescence of CDBM may relate to the intramolecular proton transfer reaction. Based on the experimental and theoretical studies of CDBM, N-(4-cyanophenyl)carbazole (CBN) and Al(CDBM) 3, a "ground and excited state intramolecular proton transfer controlled intramolecular charge separation and recombination" mechanism is proposed to explain the unusual excitation-dependent dual fluorescence of CDBM.

  5. Quantum information transfer between topological and conventional charge qubits

    NASA Astrophysics Data System (ADS)

    Jun, Li; Yan, Zou

    2016-02-01

    We propose a scheme to realize coherent quantum information transfer between topological and conventional charge qubits. We first consider a hybrid system where a quantum dot (QD) is tunnel-coupled to a semiconductor Majorana-hosted nanowire (MNW) via using gated control as a switch, the information encoded in the superposition state of electron empty and occupied state can be transferred to each other through choosing the proper interaction time to make measurements. Then we consider another system including a double QDs and a pair of parallel MNWs, it is shown that the entanglement information transfer can be realized between the two kinds of systems. We also realize long distance quantum information transfer between two quantum dots separated by an MNW, by making use of the nonlocal fermionic level formed with the pared Majorana feimions (MFs) emerging at the two ends of the MNW. Furthermore, we analyze the teleportationlike electron transfer phenomenon predicted by Tewari et al. [Phys. Rev. Lett. 100, 027001 (2008)] in our considered system. Interestingly, we find that this phenomenon exactly corresponds to the case that the information encoded in one QD just returns back to its original place during the dynamical evolution of the combined system from the perspective of quantum state transfer. Project supported by the National Natural Science Foundation of China (Grant No. 11304031).

  6. Charge transfer in multi-component low-dimensional materials stacks (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Bersuker, Gennadi

    2016-09-01

    Advanced electronics, energy storage and harvesting, etc. applications employ devices combining nano-thick layers of dielectric, semiconductor and metal materials. Electrical characteristics of such highly-scaled materials stacks are found to be strongly influenced by the charge transfer across the layers. Charge transfer processes are controlled, to a great degree, by the interface regions, their structure and composition being modified by the inter-materials interaction affected by stack fabrication conditions. These complex systems pose new challenges for analyzing charge transfer processes, which are sensitive to even extremely small concentrations of electrically active defects. In order to identify these defects, the critical task is to link the atomic-level structural features of multicomponent ultra-thin material stacks to their electrical characteristics affected by charge transfer. We focus on analyzing oxide structural features responsible for the charge transfer by combining a variety of electrical measurement techniques with high time and spatial resolutions that allow capturing fast transient charging processes and differentiating signals from different regions through the depth of the multi-layer stacks. These data are used to fit the results of simulations of the physical processes underlying the electrical measurements in order to extract spatial and energy profiles of electrically active centers. The extracted characteristics are, in turn, compared to the atomic-level material modeling data to pinpoint atomic and energy material characteristics responsible for the electrical properties, thus, providing a helpful feedback to optimize the device fabrication process. We discuss examples of implementations of this approach for analysis and optimization of a variety of ultra-thin layers devices.

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

    SciTech Connect

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

    2013-07-28

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

  8. Theory of ultrafast heterogeneous electron transfer: Contributions of direct charge transfer excitations to the absorbance

    SciTech Connect

    Wang, Luxia; Willig, Frank; May, Volkhard

    2007-04-07

    Absorption spectra related to heterogeneous electron transfer are analyzed with the focus on direct charge transfer transition from the surface attached molecule into the semiconductor band states. The computations are based on a model of reduced dimensionality with a single intramolecular vibrational coordinate but a complete account for the continuum of conduction band states. The applicability of this model to perylene on TiO{sub 2} has been demonstrated in a series of earlier papers. Here, based on a time-dependent formulation, the absorbance is calculated with the inclusion of charge transfer excitations. A broad parameter set inspired by the perylene TiO{sub 2} systems is considered. In particular, the description generalizes the Fano effect to heterogeneous electron transfer reactions. Preliminary simulations of measured spectra are presented for perylene-catechol attached to TiO{sub 2}.

  9. Dual Fluorescence in GFP Chromophore Analogues: Chemical Modulation of Charge Transfer and Proton Transfer Bands.

    PubMed

    Chatterjee, Tanmay; Mandal, Mrinal; Das, Ananya; Bhattacharyya, Kalishankar; Datta, Ayan; Mandal, Prasun K

    2016-04-14

    Dual fluorescence of GFP chromophore analogues has been observed for the first time. OHIM (o-hydroxy imidazolidinone) shows only a charge transfer (CT) band, CHBDI (p-cyclicamino o-hydroxy benzimidazolidinone) shows a comparable intensity CT and PT (proton transfer) band, and MHBDI (p-methoxy o-hydroxy benzimidazolidinone) shows a higher intensity PT band. It could be shown that the differential optical behavior is not due to conformational variation in the solid or solution phase. Rather, control of the excited state electronic energy level and excited state acidity constant by functional group modification could be shown to be responsible for the differential optical behavior. Chemical modification-induced electronic control over the relative intensity of the charge transfer and proton transfer bands could thus be evidenced. Support from single-crystal X-ray structure, NMR, femtosecond to nanosecond fluorescence decay analysis, and TDDFT-based calculation provided important information and thus helped us understand the photophysics better.

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

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

    PubMed Central

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

    2015-01-01

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

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

    PubMed

    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 between transition metal and oxygen ions. Such electronic correlations offer a rich playground to engineer functional interfaces but their compatibility with the classical band alignment picture remains an open question. Here we show that beyond differences in electron affinities and polar effects, a key parameter determining charge transfer at correlated oxide interfaces is the energy required to alter the covalence of the metal-oxygen bond. Using the perovskite nickelate (RNiO3) family as a template, we probe charge reconstruction at interfaces with gadolinium titanate GdTiO3. X-ray absorption spectroscopy shows that the charge transfer is thwarted by hybridization effects tuned by the rare-earth (R) size. Charge transfer results in an induced ferromagnetic-like state in the nickelate, exemplifying the potential of correlated interfaces to design novel phases. Further, our work clarifies strategies to engineer two-dimensional systems through the control of both doping and covalence.

  13. Towards first-principles prediction of valence instabilities in mixed stack charge-transfer crystals

    NASA Astrophysics Data System (ADS)

    Delchiaro, Francesca; Girlando, Alberto; Painelli, Anna; Bandyopadhyay, Arkamita; Pati, Swapan K.; D'Avino, Gabriele

    2017-04-01

    Strongly correlated electrons delocalized on one-dimensional (1D) soft stacks govern the complex physics of mixed stack charge-transfer crystals, a well-known family of materials composed of electron-donor (D) and acceptor (A) molecules alternating along the 1D chain. The complex physics of these systems is well captured by a modified Hubbard model that also accounts for the coupling of electrons to molecular and lattice vibrational modes and for three-dimensional electrostatic interactions. Here we study several experimental systems to estimate relevant model parameters via density-functional theory calculations on DA units and isolated molecules and ions. Electrostatic intermolecular interactions, an important quantity not just to define the degree of charge transfer of the ground state but also to predict the propensity of the system towards multistability and hence towards discontinuous phase transitions, are also addressed. Results compare favorably with experimental data.

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

    PubMed

    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 (<3 eV) via the formation of a metastable Cf(ii) state. It is shown that the systematic trend in CT transitions of the lanthanide series is not paralleled by actinide elements lighter than Cf(iii), and californium represents a turning point in the periodicity of the actinide series. Analyses and modeling of the temperature-dependent luminescence dynamics indicate that the metastable Cf(ii) charge-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).

  15. Super-iron Nanoparticles with Facile Cathodic Charge Transfer

    SciTech Connect

    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.

  16. Polaron assisted charge transfer in model biological systems

    NASA Astrophysics Data System (ADS)

    Li, Guangqi; Movaghar, Bijan

    2016-11-01

    We use a tight binding Hamiltonian to simulate the electron transfer from an initial charge-separating exciton to a final target state through a two-arm transfer model. The structure is copied from the model frequently used to describe electron harvesting in photosynthesis (photosystems I). We use this network to provide proof of principle for dynamics, in quantum system/bath networks, especially those involving interference pathways, and use these results to make predictions on artificially realizable systems. Each site is coupled to the phonon bath via several electron-phonon couplings. The assumed large energy gaps and weak tunneling integrals linking the last 3 sites give rise to"Stark Wannier like" quantum localization; electron transfer to the target cluster becomes impossible without bath coupling. As a result of the electron-phonon coupling, local electronic energies relax when the site is occupied, and transient polaronic states are formed as photo-generated electrons traverse the system. For a symmetric constructively interfering two pathway network, the population is shared equally between two sets of equivalent sites and therefore the polaron energy shift is smaller. The smaller energy shift however makes the tunnel transfer to the last site slower or blocks it altogether. Slight disorder (or thermal noise) can break the symmetry, permitting essentially a "one path", and correspondingly more efficient transfer.

  17. Highly Twisted Triarylamines for Photoinduced Intramoleculer ChargeTransfer

    SciTech Connect

    Chudomel, J. M.; Yang, B. Q.; Barnes, M. D.; Achermann, M.; Mague, J. T.; Lahti, P. M.

    2011-08-04

    9-(N,N-Dianisylamino)anthracene (9DAAA), 9-(N,N-dianisylamino)dinaphth([1,2-a:2'-1'-j]-anthracene (9DAAH), and 9,10-bis(N,N-dianisylamino)anthracene (910BAA) were synthesized as highly twisted triarylamines with potential for photoexcited internal charge transfer. Crystallography of 9DAAA shows its dianisylamino group to be twisted nearly perpendicular to its anthracene unit, similar to a report for 910BAA. The solution fluorescence spectra show strong bathochromic shifts for each of the three molecular systems with strongly decreased quantum efficiency in higher polarity solvents. Solution-phase (ensemble) time-resolved photoluminescence measurements show up to 4-fold decreases in fluorescence lifetime in acetonitrile compared to hexane. The combined results are consistent with photoinduced, transient intramolecular charge-transfer from the bis-anisylamine unit to the polycyclic aromatic unit. Computational modeling is in accord with intramolecular transfer of electron density from the bis-anisylamino unit to the anthracene, based on in comparisons of HOMO and LUMO.

  18. Dielectric Properties of Organic Charge-Transfer Salts

    NASA Astrophysics Data System (ADS)

    Fischer, J. K. H.; Lunkenheimer, P.; Krohns, S.; Manna, R. S.; Hartmann, B.; Schubert, H.; Lang, M.; Müller, J.; Schlueter, J. A.; Mézière, C.; Batail, P.; Loidl, A.

    The BEDT-TTF-based charge-transfer salts have attracted considerable attention due to their often intriguing dielectric properties. An example is κ-(BEDT-TTF)2Cu[N(CN)2]Cl. It was recently found to exhibit multiferroicity, for which a new electric-dipole driven mechanism was proposed. The polar moment in this system was suggested to arise from the dimerization of the BEDT-TTF molecules, combined with charge order. Another interesting recent example is α-(BEDT-TTF)2I3, which shows the signature of relaxor-ferroelectric behavior. Here, we will present an overview of the dielectric properties of the above systems and provide new results on κ-(BEDT-TTF)2Hg(SCN)2Cl, which also seems to show relaxor-ferroelectric behavior in its charge-ordered state. In addition, we present measurements of δ-(EDT-TTF-CONMe2)2Br. This compound lacks dimerization, but exhibits charge order already at room temperature.

  19. Modeling of Transient Absorption Spectra in Exciton-Charge-Transfer Systems.

    PubMed

    Kramer, Tobias; Rodríguez, Mirta; Zelinskyy, Yaroslav

    2017-01-26

    Time-resolved spectroscopy provides the main tool for analyzing the dynamics of excitonic energy transfer in light-harvesting complexes. Inferring the time scales and effective coupling parameters from experimental data requires the development of numerically exact theoretical models. The finite duration of the laser-molecule interactions and the reorganization process during the exciton migration affect the location and strength of spectroscopic signals. We show that the nonperturbative hierarchical equations of motion method captures these processes in a model exciton system, including the charge-transfer state.

  20. Metal-organic charge transfer can produce biradical states and is mediated by conical intersections

    PubMed Central

    Tishchenko, Oksana; Li, Ruifang; Truhlar, Donald G.

    2010-01-01

    The present paper illustrates key features of charge transfer between calcium atoms and prototype conjugated hydrocarbons (ethylene, benzene, and coronene) as elucidated by electronic structure calculations. One- and two-electron charge transfer is controlled by two sequential conical intersections. The two lowest electronic states that undergo a conical intersection have closed-shell and open-shell dominant configurations correlating with the 4s2 and 4s13d1 states of Ca, respectively. Unlike the neutral-ionic state crossing in, for example, hydrogen halides or alkali halides, the path from separated reactants to the conical intersection region is uphill and the charge-transferred state is a biradical. The lowest-energy adiabatic singlet state shows at least two minima along a single approach path of Ca to the π system: (i) a van der Waals complex with a doubly occupied highest molecular orbital, denoted , and a small negative charge on Ca and (ii) an open-shell singlet (biradical) at intermediate approach (Ca⋯C distance ≈2.5–2.7 Å) with molecular orbital structure ϕ1ϕ2, where ϕ2 is an orbital showing significant charge transfer form Ca to the π-system, leading to a one-electron multicentered bond. A third minimum (iii) at shorter distances along the same path corresponding to a closed-shell state with molecular orbital structure has also been found; however, it does not necessarily represent the ground state at a given Ca⋯C distance in all three systems. The topography of the lowest adiabatic singlet potential energy surface is due to the one- and two-electron bonding patterns in Ca-π complexes. PMID:21037111

  1. Charge transfer in proton-hydrogen collisions under Debye plasma

    SciTech Connect

    Bhattacharya, Arka; Kamali, M. Z. M.; Ghoshal, Arijit; Ratnavelu, K.

    2015-02-15

    The effect of plasma environment on the 1s → nlm charge transfer, for arbitrary n, l, and m, in proton-hydrogen collisions has been investigated within the framework of a distorted wave approximation. The effect of external plasma has been incorporated using Debye screening model of the interacting charge particles. Making use of a simple variationally determined hydrogenic wave function, it has been possible to obtain the scattering amplitude in closed form. A detailed study has been made to investigate the effect of external plasma environment on the differential and total cross sections for electron capture into different angular momentum states for the incident energy in the range of 20–1000 keV. For the unscreened case, our results are in close agreement with some of the most accurate results available in the literature.

  2. Tunable charge transfer properties in metal-phthalocyanine heterojunctions

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

    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.Organic materials such as phthalocyanine-based systems present a great potential for organic device applications due to the possibility of integrating films of

  3. Promoting Transfer by Grounding Complex Systems Principles

    ERIC Educational Resources Information Center

    Goldstone, Robert L.; Wilensky, Uri

    2008-01-01

    Understanding scientific phenomena in terms of complex systems principles is both scientifically and pedagogically important. Situations from different disciplines of science are often governed by the same principle, and so promoting knowledge transfer across disciplines makes valuable cross-fertilization and scientific unification possible.…

  4. Promoting Transfer by Grounding Complex Systems Principles

    ERIC Educational Resources Information Center

    Goldstone, Robert L.; Wilensky, Uri

    2008-01-01

    Understanding scientific phenomena in terms of complex systems principles is both scientifically and pedagogically important. Situations from different disciplines of science are often governed by the same principle, and so promoting knowledge transfer across disciplines makes valuable cross-fertilization and scientific unification possible.…

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

    SciTech Connect

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

    2010-01-07

    A theoretical study of the structural and electronic properties of the chloride ion and water molecules in the first hydration shell is presented. The calculations are performed on an ensemble of configurations obtained from molecular dynamics simulations of a single chloride ion in bulk water. The simulations utilize the polarizable AMOEBA force field for trajectory generation and MP2-level calculations are performed to examine the electronic structure properties of the ions and surrounding waters in the external field of more distant waters. The ChelpG method is employed to explore the effective charges and dipoles on the chloride ions and first-shell waters. The quantum theory of atoms in molecules (QTAIM) is further utilized to examine charge transfer from the anion to surrounding water molecules. The clusters extracted from the AMOEBA simulations exhibit high probabilities of anisotropic solvation for chloride ions in bulk water. From the QTAIM analysis, 0.2 elementary charges are transferred from the ion to the first-shell water molecules. The default AMOEBA model overestimates the average dipole moment magnitude of the ion compared to the quantum mechanical value. The average magnitude of the dipole moment of the water molecules in the first shell treated at the MP2-level, with the more distant waters handled with an AMOEBA effective charge model, is 2.67 D. This value is close to the AMOEBA result for first-shell waters (2.72 D) and is slightly reduced from the bulk AMOEBA value (2.78 D). The magnitude of the dipole moment of the water molecules in the first solvation shell is most strongly affected by the local water-water interactions and hydrogen bonds with the second solvation shell, rather than by interactions with the ion.

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

    PubMed

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

    2016-04-28

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

  7. Negative thermal expansion induced by intermetallic charge transfer.

    PubMed

    Azuma, Masaki; Oka, Kengo; Nabetani, Koichiro

    2015-06-01

    Suppression of thermal expansion is of great importance for industry. Negative thermal expansion (NTE) materials which shrink on heating and expand on cooling are therefore attracting keen attention. Here we provide a brief overview of NTE induced by intermetallic charge transfer in A-site ordered double perovskites SaCu3Fe4O12 and LaCu3Fe4-x Mn x O12, as well as in Bi or Ni substituted BiNiO3. The last compound shows a colossal dilatometric linear thermal expansion coefficient exceeding -70 × 10(-6) K(-1) near room temperature, in the temperature range which can be controlled by substitution.

  8. Intramolecular charge transfer in donor-acceptor molecules

    SciTech Connect

    Slama-Schwok, A.; Blanchard-Desce, M.; Lehn, J.M. )

    1990-05-17

    The photophysical properties of donor-acceptor molecules, push-pull polyenes and carotenoids, have been studied by absorption and fluorescence spectroscopy. The compounds bear various acceptor and donor groups, linked together by chains of different length and structure. The position of the absorption and fluorescence maxima and their variation in solvents of increasing polarity are in agreement with long-distance intramolecular charge-transfer processes, the linker acting as a molecular wire. The effects of the linker length and structure and of the nature of acceptor and donor are presented.

  9. Modulating unimolecular charge transfer by exciting bridge vibrations.

    PubMed

    Lin, Zhiwei; Lawrence, Candace M; Xiao, Dequan; Kireev, Victor V; Skourtis, Spiros S; Sessler, Jonathan L; Beratan, David N; Rubtsov, Igor V

    2009-12-23

    Ultrafast UV-vibrational spectroscopy was used to investigate how vibrational excitation of the bridge changes photoinduced electron transfer between donor (dimethylaniline) and acceptor (anthracene) moieties bridged by a guanosine-cytidine base pair (GC). The charge-separated (CS) state yield is found to be lowered by high-frequency bridge mode excitation. The effect is linked to a dynamic modulation of the donor-acceptor coupling interaction by weakening of H-bonding and/or by disruption of the bridging base-pair planarity.

  10. Minimal model for charge transfer excitons at the dielectric interface

    NASA Astrophysics Data System (ADS)

    Ono, Shota; Ohno, Kaoru

    2016-03-01

    A theoretical description of the charge transfer (CT) exciton across the donor-acceptor interface without the use of a completely localized hole (or electron) is a challenge in the field of organic solar cells. We calculate the total wave function of the CT exciton by solving an effective two-particle Schrödinger equation for the inhomogeneous dielectric interface. We formulate the magnitude of the CT and construct a minimal model of the CT exciton under the breakdown of inversion symmetry. We demonstrate that both a light hole mass and a hole localization along the normal to the dielectric interface are crucial to yield the CT exciton.

  11. Diamagnetism and charge transfer in bromine graphite intercalation compounds

    NASA Astrophysics Data System (ADS)

    Marchand, A.

    1985-04-01

    The relationship of the magnetic susceptibility anisotropy and the charge-transfer parameter f in graphite-Br intercalation compounds is investigated theoretically. It is argued that the good fit to experimental data obtained by Tsang and Resing (1984) in calculations with f = 0.3 is based on an error in plotting the data of Hennig and McClelland (1955), indicating that the true value of f for these compounds must be significantly smaller. A corrected plot is shown, and the treatment of several other experimental details by Tsang and Resing is discussed.

  12. Photoinduced charge-transfer materials for nonlinear optical applications

    DOEpatents

    McBranch, Duncan W.

    2006-10-24

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

  13. Characterization and control of charge transfer in a tunnel junction

    NASA Astrophysics Data System (ADS)

    Gabelli, Julien; Thibault, Karl; Gasse, Gabriel; Lupien, Christian; Reulet, Bertrand

    2017-03-01

    Charge transfer in a tunnel junction is studied under dc and ac voltage bias using quantum shot noise. Under dc voltage bias $V$, spectral density of noise measured within a very large bandwidth enables to deduce the current-current correlator in the time domain by Fourier transform. This correlator exhibits regular oscillations proving that electrons try to cross the junction regularly, every $h/eV$. Using harmonic and bi-harmonic ac voltage bias, we then show that quasiparticles excitations can be transferred through the junction in a controlled way. By measuring the reduction of the excess shot noise, we are able to determine the number of electron-hole pairs surrounding the injected electrons and demonstrate that bi-harmonic voltage pulses realize an on-demand electron source with a very small admixture of electron-hole pairs.

  14. Studies of Photosynthetic Energy and Charge Transfer by Two-dimensional Fourier transform electronic spectroscopy

    NASA Astrophysics Data System (ADS)

    Ogilvie, Jennifer

    2010-03-01

    Two-dimensional (2D) Fourier transform electronic spectroscopy has recently emerged as a powerful tool for the study of energy transfer in complex condensed-phase systems. Its experimental implementation is challenging but can be greatly simplified by implementing a pump-probe geometry, where the two phase-stable collinear pump pulses are created with an acousto-optic pulse-shaper. This approach also allows the use of a continuum probe pulse, expanding the available frequency range of the detection axis and allowing studies of energy transfer and electronic coupling over a broad range of frequencies. We discuss several benefits of 2D electronic spectroscopy and present 2D data on the D1-D2 reaction center complex of Photosystem II from spinach. We discuss the ability of 2D spectroscopy to distinguish between current models of energy and charge transfer in this system.

  15. A Series of Diamagnetic Pyridine Monoimine Rhenium Complexes with Different Degrees of Metal-to-Ligand Charge Transfer: Correlating (13) C NMR Chemical Shifts with Bond Lengths in Redox-Active Ligands.

    PubMed

    Sieh, Daniel; Kubiak, Clifford P

    2016-07-18

    A set of pyridine monoimine (PMI) rhenium(I) tricarbonyl chlorido complexes with substituents of different steric and electronic properties was synthesized and fully characterized. Spectroscopic (NMR and IR) and single-crystal X-ray diffraction analyses of these complexes showed that the redox-active PMI ligands are neutral and that the overall electronic structure is little affected by the choices of the substituent at the ligand backbone. One- and two-electron reduction products were prepared from selected starting compounds and could also be characterized by multiple spectroscopic methods and X-ray diffraction. The final product of a one-electron reduction in THF is a diamagnetic metal-metal-bonded dimer after loss of the chlorido ligand. Bond lengths in and NMR chemical shifts of the PMI ligand backbone indicate partial electron transfer to the ligand. Two-electron reduction in THF also leads to the loss of the chlorido ligand and a pentacoordinate complex is obtained. The comparison with reported bond lengths and (13) C NMR chemical shifts of doubly reduced free pyridine monoaldimine ligands indicates that both redox equivalents in the doubly reduced rhenium complex investigated here are located in the PMI ligand. With diamagnetic complexes varying over three formal reduction stages at the PMI ligand we were, for the first time, able to establish correlations of the (13) C NMR chemical shifts with the relevant bond lengths in redox-active ligands over a full redox series.

  16. Radiative charge transfer and radiative association in He++ Ne collisions

    NASA Astrophysics Data System (ADS)

    Liu, X. J.; Qu, Y. Z.; Xiao, B. J.; Liu, C. H.; Zhou, Y.; Wang, J. G.; Buenker, R. J.

    2010-02-01

    A fully quantum-mechanical approach is utilized to study the collision process of He+ with neutral neon, and the radiative charge transfer (RCT) and radiative association (RA) cross sections are presented in the energy range from 0.08 meV to 1 eV, while the optical potential and semiclassical methods are adopted to calculate the total radiative decay cross sections for energies from 0.08 meV to 5 keV. The potential energy curves and dipole transition matrix elements are obtained by an ab initio multireference configuration interaction package. For the related three lowest X 2Σ+, A 2Π, and B 2Σ+ states, the spectroscopic data are in good agreement with other theoretical calculations and experimental measurements. Our results indicate that the RCT cross section is much larger than the nonradiative charge transfer cross section for collision energy E < 20 eV, and when E > 40 eV, the nonradiative process becomes dominant. Especially, we found that in the present collision system the RA process is more important than the RCT process when E < 1 meV. The RCT and RA rate coefficients are also given for temperatures from 1 to 4 ×103 K.

  17. Ultrafast charge transfer via a conical intersection in dimethylaminobenzonitrile.

    PubMed

    Fuss, Werner; Pushpa, Kumbil Kuttan; Rettig, Wolfgang; Schmid, Wolfram E; Trushin, Sergei A

    2002-04-01

    The L(a)-like S2 state (2A) of 4-(dimethylamino)benzonitrile was pumped at 267 nm in the gas phase at 130 degrees C. Nonresonant multiphoton ionization at 800 nm with mass-selective detection then probed the subsequent processes. Whereas ionization at the Franck-Condon geometry only gave rise to the parent ion, fragmentation increased on motion towards the charge-transfer (CT) state. This useful difference is ascribed to a geometry-dependent resonance in the ion. The time constants found are interpreted by ultrafast (approximately 68 fs) relaxation through a conical intersection to both the CT and the L(b)-type S1 state (1B). Then the population equilibrates between these two states within 1 ps. From there the molecule relaxes within 90 ps to a lower excited state which can only be a triplet state (T(n)) and then decomposes within 300 ps. Previous experiments either investigated only 1B --> CT relaxation-which does not take place in the gas phase or nonpolar solvents for energetic reasons--or, starting from S2 excitation, typically had insufficient time resolution (>1 ps) to detect the temporary charge transfer. Only recently temporary population of the CT state was found in a nonpolar solvent (Kwok et al., J. Phys. Chem. A. 2000, 104, 4188), a result fully consistent with our mechanism. We also show that S2 --> S1 relaxation does not occur vertically but involves an intermediate strong geometrical distortion, passing through a conical intersection.

  18. Radiative charge transfer and association in slow Li- + H collisions

    NASA Astrophysics Data System (ADS)

    Lin, Xiaohe; Peng, Yigeng; Wu, Yong; Wang, Jianguo; Janev, Ratko; Shao, Bin

    2017-02-01

    Aims: The radiative charge transfer and association processes in Li- + H collisions are studied in the 10-10-10 eV center-of-mass energy range. Methods: we carried out total and ν-resolved state-selective cross sections have been carried out by using the fully quantum, optical potential, and semiclassical methods. Results: In the energy region below 0.8 eV, the radiative association process is the dominant decay channel, while radiative charge transfer dominates at higher energies. Rich resonance structures are observed in the cross sections of both processes in the 0.1-1.5 eV energy range; These structures are associated with the quasi-bound states below the top of the centrifugal barrier of the effective potential in the entrance channel for specific vibrational and angular momentum states. It is found that with the increase of collision energy, the resonances occur for higher angular momentum states and lower vibrational states. Besides the cross sections for the studied processes we also present their reaction rate coefficients in the 10-6-106K temperature range.

  19. Charge transfer during alkali-surface adsorbate collisions

    NASA Astrophysics Data System (ADS)

    Yang, Ye

    The study of charge transfer process between atomic particles and surface adsorbates is important, from both fundamental and practical points of view. Resonant charge transfer (RCT) process during the scattering of low-energy alkali ions from surfaces is proven to depend on the surface local electrostatic potential (LEP). This dissertation investigates the surface electronic environment around halogen and hydrogen adatoms on transition metal and silicon surfaces by using alkali ion scattering. Charge transfer in 7Li+ scattering from clean Si surfaces was shown to involve RCT between the Li 2s level and the Si dangling bonds. Hydrogen adsorption decreases the neutralization because it ties up the dangling bonds. The neutral fractions in 7Li + scattering from Cs/Si are also determined primarily by the dangling bond states, so that the surface LEP cannot be directly probed. Hydrogen adsorption on Cs/Si ties up the dangling bonds, thereby revealing the local potentials. The neutralization probabilities of Li+ backscattered from the hydrogen- and iodine-covered Ni(100) surface were measured. The neutral fraction does not change significantly on H-adsorbed surface. For iodine adsorption, however, unexpected high neutralization probabilities were found for Li scattered directly from iodine sites. Similar behavior were observed for Li+ scattering from I- and Br-covered Fe(100) and Fe(110). The neutralization of Li+ was measured as a function of the incident energy, adatom charge and coverage, and exit angle. It was found that the larger neutral fractions of Li scattered from the halogen sites are caused by a lower potential directly above the adatoms due to internal polarization. As the exit beam moves off-normal, the neutral fraction of Li scattered from iodine decreases. This is in contrast to Cs and Ag adsorbates where the neutral fractions increase for glancing exit trajectories. These angular-dependences are verified by a semi-quantitative theoretical analysis. To

  20. Mutation induction by charged particles of defined linear energy transfer.

    PubMed

    Hei, T K; Chen, D J; Brenner, D J; Hall, E J

    1988-07-01

    The mutagenic potential of charged particles of defined linear energy transfer (LET) was assessed using the hypoxanthine-guanine phosphoribosyl transferase locus (HGPRT) in primary human fibroblasts. Exponentially growing cultures of early passaged fibroblasts were grown as monolayers on thin mylar sheets and were irradiated with accelerated protons, deuterons or helium-3 ions. The mutation rates were compared with those generated by 137Cs gamma-rays. LET values for charged particles accelerated at the Radiological Research Accelerator Facility, using the track segment mode, ranged from 10 to 150 keV/micron. After irradiation, cells were trypsinized, subcultured and assayed for both cytotoxicity and 6-thioguanine resistance. For gamma-rays, and for the charged particles of lower LET, the dose-response curves for cell survival were characterized by a marked initial shoulder, but approximated to an exponential function of dose for higher LETs. Mutation frequencies, likewise, showed a direct correlation to LET over the dose range examined. Relative biological effectiveness (RBE) for mutagenesis, based on the initial slopes of the dose-response curves, ranged from 1.30 for 10 keV/micron protons to 9.40 for 150 keV/micron helium-3 ions. Results of the present studies indicate that high-LET radiations, apart from being efficient inducers of cell lethality, are even more efficient in mutation induction as compared to low-LET ionizing radiation. These data are consistent with results previously obtained with both rodent and human fibroblast cell lines.

  1. Symmetry-Breaking Charge Transfer of Visible Light Absorbing Systems: Zinc Dipyrrins

    PubMed Central

    2015-01-01

    Zinc dipyrrin complexes with two identical dipyrrin ligands absorb strongly at 450–550 nm and exhibit high fluorescence quantum yields in nonpolar solvents (e.g., 0.16–0.66 in cyclohexane) and weak to nonexistent emission in polar solvents (i.e., <10–3, in acetonitrile). The low quantum efficiencies in polar solvents are attributed to the formation of a nonemissive symmetry-breaking charge transfer (SBCT) state, which is not formed in nonpolar solvents. Analysis using ultrafast spectroscopy shows that in polar solvents the singlet excited state relaxes to the SBCT state in 1.0–5.5 ps and then decays via recombination to the triplet or ground states in 0.9–3.3 ns. In the weakly polar solvent toluene, the equilibrium between a localized excited state and the charge transfer state is established in 11–22 ps. PMID:25270268

  2. On Limiting Values of Dust Charges in Complex Plasmas

    SciTech Connect

    Kopnin, S. I.; Morozova, T. I.; Popel, S. I.

    2011-11-29

    We investigate limiting values of charges of microparticles for two possibilities of complex (dusty) plasmas in the presence of electromagnetic radiation. The first possibility assumes solid dust grains contained in the plasma while the second one implies the liquid droplets. We obtain analytical expression describing dust particle charging as a result of intensive photoelectric effect. We show that the electrostatic pressure on the surface of charged solid dust particles can affect the strength characteristics of these particles. We obtain the limiting values of the charges of solid dusts, the dusts exceeding this charge value are subjected to total or partial destruction. Necessary conditions and parameters for X-ray sources of electromagnetic radiation are defined to reach these limiting values of dust charges.

  3. Charge-transfer interactions of metoclopramide nausea drug against six kind of π-acceptors: spectral and thermal discussions.

    PubMed

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

    2014-04-05

    The target of this paper is aimed to discuss the fast and newly techniques in order to assessment the metoclopramide (Mcp) nausea drug in pure form in solid and solution shape with different kind of π-acceptors upon charge transfer interactions. Charge-transfer complexes (CTC) of metoclopramide with picric acid (PA), 2,3-dichloro-5,6-dicyano-p-benzoquinon (DDQ), tetracyanoquinodimethane (TCNQ), m-dinitrobenzene (DNB), p-nitrobenzoic acid (p-NBA) and tetrachloro-p-quinon (p-CL) have been studied spectrophotometrically in absolute methanol at room temperature. The stoichiometries of the complexes were found to be 1:1 ratio by the spectrophotometric titration between metoclopramide and represented π-acceptors. The equilibrium constants, molar extinction coefficient (εCT) and spectroscopic-physical parameters (standard free energy (ΔG°), oscillator strength (ƒ), transition dipole moment (μ), resonance energy (RN) and ionization potential (ID)) of the complexes were determined upon the modified Benesi-Hildebrand equation. The results indicate that the formation constants for the complexes depend on the nature of electron acceptors and configuration of drug donor, and also the spectral studies of the complexes were determined by (infrared, Raman, and (1)H NMR) spectra and X-ray powder diffraction (XRD). The charge-transfer complexes are formed during the interaction of electron-acceptors and electron-donors as result of partial or complete transfer of a negative charge from (D(+)-A(-)). Copyright © 2013 Elsevier B.V. All rights reserved.

  4. Photoinduced energy transfer in transition metal complex oligomers

    SciTech Connect

    1997-04-01

    The work we have done over the past three years has been directed toward the preparation, characterization and photophysical examination of mono- and bimetallic diimine complexes. The work is part of a broader project directed toward the development of stable, efficient, light harvesting arrays of transition metal complex chromophores. One focus has been the synthesis of rigid bis-bidentate and bis-tridentate bridging ligands. We have managed to make the ligand bphb in multigram quantities from inexpensive starting materials. The synthetic approach used has allowed us prepare a variety of other ligands which may have unique applications (vide infra). We have prepared, characterized and examined the photophysical behavior of Ru(II) and Re(I) complexes of the ligands. Energy donor/acceptor complexes of bphb have been prepared which exhibit nearly activationless energy transfer. Complexes of Ru(II) and Re(I) have also been prepared with other polyunsaturated ligands in which two different long lived ( > 50 ns) excited states exist; results of luminescence and transient absorbance measurements suggest the two states are metal-to-ligand charge transfer and ligand localized {pi}{r_arrow}{pi}* triplets. Finally, we have developed methods to prepare polymetallic complexes which are covalently bound to various surfaces. The long term objective of this work is to make light harvesting arrays for the sensitization of large band gap semiconductors. Details of this work are provided in the body of the report.

  5. Photoinduced energy transfer in transition metal complex oligomers

    SciTech Connect

    1997-06-01

    The work done over the past three years has been directed toward the preparation, characterization and photophysical examination of mono- and bimetallic diimine complexes. The work is part of a broader project directed toward the development of stable, efficient, light harvesting arrays of transition metal complex chromophores. One focus has been the synthesis of rigid bis-bidentate and bis-tridentate bridging ligands. The authors have managed to make the ligand bphb in multigram quantities from inexpensive starting materials. The synthetic approach used has allowed them to prepare a variety of other ligands which may have unique applications (vide infra). They have prepared, characterized and examined the photophysical behavior of Ru(II) and Re(I) complexes of the ligands. Energy donor/acceptor complexes of bphb have been prepared which exhibit nearly activationless energy transfer. Complexes of Ru(II) and Re(I) have also been prepared with other polyunsaturated ligands in which two different long lived (> 50 ns) excited states exist; results of luminescence and transient absorbance measurements suggest the two states are metal-to-ligand charge transfer and ligand localized {pi}{r_arrow}{pi}* triplets. Finally, the authors have developed methods to prepare polymetallic complexes which are covalently bound to various surfaces. The long term objective of this work is to make light harvesting arrays for the sensitization of large band gap semiconductors. Details of this work are provided in the body of the report.

  6. Cooperative coupling of the Li cation and groups to amplify the charge transfer between C60 and corannulene

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

    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

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

    PubMed

    Zhou, Xiaolong; Wang, Enduo

    2013-10-01

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

  9. Phosphine passivated gold clusters: how charge transfer affects electronic structure and stability.

    PubMed

    Mollenhauer, Doreen; Gaston, Nicola

    2016-11-02

    A systematic evaluation of small phosphine ligand-protected gold clusters with six to nine gold atoms using density functional theory with dispersion correction has been performed in order to understand the major factors determining stability, including its size, shape, and charge dependence. We show that the charge per atom of the cluster is much more important for the interaction between the ligand shell and gold cluster than the system size. Thus, strong charge transfer effects determine the binding strength between the ligand shell and cluster. The clusters in this series are all non-spherical and exhibit large HOMO-LUMO gaps (above 2.7 eV). Analysis of the delocalized nature of the electronic states at the centre of the clusters demonstrates the presence of nascent superatomic states. However the number of delocalized electrons in these systems is significantly influenced by the charge transfer from the phosphine ligands, contrary to the usual accounting rule for superatom complex systems. Thus, not only electron withdrawing but also charge transfer effects should be considered to influence the superatomic structure of charged ligand surrounded clusters. In consequence in the phosphine gold cluster series under consideration the systems Au7(PPh3)7(+) and Au8(PPh3)8(2+) exhibit nearly fully filled S and P states and the HOMO-LUMO gap increases by 0.2 eV and 0.9 eV, respectively. The interpretation for the stability of the gold phosphine systems is in agreement with experimental results and demonstrates the importance of the superatomic concept.

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

    PubMed

    Duarte, Leonardo José; Richter, Wagner Eduardo; Silva, Arnaldo F; Bruns, Roy Edward

    2017-10-02

    Fundamental infrared intensities of gas-phase molecules are sensitive probes of changes in electronic structure accompanying small molecular distortions. Models containing charge, charge transfer and dipolar polarization effects are necessary for a successful classification of the C-H, C-F and C-Cl stretching and bending intensities. C-H stretching and in-plane bending vibrations involving sp3 carbon atoms have small equilibrium charge contributions and are accurately modeled by the charge transfer- counterpolarization contribution and its interaction with equilibrium charge movement. Large C-F and C=O stretching intensities have dominant equilibrium charge movement contributions compared to their charge transfer-dipolar polarization ones and are accurately estimated by equilibrium charge and the interaction contribution. The C-F and C-Cl bending modes have charge and charge transfer-dipolar polarization contribution sums that are of similar size but opposite sign to their interaction values resulting in small intensities. Experimental in-plane C-H bends have small average intensities of 12.6±10.4 km mol-1 owing to negligible charge contributions and charge transfer-counterpolarization cancellations, whereas their average out-of-plane experimental intensities are much larger, 65.7±20.0 km mol-1,as charge transfer is zero and only dipolar polarization takes place. The C-F bending intensities have large charge contributions but very small intensities. Their average experimental out-of-plane intensity of 9.9±12.6 km mol-1 arises from the cancellation of large charge contributions by dipolar polarization contributions. The experimental average in-plane C-F bending intensities, 5.8±7.3 km mol-1 is also small owing to charge and charge transfer-counterpolarization sums being cancelled by their interaction contributions. Models containing only atomic charges and their fluxes are incapable of describing electronic structure changes for simple molecular distortions that

  11. Charge transfer excitations from excited state Hartree-Fock subsequent minimization scheme

    SciTech Connect

    Theophilou, Iris; Tassi, M.; Thanos, S.

    2014-04-28

    Photoinduced charge-transfer processes play a key role for novel photovoltaic phenomena and devices. Thus, the development of ab initio methods that allow for an accurate and computationally inexpensive treatment of charge-transfer excitations is a topic that nowadays attracts a lot of scientific attention. In this paper we extend an approach recently introduced for the description of single and double excitations [M. Tassi, I. Theophilou, and S. Thanos, Int. J. Quantum Chem. 113, 690 (2013); M. Tassi, I. Theophilou, and S. Thanos, J. Chem. Phys. 138, 124107 (2013)] to allow for the description of intermolecular charge-transfer excitations. We describe an excitation where an electron is transferred from a donor system to an acceptor one, keeping the excited state orthogonal to the ground state and avoiding variational collapse. These conditions are achieved by decomposing the space spanned by the Hartree-Fock (HF) ground state orbitals into four subspaces: The subspace spanned by the occupied orbitals that are localized in the region of the donor molecule, the corresponding for the acceptor ones and two more subspaces containing the virtual orbitals that are localized in the neighborhood of the donor and the acceptor, respectively. Next, we create a Slater determinant with a hole in the subspace of occupied orbitals of the donor and a particle in the virtual subspace of the acceptor. Subsequently we optimize both the hole and the particle by minimizing the HF energy functional in the corresponding subspaces. Finally, we test our approach by calculating the lowest charge-transfer excitation energies for a set of tetracyanoethylene-hydrocarbon complexes that have been used earlier as a test set for such kind of excitations.

  12. Complexation of a polyelectrolyte with oppositely charged spherical macroions: Giant inversion of charge.[1

    NASA Astrophysics Data System (ADS)

    Nguyen, Toan T.; Shklovskii, Boris I.

    2001-03-01

    Complexation of a long flexible polyelectrolyte (PE) molecule with oppositely charged spherical particles such as colloids, micelles, or globular proteins in a salty water solution is studied. PE binds spheres winding around them, while spheres repel each other and form almost periodic necklace. If the total charge of PE is larger than total charge of spheres, repulsive correlations of PE turns on a sphere lead to inversion of the net charge of each sphere. In the opposite case, we predict another correlation effect: under-screened by PE spheres bind to PE in such a great number that they invert the charge of PE. The inverted charge by absolute value can be larger than the bare charge of PE even when screening by monovalent salt is weak. At larger concentrations of monovalent salt, the inverted charge can reach giant proportions. Our theory is in qualitative agreement with recent experiments on micelles-PE systems[2]. A stiff PE is also considered and compared to a flexible one of the same linear charge density. Charge inversion for a stiff PE is found to be stronger than for a flexible PE at large monovalent salt concentration and weaker at small salt concentration. [1]Toan The Nguyen and Boris I. Shklovskii, cond-mat/0011096 (2000), submitted to J. Chem. Phys. [2]Y. Wang, K. Kimura, Q. Huang, P. L. Dubin, W. Jaeger, Macromolecules, 32 (1999) 7128.

  13. HST WFC3/UVIS: charge transfer efficiency monitoring and mitigation

    NASA Astrophysics Data System (ADS)

    Baggett, Sylvia M.; Sosey, Megan L.; Anderson, Jay; Gosmeyer, Catherine; Bourque, Matthew; Bajaj, Varun; Khandrika, Harish G.; Martlin, Catherine; Kozhurina-Platais, Vera; Sabbi, Elena; WFC3 Team

    2016-01-01

    The harsh low-earth orbit environment is known to damage CCD devices and the HST WFC3/UVIS camera is no exception. One consequence of the radiation damage is charge-transfer efficiency (CTE) loss over time. We summarize the level of the CTE losses, the effect on science data, and the pre- and post-observation mitigation options available. Among them is the pixel-based CTE correction, which has been incorporated into the HST automatic data processing pipeline. The pipeline now provides both standard and CTE-corrected data products; observers with older data can re-retrieve their images via the the Mikulski Archive for Space Telescopes (MAST) to obtain the new products.

  14. Charge transfer between O{sup +} ions and helium

    SciTech Connect

    Zhao, L.B.; Stancil, P.C.; Liebermann, H.P.; Funke, P.; Buenker, R.J.

    2005-06-15

    The charge-transfer processes O{sup +}({sup 4}S{sup 0},{sup 2}D{sup 0},{sup 2}P{sup 0})+He{yields}O({sup 3}P)+He{sup +} have been investigated by using a fully quantal molecular-orbital close-coupling (QMOCC) approach. Cross sections are presented for ion energies from 0.5 to 10 keV and compared with those from recent experiments and semiclassical theory. Good agreement is found between the QMOCC results and the measurements. Particular attention is given to addressing the metastable component of the experimental ion beams. We further argue that the so-called 'suppressed electron-capture effect' for metastable ions proposed by Wolfrum et al. is not a viable mechanism to explain their measurements. However, the current QMOCC calculations were found to reproduce neither the ground-state nor metastable-state cross sections predicted by the semiclassical method.

  15. Charge transfer in heterostructures of strongly correlated materials

    SciTech Connect

    Gonzalez Lopez Del Castillo, Ivan; Okamoto, Satoshi; Yunoki, Seiji; Moreo, Adriana; Dagotto, Elbio R

    2008-01-01

    In this work, recent theoretical investigations by the authors in the area of oxide multilayers are briefly reviewed. The calculations were carried out using model Hamiltonians and a variety of non-perturbative techniques. Moreover, new results are also included here. They correspond to the generation of a metallic state by mixing insulators in a multilayer geometry, using the Hubbard and double-exchange models. For the latter, the resulting metallic state is also ferromagnetic. This illustrates how electron or hole doping via transfer of charge in multilayers can lead to the study of phase diagrams of transition metal oxides in the clean limit. Currently, these phase diagrams are much affected by the disordering standard chemical doping procedure, which introduces quenched disorder in the material.

  16. Charge transfer in heterostructures of strongly correlated materials.

    PubMed

    González, I; Okamoto, S; Yunoki, S; Moreo, A; Dagotto, E

    2008-07-02

    In this work, recent theoretical investigations by the authors in the area of oxide multilayers are briefly reviewed. The calculations were carried out using model Hamiltonians and a variety of non-perturbative techniques. Moreover, new results are also included here. They correspond to the generation of a metallic state by mixing insulators in a multilayer geometry, using the Hubbard and double-exchange models. For the latter, the resulting metallic state is also ferromagnetic. This illustrates how electron or hole doping via transfer of charge in multilayers can lead to the study of phase diagrams of transition metal oxides in the clean limit. Currently, these phase diagrams are much affected by the disordering standard chemical doping procedure, which introduces quenched disorder in the material.

  17. Charge transfer doping of graphene without degrading carrier mobility

    NASA Astrophysics Data System (ADS)

    Lu, Haichang; Guo, Yuzheng; Robertson, John

    2017-06-01

    Density functional calculations are used to analyze the charge transfer doping mechanism by molecules absorbed onto graphene. Typical dopants studied are AuCl3, FeCl3, SbF5, HNO3, MoO3, Cs2O, O2, and OH. The Fermi level shifts are correlated with the electron affinity or ionization potential of the dopants. We pay particular attention to whether the dopants form direct chemisorptive bonds which cause the underlying carbon atoms to pucker to form sp3 sites as these interrupt the π bonding of the basal plane, and cause carrier scattering and thus degrade the carrier mobility. Most species even those with high or low electronegativity do not cause puckering. In contrast, reactive radicals like -OH cause puckering of the basal plane, creating sp3 sites which degrade mobility.

  18. Charge transfer processes: the role of optimized molecular orbitals.

    PubMed

    Meyer, Benjamin; Domingo, Alex; Krah, Tim; Robert, Vincent

    2014-08-07

    The influence of the molecular orbitals on charge transfer (CT) reactions is analyzed through wave function-based calculations. Characteristic CT processes in the organic radical 2,5-di-tert-butyl-6-oxophenalenoxyl linked with tetrathiafulvalene and the inorganic crystalline material LaMnO3 show that changes in the inner shells must be explicitly taken into account. Such electronic reorganization can lead to a reduction of the CT vertical transition energy up to 66%. A state-specific approach accessible through an adapted CASSCF (complete active space self-consistent field) methodology is capable of reaching good agreement with the experimental spectroscopy of CT processes. A partitioning of the relaxation energy in terms of valence- and inner-shells is offered and sheds light on their relative importance. This work paves the way to the intimate description of redox reactions using quantum chemistry methods.

  19. Hydrogen Ion-Molecule Isotopomer Collisions: Charge Transfer and Rearrangement

    NASA Astrophysics Data System (ADS)

    Wang, J. G.; Stancil, P. C.

    A survey of existing data for collisions of isotopes of hydrogen atoms, ions, and molecules is presented. The survey was limited to atom - diatom ionic collisions and to energies generally less than about 10 keV/u. The processes include particle-rearrangement and charge transfer, including both dissociative and non-dissociative channels, with an emphasis on state-to-state (or state-selected) data, where available. Since the last survey (Linder, Janev and Botero 1995), a small number of investigations for deuterium and tritium ion-diatom systems have been performed, with some involving state-resolved data, which include the initial-state-resolved and state-to-state processes. While some progress has been made since the last survey, the database involving hydrogen isotope collisional processes, both total and state- resolved, is far from complete.

  20. Negative thermal expansion induced by intermetallic charge transfer

    PubMed Central

    Azuma, Masaki; Oka, Kengo; Nabetani, Koichiro

    2015-01-01

    Suppression of thermal expansion is of great importance for industry. Negative thermal expansion (NTE) materials which shrink on heating and expand on cooling are therefore attracting keen attention. Here we provide a brief overview of NTE induced by intermetallic charge transfer in A-site ordered double perovskites SaCu3Fe4O12 and LaCu3Fe4−xMnxO12, as well as in Bi or Ni substituted BiNiO3. The last compound shows a colossal dilatometric linear thermal expansion coefficient exceeding −70 × 10−6 K−1 near room temperature, in the temperature range which can be controlled by substitution. PMID:27877801

  1. Charge transfer processes in SiH 2+

    NASA Astrophysics Data System (ADS)

    Chambaud, G.; Bliman, S.; Rosmus, P.; Senekowitsch, J.; ONeil, S.

    1995-05-01

    For SiH 2+ potential energy functions for the doublet and quartet electronic states resulting from the Si 2+y( 1S, 3P) + H( 2S) and Si +( 2P, 4P, 2D) + H + asymptotes have been calculated using CASSCF-CI electronic wavefunctions. At low collision energies the charge transfer reactions Si 2+ + H → Si + + H + are found to proceed via avoided crossing regions on the potential energy functions around RSiH = 10 bohr for the doublet states and around RSiH = 8 bohr for the quartet states. No such pathway connecting the metastable Si 2+( 3P) ion with the electronic ground state of the Si + ion was found. Spectroscopic constants and radiative transition probabilities for several low lying doublet and quartet states of SiH 2+ have been evaluated.

  2. Charge transfer emission of ytterbium-doped oxyborates.

    PubMed

    Sablayrolles, J; Jubera, V; Guillen, F; Garcia, A

    2008-03-01

    The ultraviolet spectroscopic properties of trivalent ytterbium have been studied at low temperature in one borate and two oxyborates in the ternary diagram Li(2)O-Y(2)O(3)-B(2)O(3). The UV luminescence was detected in the two ytterbium-doped oxyborates. The evolution of these emissions was studied as a function of the temperature. A determination of the configurational coordinate diagrams based on the Struck and Fonger model is proposed to calculate the position in energy of the charge transfer band afforded by the simulation of spectral distribution of these excitation and emission bands. The strong correlation between the luminescent properties and the environments of the rare earth is pointed out.

  3. Photoinduced Charge Transfer from Titania to Surface Doping Site

    PubMed Central

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

    2013-01-01

    We evaluate a theoretical model in which Ru is substituting for Ti at the (100) surface of anatase TiO2. Charge transfer from the photo-excited TiO2 substrate to the catalytic site triggers the photo-catalytic event (such as water oxidation or reduction half-reaction). We perform ab-initio computational modeling of the charge transfer dynamics on the interface of TiO2 nanorod and catalytic site. A slab of TiO2 represents a fragment of TiO2 nanorod in the anatase phase. Titanium to ruthenium replacement is performed in a way to match the symmetry of TiO2 substrate. One molecular layer of adsorbed water is taken into consideration to mimic the experimental conditions. It is found that these adsorbed water molecules saturate dangling surface bonds and drastically affect the electronic properties of systems investigated. The modeling is performed by reduced density matrix method in the basis of Kohn-Sham orbitals. A nano-catalyst modeled through replacement defect contributes energy levels near the bottom of the conduction band of TiO2 nano-structure. An exciton in the nano-rod is dissipating due to interaction with lattice vibrations, treated through non-adiabatic coupling. The electron relaxes to conduction band edge and then to the Ru cite with faster rate than hole relaxes to the Ru cite. These results are of the importance for an optimal design of nano-materials for photo-catalytic water splitting and solar energy harvesting. PMID:23795229

  4. Charge-Transfer Emitting Triarylborane π-Electron Systems.

    PubMed

    Li, Sheng-Yong; Sun, Zuo-Bang; Zhao, Cui-Hua

    2017-02-06

    Triarylboranes have attracted significantly increasing research interest as a remarkable class of photoelectronic π-electron materials. Because of the presence of vacant p orbital on the B center, the boryl group is a very unique electron acceptor that exhibits not only electron-accepting ability through p-π* conjugation but also high Lewis acidity to coordinate with Lewis bases and steric bulk arising from the aryl substituent on the B center to get enough kinetic stability. Thus, the incorporation of a trivalent B element into π-conjugated systems is an efficient strategy to tune the electronic and stereo structures and thus the photoelectronic properties of π-electron systems. When an electron-donating group, such as amino, is present, triarylboranes would likely display intramolecular charge-transfer transitions. These kinds of molecules are often highly emissive. In addition, the geometry of the molecules has a great impact on the emission properties. In this Forum Article, we herein describe our recent progress on the charge-transfer emitting triarylborane π-electron systems with novel geometries, which include the lateral boryl-substituted π-system with amino groups at the terminal positions, the o,o'-substituted biaryl π-system with boryl and amino groups at the o,o'-positions, a triarylborane-based BODIPY system, and a B,N/S-bridged ladder-type π-system. We mainly put the emphasis on the molecular design concept, structure-property relationships, intriguing emission properties and great applications of the corresponding triarylborane π-systems.

  5. Laser assisted charge transfer in the realm of cold collisions

    NASA Astrophysics Data System (ADS)

    Petrov, Alexander; Makrides, Constantinos; Kotochigova, Svetlana

    2015-05-01

    We study two colliding particles, Ca and Yb+, which can undergo non-radiative charge-exchange transitions from the scattering continuum in the excited A2Σ+ state to the continuum of the ground X2Σ+ state. This reaction can be controlled by linearly-polarized laser radiation of frequency ω, which is in the range of quasi-molecular electronic energy separation. Using the dressed-state picture or the Floquet Ansatz we construct coupled time-independent Schrödinger equations for the interatomic separation R. The mechanism of electromagnetic field control is based on an interplay between intra-molecular couplings and molecule-field interactions. We show that laser field affects the chemical reaction through reversible modification of an effective Hamiltonian via either non-resonant temporal Stark shifts or resonant ``dipolar'' interactions, leading to both transient- and cw-light-induced non-adiabatic charge transfer. We investigate these processes for various collision energies as well as over a wide range of laser intensities and frequencies. Research at Temple University is supported by MURI-ARO (W911NF-14-1-0378) and NSF (No. PHY-1308573) grants.

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

    NASA Astrophysics Data System (ADS)

    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.

  7. Carbon atomic wires: charge transfer induced electron conduction

    NASA Astrophysics Data System (ADS)

    Larade, Brian; Taylor, Jeremy; Mehrez, Hatem; Guo, Hong

    2001-03-01

    We report a first principles theoretical analysis of quantum transport properties of carbon atomic wires. Our theory is based on density functional theory within the LDA approximation, with standard norm conserving pseudopotentials defining the atomic core, and a localized orbital basis set to model the valence states. The charge density for the open atomic wire system is calculated using the non-equilibrium Green's functions. This theory is implemented in our molecular electronics modeling package McDCAL. For carbon atomic chains with different lengths in contact with metallic electrodes, we calculated linear DC conductance as a function of the chain-electrode distance and the current-voltage characteristics. Our results show that charge transfer from the electrodes to the atomic wire plays a most important role in aligning the Fermi level of the electrodes to the LUMO state of the atomic wire, inducing a substantial conductance variation due to this effect. Our results also show that the eigenstates of the carbon chain and band structure of the electrodes are of particular importance to the transport properties. We will compare our results to those obtained previously.

  8. Charge Transfer Efficiency in the WFPC2 CCD Arrays

    NASA Astrophysics Data System (ADS)

    Biretta, J.; Baggett, S.; Riess, A.; Schultz, A.; Casertano, S.; Gonzaga, S.; Heyer, I.; Koekemoer, A.; Mack, J.; McMaster, M.

    2001-05-01

    We present an overview of Charge Transfer Efficiency (CTE) issues in the WFPC2 CCDs, including results of recent on-orbit tests, and advice on mitigating CTE effects. CTE causes targets far from the CCD readout amplifier to appear fainter than similar targets near the amplifier. For bright targets, the maximum effect is only a few percent, but for faint stellar targets in recent images with very low background, the CTE effects can reach 50% or more. Studies using hotpixels, cosmic rays, and residual images as probes of CTE have revealed at least four distinct components of CTE losses. The largest effect appears related to trapping and release of charge on timescales of hundreds of milliseconds during the readout process. This is manifest as tails on images which extend for dozens of pixels in the Y-direction (parallel register direction) on the CCDs, which have the effect of robbing counts from typical small apertures used for photometry. Extended targets also are subject to CTE effects. Recent work shows that within small apertures, the CTE losses for faint galaxies are roughly similar to those for stellar targets with the same total counts. There are also small effects on the shapes of faint galaxies: the average profiles are asymmetric and consistent with charge being lost primarily from the amplifier side of the galaxy. We present current results of long-term photometric monitoring which show CTE problems steadily increasing with time. There is also some evidence for an acceleration of the effect. Preflashing the CCDs can reduce CTE effects, but the added noise usually makes this unattractive. A noise-less preflash technique has been tested, but only provides modest improvement. We discuss photometric CTE corrections which can be applied during data analysis, including the new Dolphin (2000) CTE corrections and their relation to the Whitmore et al. (1999) corrections.

  9. Real-time observation of interfragment vibration and charge transfer within the TCNQF4 dimer

    NASA Astrophysics Data System (ADS)

    Hashimoto, Sena; Yabushita, Atsushi; Iwakura, Izumi

    2017-08-01

    The organic electron acceptors, 7,7,8,8-tetracyanoquinodimethane (TCNQ) and 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (TCNQF4), are widely used to synthesize multivalent charge-transfer complexes. Their corresponding radical anion complexes have specific electronic, optical, and magnetic characters that have attracted attention in the field of materials development. In the present work, we have performed time-resolved absorption spectroscopy of the (Na+)2(TCNQF4rad -)2 radical anion complex to elucidate the reaction dynamics ([TCNQF4rad -]2 → TCNQF4 + TCNQF42-). A visible sub-10 fs laser pulse was used to observe the ultrafast dynamics of the charge transfer and real-time change of the molecular structure during the reaction. Unlike our previous work on the (Na+)2(TCNQrad -)2 radical anion complex, the interfragment vibrational mode was clearly observed for (Na+)2(TCNQF4rad -)2. The difference in the intermolecular interaction is considered to reflect the difference in the π-π interaction and/or the difference in the flexibility of the molecular plane predicted by theoretical calculations.

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

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

    Bibes, Manuel

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

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

    NASA Astrophysics Data System (ADS)

    Benson, Michelle C.

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

  13. Reaction dynamics and proton coupled electron transfer: studies of tyrosine-based charge transfer in natural and biomimetic systems.

    PubMed

    Barry, Bridgette A

    2015-01-01

    In bioenergetic reactions, electrons are transferred long distances via a hopping mechanism. In photosynthesis and DNA synthesis, the aromatic amino acid residue, tyrosine, functions as an intermediate that is transiently oxidized and reduced during long distance electron transfer. At physiological pH values, oxidation of tyrosine is associated with a deprotonation of the phenolic oxygen, giving rise to a proton coupled electron transfer (PCET) reaction. Tyrosine-based PCET reactions are important in photosystem II, which carries out the light-induced oxidation of water, and in ribonucleotide reductase, which reduces ribonucleotides to form deoxynucleotides. Photosystem II contains two redox-active tyrosines, YD (Y160 in the D2 polypeptide) and YZ (Y161 in the D1 polypeptide). YD forms a light-induced stable radical, while YZ functions as an essential charge relay, oxidizing the catalytic Mn₄CaO₅ cluster on each of four photo-oxidation reactions. In Escherichia coli class 1a RNR, the β2 subunit contains the radical initiator, Y122O•, which is reversibly reduced and oxidized in long range electron transfer with the α2 subunit. In the isolated E. coli β2 subunit, Y122O• is a stable radical, but Y122O• is activated for rapid PCET in an α2β2 substrate/effector complex. Recent results concerning the structure and function of YD, YZ, and Y122 are reviewed here. Comparison is made to recent results derived from bioengineered proteins and biomimetic compounds, in which tyrosine-based charge transfer mechanisms have been investigated. This article is part of a Special Issue entitled: Vibrational spectroscopies and bioenergetic systems. Copyright © 2014 Elsevier B.V. All rights reserved.

  14. Charge transfer in graphene oxide-dye system for photonic applications

    SciTech Connect

    Bongu, Sudhakara Reddy Bisht, Prem B.; Thu, Tran V.; Sandhu, Adarsh

    2014-02-20

    The fluorescence of a standard dye Rhodamine 6G (R6G) in solution decreases on addition of reduced graphene oxide (rGO). The absorption spectra and lifetime measurements confirm that no excited-state but a ground-state complex formation is responsible for this effect. For silver decorated rGO (Ag-rGO), the quenching efficiency and ground state complex formation process is small. Z-scan measurements have been done to study the optical nonlinearity at 532 nm under ps time scale. Remarkable reduction in the saturable absorption (SA) effect of R6G indicates no nonlinear contribution from the ground state complex. The results have been explained with varying charge transfer rates and non-fluorescence nature of the complex.

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

    DOE PAGES

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

    2016-07-01

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

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

    SciTech Connect

    Wang, Lei; Han, Jinkyu; Sundahl, Bryan; Thornton, Scott; Zhu, Yuqi; Zhou, Ruiping; Jaye, Cherno; Liu, Haiqing; Li, Zhuo-Qun; Taylor, Gordon T.; Fischer, Daniel A.; Appenzeller, Joerg; Harrison, Robert J.; Wong, Stanislaus S.

    2016-07-01

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

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

    SciTech Connect

    Wang, Lei; Han, Jinkyu; Sundahl, Bryan; Thornton, Scott; Zhu, Yuqi; Zhou, Ruiping; Jaye, Cherno; Liu, Haiqing; Li, Zhuo-Qun; Taylor, Gordon T.; Fischer, Daniel A.; Appenzeller, Joerg; Harrison, Robert J.; Wong, Stanislaus S.

    2016-07-01

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

  18. Complex formation between polyelectrolytes and oppositely charged oligoelectrolytes

    NASA Astrophysics Data System (ADS)

    Zhou, Jiajia; Barz, Matthias; Schmid, Friederike

    2016-04-01

    We study the complex formation between one long polyanion chain and many short oligocation chains by computer simulations. We employ a coarse-grained bead-spring model for the polyelectrolyte chains and model explicitly the small salt ions. We systematically vary the concentration and the length of the oligocation and examine how the oligocations affects the chain conformation, the static structure factor, the radial and axial distribution of various charged species, and the number of bound ions in the complex. At low oligocation concentration, the polyanion has an extended structure. Upon increasing the oligocation concentration, the polyanion chain collapses and forms a compact globule, but the complex still carries a net negative charge. Once the total charge of the oligocations is equal to that of the polyanion, the collapse stops and is replaced by a slow expansion. In this regime, the net charge on the complexes is positive or neutral, depending on the microion concentration in solution. The expansion can be explained by the reduction of the oligocation bridging. We find that the behavior and the structure of the complex are largely independent of the length of oligocations, and very similar to that observed when replacing the oligocations by multivalent salt cations, and conclude that the main driving force keeping the complex together is the release of monovalent counterions and coions. We speculate on the implications of this finding for the problem of controlled oligolyte release and oligolyte substitution.

  19. Laser Studies of - and Charge-Transfer Dynamics

    NASA Astrophysics Data System (ADS)

    Goldman, Jay Robert

    This thesis presents the results of three experiments which use lasers to investigate energy-transfer and charge -transfer dynamics. The dynamical processes studied include nanosecond vibrational energy transfer in molecules, subpicosecond electron relaxation in semiconductors, and subpicosecond initiation of surface bimolecular reactions on a metal crystal. In experiments using time-resolved coherent Raman spectroscopy to probe infrared multiphoton excited molecules, we study CO_2-laser excited SO _2 and SF_6. In SO _2 we observe direct nu _1-mode excitation and distinguish between this process and excitation of the nearly resonant nu_2-mode overtone. In SF _6, we directly observe nu _3-mode excitation followed by collisional energy redistribution to a heat bath of non-pumped modes. Quantitative modeling of the SF_6^ectra yields excited vibrational population distributions and resolves some long-standing inconsistencies between different previously published reports. In an experiment using time-resolved photoelectron spectroscopy, we observe the subpicosecond evolution of an optically-excited nonequilibrium electron distribution in silicon. We observe an electron thermalization time of less than 120 fs, electron equilibration with the lattice in 1 ps, and an energy-dependent electron cooling rate consistent with published calculations of the electron -phonon scattering rate. The results indicate the formation, in 1 ps, of a surface space-charge electron layer with an electron density two orders of magnitude greater than the bulk electron density. In an experiment using 100-fs laser pulses to induce desorption of O_2 and reaction of O_2+CO to form CO_2 on a Pt(111) surface, we present desorption and reaction data obtained over an absorbed fluence range of 1-20 mJ/cm_2 at wavelengths of 800, 400, and 266 nm. We observe a highly nonlinear desorption and reaction yield fluence dependence; the data are fit by a power law model in which the yield is proportional to

  20. Charge Transfer and Support Effects in Heterogeneous Catalysis

    SciTech Connect

    Hervier, Antoine

    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

  1. Complexation of Oppositely Charged Polyelctrolytes and Diblock Polyampholytes

    NASA Astrophysics Data System (ADS)

    Rubinstein, Michael

    2014-03-01

    The conformational properties of both symmetric and asymmetric flexible diblock polyampholytes and oppositely charged polyelectrolytes are investigated by molecular dynamics simulations and scaling theory. The electrostatically driven coil-globule transition of a symmetric diblock polyampholyte consist of three regimes identified with increasing electrostatic interaction strength: the folding regime, the weak association regime dominated by the fluctuation-induced attractions between oppositely charged sections of the chains, and the ion binding regime that starts with direct binding of oppositely charged monomers (dipole formation), followed by a cascade of multipole formation leading to multiplets analogous to those found in ionomers. In asymmetric block polyampholytes we find the globule to tadpole transition with the increase of charge asymmetry. In the weak association regime this transition is controlled by the balance of net charge and surface tension of the complex and characterized by the ratio of the difference in the number of electrostatic ``blobs'' between oppositely charged blocks and one third power of the total number of electrostatic blobs. We find the maximum overcharging of the complexes formed by either asymmetric diblock polyampholytes or by pairs of oppositely charged polyelectrolytes is by 50% independent of system parameters. We use scaling theory to estimate the average size of the complex and the electrostatic correlation length as functions of chains length, strength of electrostatic interactions, charge fractions, and solvent quality. The theoretically predicted scaling laws of these conformational properties are in good agreement with our simulation results. This work was done in collaboration with Dr. Zuowei Wang and supported by National Science Foundation and National Institutes of Health.

  2. Supramolecular assemblies built with host-stabilized charge-transfer interactions.

    PubMed

    Ko, Young Ho; Kim, Eunju; Hwang, Ilha; Kim, Kimoon

    2007-04-07

    Host-stabilized charge-transfer (CT) interactions and supramolecular assemblies built with these interactions are described. A variety of supramolecular assemblies including polyrotaxanes, molecular necklaces, and rotaxane dendrimers were synthesized through the intramolecular or intermolecular host-stabilized CT complex formation using cucurbit[8]uril (CB[8]) and D-A molecules having both electron-donor and electron-acceptor units connected by various types of linkers. Applications, including the design and synthesis of redox-driven molecular machines such as molecular loop locks, development of redox-controllable vesicles and detection of biologically important molecules, are also described.

  3. The role of charge transfer in the stability and reactivity of chemical systems from experimental findings.

    PubMed

    Falcinelli, S; Candori, P; Pirani, F; Vecchiocattivi, F

    2017-03-08

    A variety of phenomena, of apparently different natures, are described within a unifying picture, by properly isolating the role of charge/electron transfer as an interaction component triggering chemical reactivity. This basic quantity is isolated by analyzing, with advanced theoretical methods developed by our group, experimental findings characterized with different techniques, such as double photo-ionization spectra, scattering cross sections and auto-ionization reaction probabilities. Suitable rationalization of such phenomena appears to be crucial for modeling the selectivity of basic elementary processes occurring in systems at increasing complexity of fundamental/applied interest, such as plasmas, flames, interstellar media, planetary atmospheres and biological environments.

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

    NASA Technical Reports Server (NTRS)

    Kwong, Victor H. S.

    1996-01-01

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

  5. Scaling laws for charge transfer in multiply bridged donor/acceptor molecules in a dissipative environment.

    PubMed

    Goldsmith, Randall H; Wasielewski, Michael R; Ratner, Mark A

    2007-10-31

    The ability of multiple spatial pathways to sum coherently and facilitate charge transfer is examined theoretically. The role of multiple spatial pathways in mediating charge transfer has been invoked several times in the recent literature while discussing charge transfer in proteins, while multiple spatial pathways are known to contribute to charge transport in metal-molecule-metal junctions. We look at scaling laws for charge transfer in donor-bridge-acceptor (D-B-A) molecules and show that these scaling laws change significantly when environment-induced dephasing is included. In some cases, D-B-A systems are expected to show no enhancement in the rate of charge transfer with the addition of multiple degenerate pathways. The origins of these different scaling laws are investigated by looking at which Liouville space pathways are active in different dephasing regimes.

  6. Density functional investigation of the electronic structure and charge transfer excited states of a multichromophoric antenna

    NASA Astrophysics Data System (ADS)

    Basurto, Luis; Zope, Rajendra R.; Baruah, Tunna

    2016-05-01

    We report an electronic structure study of a multichromophoric molecular complex containing two of each borondipyrromethane dye, Zn-tetraphenyl-porphyrin, bisphenyl anthracene and a fullerene. The snowflake shaped molecule behaves like an antenna capturing photon at different frequencies and transferring the photon energy to the porphyrin where electron transfer occurs from the porphyrin to the fullerene. The study is performed within density functional formalism using large polarized Guassian basis sets (12,478 basis functions in total). The energies of the HOMO and LUMO states in the complex, as adjudged by the ionization potential and the electron affinity values, show significant differences with respect to their values in participating subunits in isolation. These differences are also larger than the variations of the ionization potential and electron affinity values observed in non-bonded C60-ZnTPP complexes in co-facial arrangement or end-on orientations. An understanding of the origin of these differences is obtained by a systematic study of the effect of structural strain, the presence of ligands, the effect of orbital delocalization on the ionization energy and the electron affinity. Finally, a few lowest charge transfer energies involving electronic transitions from the porphyrin component to the fullerene subunit of the complex are predicted.

  7. Complex quantum network model of energy transfer in photosynthetic complexes.

    PubMed

    Ai, Bao-Quan; Zhu, Shi-Liang

    2012-12-01

    The quantum network model with real variables is usually used to describe the excitation energy transfer (EET) in the Fenna-Matthews-Olson (FMO) complexes. In this paper we add the quantum phase factors to the hopping terms and find that the quantum phase factors play an important role in the EET. The quantum phase factors allow us to consider the space structure of the pigments. It is found that phase coherence within the complexes would allow quantum interference to affect the dynamics of the EET. There exist some optimal phase regions where the transfer efficiency takes its maxima, which indicates that when the pigments are optimally spaced, the exciton can pass through the FMO with perfect efficiency. Moreover, the optimal phase regions almost do not change with the environments. In addition, we find that the phase factors are useful in the EET just in the case of multiple pathways. Therefore, we demonstrate that the quantum phases may bring the other two factors, the optimal space of the pigments and multiple pathways, together to contribute the EET in photosynthetic complexes with perfect efficiency.

  8. Complexes of Negatively Charged Polypeptides with Cationic Lipids

    NASA Astrophysics Data System (ADS)

    Subramanian, G.; Li, Youli; Safinya, Cyrus R.

    1997-03-01

    Complexes of cationic lipids with oppositely charged proteins are promising candidates for new biomolecular materials. In addition to being used as a direct vehicle for protein transfection, they also find applications as templates for synthesis of molecular sieves. In spite of these wide ranging applications, the structure and interactions in these complexes have largely remained unclear. Here we report on the study of complexes formed between the cationic lipid didodecyldimethylammonium bromide (DDAB) with negatively charged polypeptide poly glutamic acid (PGA) both in the presence and absence of the neutral lipid dilauroylglycerophosphocholine (DLPC). X-ray diffraction of the complexes indicates a condensed lamellar lipid structure with the polypeptide intercalated between the layers. We present a comprehensive phase diagram on this system based on X-ray diffraction data. This work is supported in part by grants NSF DMR-9624091, PRF-31352 AC7, and CU LAR STP/UC 96-118.

  9. Evaluating Electronic Couplings for Excited State Charge Transfer Based on Maximum Occupation Method ΔSCF Quasi-Adiabatic States.

    PubMed

    Liu, Junzi; Zhang, Yong; Bao, Peng; Yi, Yuanping

    2017-02-14

    Electronic couplings of charge-transfer states with the ground state and localized excited states at the donor/acceptor interface are crucial parameters for controlling the dynamics of exciton dissociation and charge recombination processes in organic solar cells. Here we propose a quasi-adiabatic state approach to evaluate electronic couplings through combining maximum occupation method (mom)-ΔSCF and state diabatization schemes. Compared with time-dependent density functional theory (TDDFT) using global hybrid functional, mom-ΔSCF is superior to estimate the excitation energies of charge-transfer states; moreover it can also provide good excited electronic state for property calculation. Our approach is hence reliable to evaluate electronic couplings for excited state electron transfer processes, which is demonstrated by calculations on a typical organic photovoltaic system, oligothiophene/perylenediimide complex.

  10. Mechanisms of proton transfer in proteins: Localized charge transfer versus delocalized soliton transfer

    PubMed Central

    Stuchebrukhov, Alexei A.

    2010-01-01

    Proton translocation coupled to redox chemistry is ubiquitous for membrane enzymes involved in energy generation in cells. In such enzymes, proton transport occurs in special proton conducting channels, which consist of a series of protonatable groups of the protein connected by chains of mobile water molecules. Here we discuss two possible mechanisms of proton transport along such structures: diffusion of a localized charge and delocalized soliton transitions, in which several protons are collectively shifted along a chain of hydrogen bonds. PMID:19391991

  11. Bond patterns and charge-order amplitude in quarter-filled charge-transfer solids

    NASA Astrophysics Data System (ADS)

    Clay, R. T.; Ward, A. B.; Gomes, N.; Mazumdar, S.

    2017-03-01

    Most quasi-one-dimensional (quasi-1D) quarter-filled organic charge-transfer solids (CTS) with insulating ground states have two thermodynamic transitions: a high-temperature metal-insulator transition followed by a low-temperature magnetic transition. This sequence of transitions can be understood within the 1D Peierls-extended Hubbard (PEH) model. However, in some quasi-1D CTS both transitions occur simultaneously in a direct metal to spin-gapped insulator transition. In this second class of materials the organic stack bond distortion pattern does not follow the pattern of a second dimerization of a dimer lattice. These materials also display charge ordering of a large amplitude below the transition. Using quantum Monte Carlo methods we show that the same PEH model can be used to understand both classes of materials, however, within different parameter regions. We discuss the relevance of our work to experiments on several quarter-filled conductors, focusing in particular on the materials (EDO-TTF)2X and (DMEDO-TTF)2X .

  12. Charge transport in columnar stacked triphenylenes: Effects of conformational fluctuations on charge transfer integrals and site energies

    NASA Astrophysics Data System (ADS)

    Senthilkumar, K.; Grozema, F. C.; Bickelhaupt, F. M.; Siebbeles, L. D. A.

    2003-11-01

    Values of charge transfer integrals, spatial overlap integrals and site energies involved in transport of positive charges along columnar stacked triphenylene derivatives are provided. These parameters were calculated directly as the matrix elements of the Kohn-Sham Hamiltonian, defined in terms of the molecular orbitals on individual triphenylene molecules. This was realized by exploiting the unique feature of the Amsterdam density functional theory program that allows one to use molecular orbitals on individual molecules as a basis set in calculations on a system composed of two or more molecules. The charge transfer integrals obtained in this way differ significantly from values estimated from the energy splitting between the highest occupied molecular orbitals in a dimer. The difference is due to the nonzero spatial overlap between the molecular orbitals on adjacent molecules. Calculations were performed on unsubstituted and methoxy- or methylthio-substituted triphenylenes. Charge transfer integrals and site energies were computed as a function of the twist angle, stacking distance and lateral slide distance between adjacent molecules. The variation of the charge transfer integrals and site energies with these conformational degrees of freedom provide a qualitative explanation of the similarities and differences between the experimental charge carrier mobilities in different phases of alkoxy- and alkylthio-substituted triphenylenes. The data obtained from the present work can be used as input in quantitative studies of charge transport in columnar stacked triphenylene derivatives.

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

    PubMed

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

    2015-04-21

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

  14. Branched-linear polyion complexes at variable charge densities

    NASA Astrophysics Data System (ADS)

    Angelescu, Daniel G.; Linse, Per

    2015-08-01

    Structural behavior of complexes formed by a charged and branched copolymer and an oppositely charged and linear polyion was examined by Monte Carlo simulations employing a coarse-grained bead-spring model. The fractional bead charge and the branching density were systematically varied; the former between 0e and 1e and the latter such that both the comb-polymer and the bottle-brush limits were included. The number of beads of the main chain of the branched copolymer and of the linear polyion was always kept constant and equal, and a single side-chain length was used. Our analysis involved characterization of the complex as well as investigation of size, shape, and flexibility of the charged moieties. An interplay between Coulomb interaction and side-chain repulsion governed the structure of the polyion complex. At strong Coulomb interaction, the complexes underwent a gradual transition from a globular structure at low branching density to an extended one at high branching density. As the electrostatic coupling was decreased, the transition was smoothened and shifted to lower branching density, and, eventually, a behavior similar to that found for neutral branched polymer was observed. Structural analogies and dissimilarities with uncharged branched polymers in poor solutions are discussed.

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

    NASA Astrophysics Data System (ADS)

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

    2015-02-01

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

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

    PubMed

    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.

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

    DOE PAGES

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

    2016-05-10

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

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

    SciTech Connect

    Wang, Han; Bang, Junhyeok; Sun, Yiyang; West, Damien; Meunier, Vincent; Zhang, Shengbai; Liang, Linagbo

    2016-05-10

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

  19. Charge transfer in Sr Zintl template on Si(001)

    NASA Astrophysics Data System (ADS)

    Choi, Miri; Posadas, Agham B.; Seo, Hosung; Hatch, Richard C.; Demkov, Alexander A.

    2013-01-01

    The formation of the half monolayer (ML) Sr Zintl template layer on Si(001) is investigated in a combined experimental and theoretical work consisting of in situ reflection high energy electron diffraction, in situ x-ray photoelectron spectroscopy (XPS), and density functional theory. Starting with clean 2 × 1 reconstructed Si(001), we demonstrate that Sr deposition leads to a charge transfer from the metal to the Si substrate resulting in the disappearance of the asymmetry of Si dimers—an essential structural change that enables direct perovskite epitaxy on Si, and likely, other semiconductors. XPS reveals an unexpected shift to higher binding energy of the Si 2p core-level components, including the bulk. This unusual behavior is attributed to final state effects using first principles calculations. As measured by ultraviolet photoelectron spectroscopy, the deposition of 0.5 ML of Sr lowers the work function of the system by 1.35 eV, and is in good agreement with our theoretical calculations.

  20. Identifying interfacial charge transfer states in organic heterostructures (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Arndt, Andreas P.; Gerhard, Marina; Howard, Ian A.; Koch, Martin; Lemmer, Ulrich

    2016-09-01

    Charge transfer (CT) states play evidently an important role at the interface of organic heterostructures but their identification and characterization is often experimentally less obvious and challenging. We studied two exemplary material systems which both represented a benchmark within the research of organic photovoltaics at their time: the homopolymer P3HT blended with PC61BM and the copolymer PTB7 blended with PC71BM. In both heterostructures, we could identify a distinct CT state emission by the use of NIR time-resolved photoluminescence (PL) [1], [2]. The selectivity of this technique enables us to clearly probe the energetics and dynamics of weak emitting interfacial states and therefore to prove differences in the CT state characteristics between the two systems. We went beyond this previous work and investigated the time and temperature dependent emission anisotropy as well as the electric field dependence of the time-resolved PL for both blends and the pristine polymers, respectively. In both cases the CT state emission clearly deviates from the one of the primarily excited singlet excitons: the emission anisotropy reveals an additional relaxation pathway for the exciton which is connected with a change of the transition dipole moment of the emission, and under applied bias different quenching thresholds can give access to varying binding energies of the emissive excitons involved. Finally, we think that our findings demonstrate how interfacial CT state emission can be clearly identified as such and how it can be unambiguously distinguished from singlet exciton emission.

  1. Dynamic Peptide Library for the Discovery of Charge Transfer Hydrogels.

    PubMed

    Berdugo, Cristina; Nalluri, Siva Krishna Mohan; Javid, Nadeem; Escuder, Beatriu; Miravet, Juan F; Ulijn, Rein V

    2015-11-25

    Coupling of peptide self-assembly to dynamic sequence exchange provides a useful approach for the discovery of self-assembling materials. In here, we demonstrate the discovery and optimization of aqueous, gel-phase nanostructures based on dynamically exchanging peptide sequences that self-select to maximize charge transfer of n-type semiconducting naphthalenediimide (NDI)-dipeptide bioconjugates with various π-electron-rich donors (dialkoxy/hydroxy/amino-naphthalene or pyrene derivatives). These gel-phase peptide libraries are characterized by spectroscopy (UV-vis and fluorescence), microscopy (TEM), HPLC, and oscillatory rheology and it is found that, of the various peptide sequences explored (tyrosine Y-NDI with tyrosine Y, phenylalanine F, leucine L, valine V, alanine A or glycine G-NH2), the optimum sequence is tyrosine-phenylalanine in each case; however, both its absolute and relative yield amplification is dictated by the properties of the donor component, indicating cooperativity of peptide sequence and donor/acceptor pairs in assembly. The methodology provides an in situ discovery tool for nanostructures that enable dynamic interfacing of supramolecular electronics with aqueous (biological) systems.

  2. Self-interaction effects on charge-transfer collisions

    DOE PAGES

    Quashie, Edwin E.; Saha, Bidhan C.; Andrade, Xavier; ...

    2017-04-27

    In this article, we investigate the role of the self-interaction error in the simulation of collisions using time-dependent density functional theory (TDDFT) and Ehrenfest dynamics. In addition, we compare many different approximations of the exchange and correlation potential, using as a test system the collision of H+ + CH4 at 30 eV. We find that semilocal approximations, like the Perdew-Burke- Ernzerhof (PBE), and even hybrid functionals, such as the Becke, 3-parameter, Lee-Yang-Parr (B3LYP), produce qualitatively incorrect predictions for the scattering of the proton. This discrepancy appears because the self-interaction error allows the electrons to jump too easily to the proton,more » leading to radically different forces with respect to the non-self-interacting case. Lastly, from our results, we conclude that using a functional that is self-interaction free is essential to properly describing charge-transfer collisions between ions and molecules in TDDFT.« less

  3. Charge transfer vibronic transitions in uranyl tetrachloride compounds;

    SciTech Connect

    Liu, G. K.; Deifel, N. P.; Cahill, C. L.

    2012-01-01

    The electronic and vibronic interactions of uranyl (UO{sub 2}){sup 2+} in three tetrachloride crystals have been investigated with spectroscopic experiments and theoretical modeling. Analysis and simulation of the absorption and photoluminescence spectra have resulted in a quantitative understanding of the charge transfer vibronic transitions of uranyl in the crystals. The spectra obtained at liquid helium temperature consist of extremely narrow zero-phonon lines (ZPL) and vibronic bands. The observed ZPLs are assigned to the first group of the excited states formed by electronic excitation from the 3{sigma} ground state into the f{sub {delta}{phi}}, orbitals of uranyl. The Huang-Rhys theory of vibronic coupling is modified successfully for simulating both the absorption and luminescence spectra. It is shown that only vibronic coupling to the axially symmetric stretching mode is Franck-Condon allowed, whereas other modes are involved through coupling with the symmetric stretching mode. The energies of electronic transitions, vibration frequencies of various local modes, and changes in the O=U=O bond length of uranyl in different electronic states and in different coordination geometries are evaluated in empirical simulations of the optical spectra. Multiple uranyl sites derived from the resolution of a superlattice at low temperature are resolved by crystallographic characterization and time- and energy-resolved spectroscopic studies. The present empirical simulation provides insights into fundamental understanding of uranyl electronic interactions and is useful for quantitative characterization of uranyl coordination.

  4. Charge transfer vibronic transitions in uranyl tetrachloride compounds

    SciTech Connect

    Liu, Guokui; Deifel, Nicholas P.; Cahill, Christopher L.; Zhurov, Vladimir V.; Pinkerton, A. Alan

    2012-01-01

    The electronic and vibronic interactions of uranyl (UO₂)2+ in three tetrachloride crystals have been investigated with spectroscopic experiments and theoretical modeling. Analysis and simulation of the absorption and photoluminescence spectra have resulted in a quantitative understanding of the charge transfer vibronic transitions of uranyl in the crystals. The spectra obtained at liquid helium temperature consist of extremely narrow zero-phonon lines (ZPL) and vibronic bands. The observed ZPLs are assigned to the first group of the excited states formed by electronic excitation from the 3σ ground state into the fδ,Φ orbitals of uranyl. The Huang–Rhys theory of vibronic coupling is modified successfully for simulating both the absorption and luminescence spectra. It is shown that only vibronic coupling to the axially symmetric stretching mode is Franck–Condon allowed, whereas other modes are involved through coupling with the symmetric stretching mode. The energies of electronic transitions, vibration frequencies of various local modes, and changes in the O=U=O bond length of uranyl in different electronic states and in different coordination geometries are evaluated in empirical simulations of the optical spectra. Multiple uranyl sites derived from the resolution of a superlattice at low temperature are resolved by crystallographic characterization and time- and energy-resolved spectroscopic studies. The present empirical simulation provides insights into fundamental understanding of uranyl electronic interactions and is useful for quantitative characterization of uranyl coordination.

  5. Satellite lines at the ionization threshold in charge transfer systems

    NASA Astrophysics Data System (ADS)

    Wardermann, W.; von Niessen, W.

    1992-01-01

    This article deals with the possibility of low-energy ionizations of reduced intensity for larger organic molecules. Possible mechanisms which may lead to this phenomenon are outlined and the necessary structural features are discussed. The lowest ionization energies of some organic unsaturated nitro and nitroso compounds are calculated by the ADC(3) ab initio many-body Green's function method. The π-electron system consists either of fused five- and six-membered rings or of two fused five-membered rings with a variable number of heteroatoms. Some of the molecules contain exocylic double bonds and some are substituted with the donor groups -NH 2, -OH and -NHOH. The strongest many-body effects are found for the nitroso compounds, where in one case the spectral line at the ionization threshold has lost more than 40% of its intensity to satellites. We study the many-body effects at or close to the ionization threshold for these compounds. A particular mechanism which involves the screening of localized valence holes by charge transfer excitations appears to be capable of influencing the profile and intensities of the ionization spectrum already at the ionization threshold. The effect leads to strongly reduced relative intensities of the bands and may cause the appearance of satellite bands nearly at the ionization threshold. The spectral changes in the outermost valence region are discussed by using a simple model calculation in terms of ground-state electronic properties of the molecules.

  6. Quantifying the intrinsic surface charge density and charge-transfer resistance of the graphene-solution interface through bias-free low-level charge measurement

    NASA Astrophysics Data System (ADS)

    Ping, Jinglei; Johnson, A. T. Charlie

    2016-07-01

    Liquid-based bio-applications of graphene require a quantitative understanding of the graphene-liquid interface, with the surface charge density of adsorbed ions, the interfacial charge transfer resistance, and the interfacial charge noise being of particular importance. We quantified these properties through measurements of the zero-bias Faradaic charge-transfer between graphene electrodes and aqueous solutions of varying ionic strength using a reproducible, low-noise, minimally perturbative charge measurement technique. The measurements indicated that the adsorbed ions had a negative surface charge density of approximately -32.8 mC m-2 and that the specific charge transfer resistance was 6.5 ± 0.3 MΩ cm2. The normalized current noise power spectral density for all ionic concentrations tested collapsed onto a 1/fα characteristic with α = 1.1 ± 0.2. All the results are in excellent agreement with predictions of the theory for the graphene-solution interface. This minimally perturbative method for monitoring charge-transfer at the sub-pC scale exhibits low noise and ultra-low power consumption (˜fW), making it suitable for use in low-level bioelectronics in liquid environments.

  7. Infrared intensities and charge mobility in hydrogen bonded complexes

    SciTech Connect

    Galimberti, Daria; Milani, Alberto; Castiglioni, Chiara

    2013-08-21

    The analytical model for the study of charge mobility in the molecules presented by Galimberti et al.[J. Chem. Phys. 138, 164115 (2013)] is applied to hydrogen bonded planar dimers. Atomic charges and charge fluxes are obtained from density functional theory computed atomic polar tensors and related first derivatives, thus providing an interpretation of the IR intensity enhancement of the X–H stretching band observed upon aggregation. Our results show that both principal and non-principal charge fluxes have an important role for the rationalization of the spectral behavior; moreover, they demonstrate that the modulation of the charge distribution during vibrational motions of the –XH⋯Y– fragment is not localized exclusively on the atoms directly involved in hydrogen bonding. With these premises we made some correlations between IR intensities, interaction energies, and charge fluxes. The model was tested on small dimers and subsequently to the bigger one cytosine-guanine. Thus, the model can be applied to complex systems.

  8. Magnetically coupled resonance wireless charging technology principles and transfer mechanisms

    NASA Astrophysics Data System (ADS)

    Zhou, Jiehua; Wan, Jian; Ma, Yinping

    2017-05-01

    With the tenure of Electric-Vehicle rising around the world, the charging methods have been paid more and more attention, the current charging mode mainly has the charging posts and battery swapping station. The construction of the charging pile or battery swapping station not only require lots of manpower, material costs but the bare conductor is also easy to generate electric spark hidden safety problems, still occupies large space. Compared with the wired charging, wireless charging mode is flexible, unlimited space and location factors and charging for vehicle safety and quickly. It complements the traditional charging methods in adaptability and the independent charge deficiencies. So the researching the wireless charging system have an important practical significance and application value. In this paper, wireless charging system designed is divided into three parts: the primary side, secondary side and resonant coupling. The main function of the primary side is to generate high-frequency alternating current, so selecting CLASS-E amplifier inverter structure through the research on full bridge, half-bridge and power amplification circuit. Addition, the wireless charging system is susceptible to outside interference, frequency drift phenomenon. Combined with the wireless energy transmission characteristics, resonant parts adopt resonant coupling energy transmission scheme and the Series-Series coupling compensation structure. For the electric vehicle charging power and voltage requirements, the main circuit is a full bridge inverter and Boost circuit used as the secondary side.

  9. An efficient fluctuating charge model for transition metal complexes.

    PubMed

    Comba, Peter; Martin, Bodo; Sanyal, Avik

    2013-07-05

    A fluctuating charge model for transition metal complexes, based on the Hirshfeld partitioning scheme, spectroscopic energy data from the NIST Atomic Spectroscopy Database and the electronegativity equalization approach, has been developed and parameterized for organic ligands and their high- and low-spin Fe(II) and Fe(III), low-spin Co(III) and Cu(II) complexes, using atom types defined in the Momec force field. Based on large training sets comprising a variety of transition metal complexes, a general parameter set has been developed and independently validated which allows the efficient computation of geometry-dependent charge distributions in the field of transition metal coordination compounds. Copyright © 2013 Wiley Periodicals, Inc.

  10. Excited charge transfer states in 4-aminopyrimidines, 4-(dimethylanilino)pyrimidine and 4-(dimethylamino)pyridine

    NASA Astrophysics Data System (ADS)

    Herbich, Jerzy; Waluk, Jacek

    1994-11-01

    This paper presents a comparative study of the photoinduced electron transfer in a series of donor-acceptor compounds and their hydrogen-bonded complexes in solution. 4-(Dimethylamino)pyridine III, similarly to 4-(dimethylamino)pyrimidine I and 4-(dimethylamino)-5-methylpyrimidine II and contrary to 4-(N,N-dimethylanilino)pyrimidine IV, shows dual luminescence in a sufficiently polar and mobile environment. The results of steady-state and kinetic investigations as well as quantum chemical calculations of I-III fit well into the twisted intramolecular charge transfer (TICT) state model. On the other hand, the results suggest an enhanced planarity of the ICT fluorescent state of IV. INDO/S calculations confirm the large probability of the allowed radiative transitions in the latter compound. Photophysics of all the compounds under study is modified by hydrogen bonding: fluorescence quantum yields are strongly reduced in the presence of alcohols.

  11. Excited charge transfer states in 4-aminopyrimidines, 4-(dimethylanilino)pyrimidine and 4-(dimethylamino)pyridne

    NASA Astrophysics Data System (ADS)

    Herbich, Jerzy; Waluk, Jacek

    1994-11-01

    This paper presents a comparative study of the photoinduced electron transfer in a series of donor-acceptor compounds and their hydrogen-bonded complexes in solution. 4-(Dimethylamino) pyridine III, similarly to 4-(dimethylamino) pyrimidine I and 4-(dimethylamino)-5-methylpyrimidine II and contrary to 4-(N,N-dimethylanilino)pyrimidine IV, shows dual luminescence in a sufficiently polar and mobile environment. The results of steady-state and kinetic investigations as well as quantum chemical calculations of I-III fit well into the twisted intramolecular charge transfer (TICT) state model. On the other hand, the results suggest an enhanced planarity of the ICT fluorescent state of IV. INDO/S calculations confirm the large probability of the allowed radiative transitions in the latter compound. Photophysics of all the compounds under study is modified by hydrogen bonding: fluorescence quantum yields are strongly reduced in the presence of alcohols.

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

    PubMed

    Yukihira, Nao; Sugai, Yuko; Fujiwara, Masazumi; Kosumi, Daisuke; Iha, Masahiko; Sakaguchi, Kazuhiko; Katsumura, Shigeo; Gardiner, Alastair T; Cogdell, Richard J; Hashimoto, Hideki

    2017-03-15

    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 chlorophyll a in 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 rubrum G9+ (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 bacteriochlorophyll a when they are bound to the light-harvesting 1 apo-proteins.

  13. Photo-reactive charge trapping memory based on lanthanide complex.

    PubMed

    Zhuang, Jiaqing; Lo, Wai-Sum; Zhou, Li; Sun, Qi-Jun; Chan, Chi-Fai; Zhou, Ye; Han, Su-Ting; Yan, Yan; Wong, Wing-Tak; Wong, Ka-Leung; Roy, V A L

    2015-10-09

    Traditional utilization of photo-induced excitons is popularly but restricted in the fields of photovoltaic devices as well as photodetectors, and efforts on broadening its function have always been attempted. However, rare reports are available on organic field effect transistor (OFET) memory employing photo-induced charges. Here, we demonstrate an OFET memory containing a novel organic lanthanide complex Eu(tta)3ppta (Eu(tta)3 = Europium(III) thenoyltrifluoroacetonate, ppta = 2-phenyl-4,6-bis(pyrazol-1-yl)-1,3,5-triazine), in which the photo-induced charges can be successfully trapped and detrapped. The luminescent complex emits intense red emission upon ultraviolet (UV) light excitation and serves as a trapping element of holes injected from the pentacene semiconductor layer. Memory window can be significantly enlarged by light-assisted programming and erasing procedures, during which the photo-induced excitons in the semiconductor layer are separated by voltage bias. The enhancement of memory window is attributed to the increasing number of photo-induced excitons by the UV light. The charges are stored in this luminescent complex for at least 10(4) s after withdrawing voltage bias. The present study on photo-assisted novel memory may motivate the research on a new type of light tunable charge trapping photo-reactive memory devices.

  14. Photo-reactive charge trapping memory based on lanthanide complex

    NASA Astrophysics Data System (ADS)

    Zhuang, Jiaqing; Lo, Wai-Sum; Zhou, Li; Sun, Qi-Jun; Chan, Chi-Fai; Zhou, Ye; Han, Su-Ting; Yan, Yan; Wong, Wing-Tak; Wong, Ka-Leung; Roy, V. A. L.

    2015-10-01

    Traditional utilization of photo-induced excitons is popularly but restricted in the fields of photovoltaic devices as well as photodetectors, and efforts on broadening its function have always been attempted. However, rare reports are available on organic field effect transistor (OFET) memory employing photo-induced charges. Here, we demonstrate an OFET memory containing a novel organic lanthanide complex Eu(tta)3ppta (Eu(tta)3 = Europium(III) thenoyltrifluoroacetonate, ppta = 2-phenyl-4,6-bis(pyrazol-1-yl)-1,3,5-triazine), in which the photo-induced charges can be successfully trapped and detrapped. The luminescent complex emits intense red emission upon ultraviolet (UV) light excitation and serves as a trapping element of holes injected from the pentacene semiconductor layer. Memory window can be significantly enlarged by light-assisted programming and erasing procedures, during which the photo-induced excitons in the semiconductor layer are separated by voltage bias. The enhancement of memory window is attributed to the increasing number of photo-induced excitons by the UV light. The charges are stored in this luminescent complex for at least 104 s after withdrawing voltage bias. The present study on photo-assisted novel memory may motivate the research on a new type of light tunable charge trapping photo-reactive memory devices.

  15. Photo-reactive charge trapping memory based on lanthanide complex

    PubMed Central

    Zhuang, Jiaqing; Lo, Wai-Sum; Zhou, Li; Sun, Qi-Jun; Chan, Chi-Fai; Zhou, Ye; Han, Su-Ting; Yan, Yan; Wong, Wing-Tak; Wong, Ka-Leung; Roy, V. A. L.

    2015-01-01

    Traditional utilization of photo-induced excitons is popularly but restricted in the fields of photovoltaic devices as well as photodetectors, and efforts on broadening its function have always been attempted. However, rare reports are available on organic field effect transistor (OFET) memory employing photo-induced charges. Here, we demonstrate an OFET memory containing a novel organic lanthanide complex Eu(tta)3ppta (Eu(tta)3 = Europium(III) thenoyltrifluoroacetonate, ppta = 2-phenyl-4,6-bis(pyrazol-1-yl)-1,3,5-triazine), in which the photo-induced charges can be successfully trapped and detrapped. The luminescent complex emits intense red emission upon ultraviolet (UV) light excitation and serves as a trapping element of holes injected from the pentacene semiconductor layer. Memory window can be significantly enlarged by light-assisted programming and erasing procedures, during which the photo-induced excitons in the semiconductor layer are separated by voltage bias. The enhancement of memory window is attributed to the increasing number of photo-induced excitons by the UV light. The charges are stored in this luminescent complex for at least 104 s after withdrawing voltage bias. The present study on photo-assisted novel memory may motivate the research on a new type of light tunable charge trapping photo-reactive memory devices. PMID:26449199

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

    NASA Astrophysics Data System (ADS)

    Morherr, Antonia; Witt, Sebastian; Chernenkaya, Alisa; Bäcker, Jan-Peter; Schönhense, Gerd; Bolte, Michael; Krellner, Cornelius

    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-Fx, 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.

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

    PubMed

    Wang, Han; Bang, Junhyeok; Sun, Yiyang; Liang, Liangbo; West, Damien; Meunier, Vincent; Zhang, Shengbai

    2016-05-10

    The success of van der Waals heterostructures made of graphene, metal dichalcogenides and other layered materials, hinges on the understanding of charge transfer across the interface as the foundation for new device concepts and applications. In contrast to conventional heterostructures, where a strong interfacial coupling is essential to charge transfer, recent experimental findings indicate that van der Waals heterostructues can exhibit ultrafast charge transfer despite the weak binding of these heterostructures. Here we find, using time-dependent density functional theory molecular dynamics, that the collective motion of excitons at the interface leads to plasma oscillations associated with optical excitation. By constructing a simple model of the van der Waals heterostructure, we show that there exists an unexpected criticality of the oscillations, yielding rapid charge transfer across the interface. Application to the MoS2/WS2 heterostructure yields good agreement with experiments, indicating near complete charge transfer within a timescale of 100 fs.

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

    PubMed Central

    Wang, Han; Bang, Junhyeok; Sun, Yiyang; Liang, Liangbo; West, Damien; Meunier, Vincent; Zhang, Shengbai

    2016-01-01

    The success of van der Waals heterostructures made of graphene, metal dichalcogenides and other layered materials, hinges on the understanding of charge transfer across the interface as the foundation for new device concepts and applications. In contrast to conventional heterostructures, where a strong interfacial coupling is essential to charge transfer, recent experimental findings indicate that van der Waals heterostructues can exhibit ultrafast charge transfer despite the weak binding of these heterostructures. Here we find, using time-dependent density functional theory molecular dynamics, that the collective motion of excitons at the interface leads to plasma oscillations associated with optical excitation. By constructing a simple model of the van der Waals heterostructure, we show that there exists an unexpected criticality of the oscillations, yielding rapid charge transfer across the interface. Application to the MoS2/WS2 heterostructure yields good agreement with experiments, indicating near complete charge transfer within a timescale of 100 fs. PMID:27160484

  19. Switching of the fluorescence emission of single molecules between the locally excited and charge transfer states

    NASA Astrophysics Data System (ADS)

    Angeles Izquierdo, M.; Bell, Toby D. M.; Habuchi, Satoshi; Fron, Eduard; Pilot, Roberto; Vosch, Tom; De Feyter, Steven; Verhoeven, Jan; Jacob, Josemon; Müllen, Klaus; Hofkens, Johan; De Schryver, Frans C.

    2005-01-01

    A novel perylene imide and oligo-pentaphenyl bisfluorene containing molecule is shown to undergo electron transfer to form an emissive charge transfer state in di-benzyl ether and THF. At the single molecule level in a PMMA film, fluorescence spectra characteristic of both emissive states (locally excited and charge transfer) are observed with 44% of the molecules studied showing switching between the two states. These results demonstrate that charge transfer fluorescence from single molecules can be used to report on the properties and dynamics of a molecule's immediate surroundings or nano-environment.

  20. 46 CFR 35.35-35 - Duties of person in charge of transfer-TB/ALL.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 46 Shipping 1 2013-10-01 2013-10-01 false Duties of person in charge of transfer-TB/ALL. 35.35-35 Section 35.35-35 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY TANK VESSELS OPERATIONS Cargo Handling § 35.35-35 Duties of person in charge of transfer—TB/ALL. The person in charge of the transfer of...

  1. 46 CFR 35.35-35 - Duties of person in charge of transfer-TB/ALL.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 46 Shipping 1 2011-10-01 2011-10-01 false Duties of person in charge of transfer-TB/ALL. 35.35-35 Section 35.35-35 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY TANK VESSELS OPERATIONS Cargo Handling § 35.35-35 Duties of person in charge of transfer—TB/ALL. The person in charge of the transfer of...

  2. 46 CFR 35.35-35 - Duties of person in charge of transfer-TB/ALL.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 46 Shipping 1 2010-10-01 2010-10-01 false Duties of person in charge of transfer-TB/ALL. 35.35-35 Section 35.35-35 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY TANK VESSELS OPERATIONS Cargo Handling § 35.35-35 Duties of person in charge of transfer—TB/ALL. The person in charge of the transfer of...

  3. 46 CFR 35.35-35 - Duties of person in charge of transfer-TB/ALL.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 46 Shipping 1 2012-10-01 2012-10-01 false Duties of person in charge of transfer-TB/ALL. 35.35-35 Section 35.35-35 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY TANK VESSELS OPERATIONS Cargo Handling § 35.35-35 Duties of person in charge of transfer—TB/ALL. The person in charge of the transfer of...

  4. 46 CFR 35.35-35 - Duties of person in charge of transfer-TB/ALL.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 46 Shipping 1 2014-10-01 2014-10-01 false Duties of person in charge of transfer-TB/ALL. 35.35-35 Section 35.35-35 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY TANK VESSELS OPERATIONS Cargo Handling § 35.35-35 Duties of person in charge of transfer—TB/ALL. The person in charge of the transfer of...

  5. Charge-transfer excitons at organic semiconductor surfaces and interfaces.

    PubMed

    Zhu, X-Y; Yang, Q; Muntwiler, M

    2009-11-17

    When a material of low dielectric constant is excited electronically from the absorption of a photon, the Coulomb attraction between the excited electron and the hole gives rise to an atomic H-like quasi-particle called an exciton. The bound electron-hole pair also forms across a material interface, such as the donor/acceptor interface in an organic heterojunction solar cell; the result is a charge-transfer (CT) exciton. On the basis of typical dielectric constants of organic semiconductors and the sizes of conjugated molecules, one can estimate that the binding energy of a CT exciton across a donor/acceptor interface is 1 order of magnitude greater than k(B)T at room temperature (k(B) is the Boltzmann constant and T is the temperature). How can the electron-hole pair escape this Coulomb trap in a successful photovoltaic device? To answer this question, we use a crystalline pentacene thin film as a model system and the ubiquitous image band on the surface as the electron acceptor. We observe, in time-resolved two-photon photoemission, a series of CT excitons with binding energies < or = 0.5 eV below the image band minimum. These CT excitons are essential solutions to the atomic H-like Schrodinger equation with cylindrical symmetry. They are characterized by principal and angular momentum quantum numbers. The binding energy of the lowest lying CT exciton with 1s character is more than 1 order of magnitude higher than k(B)T at room temperature. The CT(1s) exciton is essentially the so-called exciplex and has a very low probability of dissociation. We conclude that hot CT exciton states must be involved in charge separation in organic heterojunction solar cells because (1) in comparison to CT(1s), hot CT excitons are more weakly bound by the Coulomb potential and more easily dissociated, (2) density-of-states of these hot excitons increase with energy in the Coulomb potential, and (3) electronic coupling from a donor exciton to a hot CT exciton across the D

  6. A statewide teleradiology system reduces radiation exposure and charges in transferred trauma patients.

    PubMed

    Watson, Justin J J; Moren, Alexis; Diggs, Brian; Houser, Ben; Eastes, Lynn; Brand, Dawn; Bilyeu, Pamela; Schreiber, Martin; Kiraly, Laszlo

    2016-05-01

    Trauma transfer patients routinely undergo repeat imaging because of inefficiencies within the radiology system. In 2009, the virtual private network (VPN) telemedicine system was adopted throughout Oregon allowing virtual image transfer between hospitals. The startup cost was a nominal $3,000 per hospital. A retrospective review from 2007 to 2012 included 400 randomly selected adult trauma transfer patients based on a power analysis (200 pre/200 post). The primary outcome evaluated was reduction in repeat computed tomography (CT) scans. Secondary outcomes included cost savings, emergency department (ED) length of stay (LOS), and spared radiation. All data were analyzed using Mann-Whitney U and chi-square tests. P less than .05 indicated significance. Spared radiation was calculated as a weighted average per body region, and savings was calculated using charges obtained from Oregon Health and Science University radiology current procedural terminology codes. Four-hundred patients were included. Injury Severity Score, age, ED and overall LOS, mortality, trauma type, and gender were not statistically different between groups. The percentage of patients with repeat CT scans decreased after VPN implementation: CT abdomen (13.2% vs 2.8%, P < .01) and cervical spine (34.4% vs 18.2%, P < .01). Post-VPN, the total charges saved in 2012 for trauma transfer patients was $333,500, whereas the average radiation dose spared per person was 1.8 mSV. Length of stay in the ED for patients with Injury Severity Score less than 15 transferring to the ICU was decreased (P < .05). Implementation of a statewide teleradiology network resulted in fewer total repeat CT scans, significant savings, decrease in radiation exposure, and decreased LOS in the ED for patients with less complex injuries. The potential for health care savings by widespread adoption of a VPN is significant. Copyright © 2016 Elsevier Inc. All rights reserved.

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

    NASA Astrophysics Data System (ADS)

    Hendrickson, Heidi Phillips

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

  8. Orbital analysis of metal-to-ligand charge transfer and oxidation in (NH{sub 3}){sub 5}RuL{sup 2+} complexes: Effective t{sub 2g} orbital ordering and the role of ligand {pi} and {pi}{sup *} orbitals

    SciTech Connect

    Shin, Y.G.K.; Brunschwig, B.S.; Creutz, C.; Newton, M.D.; Sutin, N.

    1996-01-25

    Both metal-to-ligand charge transfer(MLCT) and oxidation(ionization) processes have been investigated for (NH{sub 3}){sub 5}RuL{sup 2+} complexes with L = pyridine, pyrazine, and protonated pyrazine. Calculations were carried out using ZINDO-95. Self-consistent-field molecular orbitals (MO`s) were obtained at the restricted Hartree-Fock level for the closed-shell ground state (t{sub 2g}){sup 6} (NH{sub 3}){sub 5}RuL{sup 2+} species. The MLCT wave functions and excitation energies were obtained by configuration interaction among all singlet configurations generated by single excitations from the highest 11 occupied MO`s to the lowest 11 unoccupied MO`s. We find that the Ru(II)d{sub {pi}} orbital is the HOMO for all three complexes. The results provide clear indication that the relative energies for removing an electron from the three types of t{sub 2g} orbital depend on the effective distance that the electron is transferred. For relatively long-distance transfers (e.g., > 5 A as for intra- or intermolecular thermal or optical electron transfer to a weakly coupled Ru(III) site), the lowest energy process involves the d{sub {pi}} orbital. In contrast, for the shorter range MLCT process, for which the electron interacts with the newly created hole to an extent determined by the relevant Coulomb and exchange integrals, the d{sub {pi}} orbital participates in the highest energy of the three possible t{sub 2g} {yields} L{sub {pi}(*)} excitations. 52 refs., 2 figs., 5 tabs.

  9. Theoretical and experimental study of charge transfer through DNA: impact of mercury mediated T-Hg-T base pair.

    PubMed

    Kratochvílová, Irena; Golan, Martin; Vala, Martin; Špérová, Miroslava; Weiter, Martin; Páv, Ondřej; Šebera, Jakub; Rosenberg, Ivan; Sychrovský, Vladimír; Tanaka, Yoshiyuki; Bickelhaupt, F Matthias

    2014-05-22

    DNA-Hg complexes may play an important role in sensing DNA defects or in detecting the presence of Hg in the environment. A fundamental way of characterizing DNA-Hg complexes is to study the way the electric charge is transferred through the molecular chain. The main goal of this contribution was to investigate the impact of a mercury metal cation that links two thymine bases in a DNA T-T mismatched base pair (T-Hg-T) on charge transfer through the DNA molecule. We compared the charge transfer efficiencies in standard DNA, DNA with mismatched T-T base pairs, and DNA with a T-Hg(II)-T base pair. For this purpose, we measured the temperature dependence of steady-state fluorescence and UV-vis of the DNA molecules. The experimental results were confronted with the results obtained employing theoretical DFT methods. Generally, the efficiency of charge transfer was driven by mercury changing the spatial overlap of bases.

  10. WFC3/UVIS Charge Transfer Efficiency 2009-2015

    NASA Astrophysics Data System (ADS)

    Baggett, S.; Gosmeyer, C.; Noeske, K.

    2015-03-01

    The longterm behavior of the charge transfer efficiency (CTE) in WFC3/UVIS is monitored using observations of external star clusters. Flux loss due to CTE degradation is a function of the source's distance from the amplifier, the source signal level, the background within the image, and the epoch of the observations. The worst-case flux losses occur in images with extremely low backgrounds. In such data, based on photometry within a 3-pixel radius aperture and losses measured across 2048 pixels, the flux losses in early 2015 for faint sources (500-2000 e-) can be as high as ~50+/-2%; losses for brighter sources (8000-32000 e-) are considerably less: ~5 ±1%. Ensuring a modest amount of background can reduce the losses substantially: ~12e-/pix, added via post-flash, reduced the losses to ~15+/-1% and ~4+/-1% for faint and bright sources, respectively. Applying the empirical pixel-based CTE correction algorithm can also reduce flux losses: to ~10+/-1% and ~0+/-1% (unflashed images, no background) and to 3+/-1% and 0.5+/-1% (post-flashed), for the faint and bright sources, respectively. We find that the CTE correction appears to slightly over-correct (1-5%) bright sources in low image backgrounds and over-correct most sources in post-flashed images. We empirically fit the flux losses as a function of source flux, observation date, background level, and distance from the amplifier with a 2nd order polynomial and provide tabulated coefficients.

  11. Intramolecular charge transfer with fluorazene and N-phenylpyrrole.

    PubMed

    Druzhinin, Sergey I; Kovalenko, Sergey A; Senyushkina, Tamara A; Demeter, Attila; Zachariasse, Klaas A

    2010-02-04

    The reaction from the initially prepared locally excited (LE) precursor to the intramolecular charge transfer (ICT) state of the planarized fluorazene (FPP) is investigated and compared with its flexible counterpart N-phenylpyrrole (PP). The fluorescence spectra of FPP and PP at 25 degrees C in solvents of different polarity reveal that the onset of a LE --> ICT reaction occurs at lower polarity (tetrahydrofuran, epsilon = 7.39) for FPP than for PP (1,2-dichloroethane, epsilon = 10.4). In accordance with this observation, the ICT reaction enthalpy -DeltaH is larger for FPP than for PP, 16.7 versus 6.7 kJ/mol in ethyl cyanide (EtCN). The larger ICT efficiency of FPP is related to the smaller energy gap between the two lowest excited singlet states DeltaE(S(1),S(2)): 3680 cm(-1) for FPP and 4070 cm(-1) for PP in n-hexane, as would be expected in the context of the PICT model. From picosecond fluorescence decays in EtCN at -45 degrees C it is found that the LE --> ICT reaction rate constant k(a) of FPP is with 9.8 x 10(10) s(-1) considerably larger than that of PP with 3.9 x 10(10) s(-1). From femtosecond transient absorption spectra in acetonitrile (MeCN) at 22 degrees C, an ICT reaction time of 1.6 ps is obtained for FPP, shorter than the 4.0 ps determined for PP. The results show that a perpendicular twist of the pyrrole and phenyl subgroups is not required for an efficient ICT reaction with PP, the planarization of FPP even making this reaction faster. The similarity of the ESA spectra of FPP with those of PP in MeCN, with ICT absorption maxima at 365 nm (FPP) and 370 nm (PP), leads to the conclusion that both ICT states have a planar structure.

  12. Charge-recombination processes in organic solar cells: the impact of charge-transfer states (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Coropceanu, Veaceslav

    2016-09-01

    We study the role of electron-vibration coupling, electronic polarization, molecular packing, system size and electron delocalization on the nature of the charge-transfer states in model donor-acceptor systems. The morphologies we consider range from a bilayer with flat interface to a bilayer with rough interface and bulk heterojunctions with coarse and fine intercalated domains of donor and acceptor molecules. The implications of the charge-transfer states, active material morphology, density of states and charge carrier concentration on non-geminate recombination kinetics is investigated by means of a three-dimensional reaction-diffusion lattice model with the charge carrier hopping rate described by the Miller-Abrahams formalism.

  13. Camptothecins guanine interactions: mechanism of charge transfer reaction upon photoactivation

    NASA Astrophysics Data System (ADS)

    Steenkeste, K.; Guiot, E.; Tfibel, F.; Pernot, P.; Mérola, F.; Georges, P.; Fontaine-Aupart, M. P.

    2002-01-01

    The potent activity exhibited by the antitumoral camptothecin (CPT) and its analog irinotecan (CPT-11) is known to be related to a close contact between the drug and the nucleic acid base guanine. This specificity of interaction between these two chromophores was examined by following changes in the photophysical properties of the drug using steady-state as well as time-resolved absorption and fluorescence methods. The observed effects on absorption, fluorescence emission and singlet excited state lifetimes give evidence for the occurrence of a stacking complex formation restricted to the quinoline part of CPT or CPT-11 and the guanine base but also with the adenine base. The triplet excited state properties of the drugs have been also characterized in absence and in presence of guanosine monophosphate and reveal the occurrence of an electron transfer from the guanine base to the drug. Support for this conclusion was obtained from the studies of a set of biological targets of various oxido-reduction potentials, adenosine monophosphate, cytidine, cytosine, tryptophan, tyrosine and phenylalanine. This finding gives an interpretation of the CPT-induced guanine photolesions previously reported in the literature. These data taken together are discussed in connection with the drug activity. The stacking complex CPT/guanine is necessary but not sufficient to explain the role of the chirality and of the lactone structure in the function of the drug. A stereospecific interaction with the enzyme topoisomerase I seems necessary to stabilize the stacking complex. The first experiments using time-resolved fluorescence by two-photon excitation confirms that CPT does not bind to the isolated enzyme.

  14. Chronoamperometry at micropipet electrodes for determination of diffusion coefficients and transferred charges at liquid/liquid interfaces.

    PubMed

    Yuan, Yi; Wang, Lei; Amemiya, Shigeru

    2004-09-15

    Chronoamperometry was carried out at liquid/liquid interfaces supported at the tip of micropipet electrodes for direct determination of the diffusion coefficient of a species in the outer solution. The diffusion coefficient was used for subsequent determination of the transferred charges per species from the diffusion-limited steady-state current. A large tip resistance of the micropipets causes prolonged charging current so that the faradic current can be measured accurately only at a long-time regime (typically t > 5 ms). At the same time, the long-time current response at the interfaces surrounded by a thin glass wall of the pipets is enhanced by diffusion of the species from behind the pipet tip. Therefore, numerical simulations of the long-time chronoamperometric response were carried out using the finite element method for accurate determination of diffusion coefficients. Validity of the simulation results was confirmed by studying simple transfer of tetraethylammonium ion. The technique was applied for transfer/adsorption reactions of the natural polypeptide protamine and also for Ca2+ and Mg2+ transfers facilitated by ionophore ETH 129. With the diffusion coefficient of protamine determined to be (1.2 +/- 0.1) x 10(-6) cm(2)/s, the ionic charge transferred by each protamine molecule was obtained as +20 +/- 1, which is close to the excess positive charge of protamine. Also, the diffusion coefficient of ETH 129 was determined to demonstrate that each ionophore molecule transfers +0.67 and +1 charge per Ca2+ and Mg2+ transfer, respectively, which corresponds to formation of 1:3 and 1:2 complexes with the respective ions.

  15. Ligand dissociation mediated charge transfer observed at colloidal W18O49 nanoparticle interfaces.

    PubMed

    Grauer, David C; Alivisatos, A Paul

    2014-03-11

    Understanding charge transfer dynamics through the ligand shell of colloidal nanoparticles has been an important pursuit in solar energy conversion. While charge transport through ligand shells of nanoparticle films has been studied intensely in static dry and electrochemical systems, its influence on charge transfer kinetics in dispersed colloidal systems has received relatively less attention. This work reports the oxidation of amine passivated tungsten oxide nanoparticles by an organically soluble tris-(1,10-phenanthroline) iron(III) derivative. By following the rate of this oxidation optically via the production of the ferroin derivative under various reaction conditions and particle derivatizations, we are able to show that the fluxional ligand shells on dispersed, colloidal nanoparticles provide a separate and more facile pathway for charge transfer, in which the rate-limiting step for charge transfer is the ligand dissociation. Since such ligand shells are frequently required for nanoparticle stability, this observation has significant implications for colloidal nanoparticle photocatalysis.

  16. A three-step kinetic model for electrochemical charge transfer in the hopping regime.

    PubMed

    Yin, Xing; Wierzbinski, Emil; Lu, Hao; Bezer, Silvia; de Leon, Arnie R; Davis, Kathryn L; Achim, Catalina; Waldeck, David H

    2014-09-04

    Single-step nonadiabatic electron tunneling models are widely used to analyze electrochemical rates through self-assembled monolayer films (SAMs). For some systems, such as nucleic acids, long-range charge transfer can occur in a "hopping" regime that involves multiple charge transfer events and intermediate states. This report describes a three-step kinetic scheme to model charge transfer in this regime. Some of the features of the three-step model are probed experimentally by changing the chemical composition of the SAM. This work uses the three-step model and a temperature dependence of the charge transfer rate to extract the charge injection barrier for a SAM composed of a 10-mer peptide nucleic acid that operates in the hopping regime.

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

    NASA Astrophysics Data System (A