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Sample records for charge-transfer complexes formed

  1. Utility of Charge Transfer and Ion-Pair Complexation for Spectrophotometric Determination of Eletriptan Hydrobromide in Pure and Dosage Forms

    Directory of Open Access Journals (Sweden)

    Ayman A. Gouda

    2013-01-01

    Full Text Available Three simple, sensitive, and accurate spectrophotometric methods have been developed for the determination of eletriptan hydrobromide (ELT in pure and dosage forms. The first two methods are based on charge transfer complex formation between ELT and chromogenic reagents quinalizarin (Quinz and alizarin red S (ARS producing charge transfer complexes which showed an absorption maximum at 569 and 533 nm for Quinz and ARS, respectively. The third method is based on the formation of ion-pair complex between ELT with molybdenum(V-thiocyanate inorganic complex in hydrochloric acid medium followed by extraction of the colored ion-pair with dichloromethane and measured at 470 nm. Different variables affecting the reactions were studied and optimized. Beer's law is obeyed in the concentration ranges 2.0–18, 1.0–8.0, and 2.0–32 μg mL−1 for Quinz, ARS, and Mo(V-thiocyanate, respectively. The molar absorptivity, Sandell sensitivity, detection, and quantification limits are also calculated. The correlation coefficients were ≥0.9994 with a relative standard deviation (R.S.D%. of ≤0.925. The proposed methods were successfully applied for simultaneous determination of ELT in tablets with good accuracy and precision and without interferences from common additives, and the validity is assessed by applying the standard addition technique, which is compared with those obtained using the reported method.

  2. Imidazole-Chloranil Charge Transfer Complex

    Institute of Scientific and Technical Information of China (English)

    Hai-long Wang; Tong-tong Lu; Tian-jing He; Dong-ming Chen

    2008-01-01

    UV-Vis absorption spectra of the molecular complex formed by imidazole (Im) and chloranil (CA) were measured in chloroform. The stoichiometry of the imidazole-chloranil (Im-CA) complex was determined as 1:1 by applying Benesi-Hildebrand's equation and Job's continuous variation method. Density function theory (DFT) and MP2 calculations were performed to study the structures and the binding energies of the Im-CA complex. The calculations located four conformations (denoted as S1-S4) for the Im-CA complex, two edge(lm)-to-face(CA) linked and two edgc(Im)-to-edge(CA) linked. It was found that the edgc-to-face conformers are more stable than the edge-to-edge ones. The bonding characteristics of these conformers were investigated with natural population analysis (NPA), topological analysis of electron density, and natural bond orbital (NBO) analysis. It was revealed that the edge-to-face conformers are charge-transfer (CT) complexes whereas the edge-to-edge conformers are the hydrogen bond complexes. For the most stable conformation of the Im-CA comp]ex (S1), the charge transfer interaction of the imidazole n(N15) lone pair orbital with the chloranil π*(C1=O7) orbital plays a crucial role in the Im-CA binding, and the binding is further strengthened by the 07… H20 hydrogen bond. The electronic excitation energies of the complex (S1) were calculated with time-dependent DFT (TDDFT), and the observed UV-Visiblc spectrum of the complex was analyzed based on the computed results.

  3. Spectroscopic investigation of the novel charge-transfer complex [(phen)(TCNE)(12)] formed in the reaction of phenacetin with tetracyanoethylene.

    Science.gov (United States)

    Alqaradawi, Siham Y; Nour, El-Metwally

    2005-11-01

    The charge-transfer (CT) interaction of the electron donor phenacetin (phen) and the pi-electron acceptor tetracyanoethylene (TCNE) has been studied in CH(2)Cl(2). The results obtained indicate the formation of the novel CT-complex with the general formula [(phen)(TCNE)(12)]. The 1:12 stoichiometry of the reaction was based on photometric titration, elemental analysis, infrared, thermal and cyclic voltametry measurements of the formed CT-complex.

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

    African Journals Online (AJOL)

    Kinetic and Thermodynamic Studies of Charge-Transfer Complex Formation ... The activation parameters, i.e. activation energy, enthalpy, and entropy of ... KEYWORDS Charge-transfer complex, imipramine, DDQ, ionization potential, kinetic, ...

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

    African Journals Online (AJOL)

    Thermodynamic study of charge-transfer complex of iodine with HT18C6 in ... Bulletin of the Chemical Society of Ethiopia ... KEY WORDS: Charge-transfer complex, Iodine, HT18C6, Stability constant, Thermodynamic data, Spectrophotometry ...

  6. spectrophotometric study of the charge transfer complexation of ...

    African Journals Online (AJOL)

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    The methods of analysis for carbocysteine and levodopa have been ... A Cary300 UV-Vis spectrophotometer (Varian, USA) was used for the absorbance ..... Foster, R. Organic Charge-Transfer Complexes, Academic Press: London; 1969; ...

  7. Positron Annihilation in Solid Charge-Transfer Complexes

    DEFF Research Database (Denmark)

    Lévay, B.; Jansen, P.

    1979-01-01

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

  8. Positron annihilation studies of some charge transfer molecular complexes

    CERN Document Server

    El-Sayed, A; Boraei, A A A

    2000-01-01

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

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

    Science.gov (United States)

    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.

  10. 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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  13. 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.

    Science.gov (United States)

    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.

  14. Structure and electronic spectra of purine-methyl viologen charge transfer complexes.

    Science.gov (United States)

    Jalilov, Almaz S; Patwardhan, Sameer; Singh, Arunoday; Simeon, Tomekia; Sarjeant, Amy A; Schatz, George C; Lewis, Frederick D

    2014-01-01

    The structure and properties of the electron donor-acceptor complexes formed between methyl viologen and purine nucleosides and nucleotides in water and the solid state have been investigated using a combination of experimental and theoretical methods. Solution studies were performed using UV-vis and (1)H NMR spectroscopy. Theoretical calculations were performed within the framework of density functional theory (DFT). Energy decomposition analysis indicates that dispersion and induction (charge-transfer) interactions dominate the total binding energy, whereas electrostatic interactions are largely repulsive. The appearance of charge transfer bands in the absorption spectra of the complexes are well-described by time-dependent DFT and are further explained in terms of the redox properties of purine monomers and solvation effects. Crystal structures are reported for complexes of methyl viologen with the purines 2'-deoxyguanosine 3'-monophosphate (DAD'DAD' type) and 7-deazaguanosine (DAD'ADAD' type). Comparison of the structures determined in the solid state and by theoretical methods in solution provides valuable insights into the nature of charge-transfer interactions involving purine bases as electron donors.

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

    Science.gov (United States)

    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.

  16. Ultrafast Charge Photogeneration in MEH-PPV Charge-Transfer Complexes

    Science.gov (United States)

    Bakulin, Artem A.; Paraschuk, Dmitry Yu.; Pshenichnikov, Maxim S.; van Loosdrecht, Paul H. M.

    Visible-pump-IR-probe spectroscopy is used to study the ultrafast charge dynamics in MEH-PPV based charge-transfer complexes and donor-acceptor blends. Transient anisotropy of the polymer polaron band provides invaluable insights into excitation localisation and charge-transfer pathways.

  17. Spectroscopy of charge transfer complexes of four amino acids as organic two-dimensional conductors

    Energy Technology Data Exchange (ETDEWEB)

    Padhiyar, Ashvin; Patel, A J; Oza, A T [Department of Physics, Sardar Patel University, Vallabh Vidyanagar-388 120, Gujarat (India)

    2007-12-05

    It is found in this study that four amino acids, namely asparagine, arginine, histidine and glutamine form two-dimensional conducting systems which are charge transfer complexes (CTCs) with organic acceptors like TCNQ, TCNE, chloranil, DDQ, TNF and iodine. It is verified using optical absorption edges that these are 2d conductors like transition metal dichalcogenides obeying absorption functions different from 1d and 3d conductors. This 2d nature is related to the network of intermolecular H-bonding in these complexes, which leads to a global H-bonded network resulting in the absence of local deformation due to the relaxation of strain.

  18. Spectroscopy of charge transfer complexes of four amino acids as organic two-dimensional conductors

    Science.gov (United States)

    Padhiyar, Ashvin; Patel, A. J.; Oza, A. T.

    2007-12-01

    It is found in this study that four amino acids, namely asparagine, arginine, histidine and glutamine form two-dimensional conducting systems which are charge transfer complexes (CTCs) with organic acceptors like TCNQ, TCNE, chloranil, DDQ, TNF and iodine. It is verified using optical absorption edges that these are 2d conductors like transition metal dichalcogenides obeying absorption functions different from 1d and 3d conductors. This 2d nature is related to the network of intermolecular H-bonding in these complexes, which leads to a global H-bonded network resulting in the absence of local deformation due to the relaxation of strain.

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

    Science.gov (United States)

    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.

  20. Turn-on fluorescence probes based on pyranine/viologen charge-transfer complexes for the determination of nucleotides

    Energy Technology Data Exchange (ETDEWEB)

    Schäferling, Michael, E-mail: Michael.schaeferling@utu.fi; Lang, Thomas; Schnettelker, Annette

    2014-10-15

    The formation of ground state charge-transfer complexes between pyranine (8-hydroxypyrene-1,3,6-trisulfonic acid) and viologen (paraquat) derivatives is utilized for the design of novel fluoroionophores for the determination of phosphate species, particularly of nucleotides. The strong quenching of the pyranine fluorescence by viologen-type charge transfer acceptors can be countermanded if these are functionalized with triethylammonium groups that serve as recognition elements for phosphate anions. We report on the fluorogenic responses of these water-soluble molecular probes in presence of different phosphates. Absorbance measurements give additional information on the charge transfer complex formation and the interaction with nucleotides. The experimental data show that these aggregates form attractive, simple and versatile fluorescence turn-on probes for nucleoside triphosphates. The reversibility of the fluorescence response is demonstrated by means of an enzymatic model assay using ATPase for the decomposition of adenosine triphosphate. - Highlights: • Pyranine/viologen charge-transfer complexes as molecular probe for ATP recognition. • Fluorescence turn on mechanism. • Selective compared to other nucleotides and phosphate anions. • Fast and reversible response applicable to monitor enzymatic reactions.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2005-09-06

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

  2. Synthesis and characterization of highly conductive charge-transfer complexes using positron annihilation spectroscopy

    Science.gov (United States)

    Adam, Abdel Majid A.; Refat, Moamen S.; Sharshar, T.; Heiba, Z. K.

    Molecular charge-transfer complexes of the tetramethylethylenediamine (TMEDA) with picric acid (Pi-OH), benzene-1,4-diol (QL), tin(IV) tetrachloride (SnCl4), iodine, bromine, and zinc chloride (ZnCl2) have been synthesized and investigated by elemental and thermal analysis, electronic, infrared, Raman and proton-NMR, energy-dispersive X-ray spectroscopy, X-ray powder diffraction and positron annihilation lifetime spectroscopy, and scanning electron microscopy. In this work, three types of acceptors π-acceptors (Pi-OH and QL), σ-acceptors (iodine and bromine), and vacant orbital acceptors (SnCl4 and ZnCl2) were covered. The results of elemental analysis indicated that the CT complexes were formed with ratios 1:1 and 1:2 for QL, SnCl4, and ZnCl2 acceptors and iodine, Pi-OH, and Br2 acceptors, respectively. The type of chelating between the TMEDA donor and the mentioned acceptors depends upon the behavior of both items. The positron annihilation lifetime parameters were found to be dependent on the structure, electronic configuration, and the power of acceptors. The correlation between these parameters and the molecular weight and biological activities of studied complexes was also observed. Regarding the electrical properties, the AC conductivity and the dielectric coefficients were measured as a function of frequency at room temperature. The TMEDA charge-transfer complexes were screened against antibacterial (Escherichia coli, Staphylococcus aureus, Bacillus subtilis, and Pseudomonas aeruginosa) and antifungal (Aspergillus flavus and Candida albicans) activities.

  3. Spectroscopic characterization of charge transfer complexes of 2,3-diaminopyridine with chloranilic acid and dihydroxy-p-benzoquinone in polar solvent.

    Science.gov (United States)

    Al-Ahmary, Khairia M

    2014-01-03

    Charge transfer (CT) complexes formed between 2,3-aminopyridine (2,3-DAP) as electron donor with the π-electron acceptors chloranilic acid (CHA) and dihydroxy-p-benzoquinone (DHBQ) were investigated spectrophotometrically in ethanol. Minimum-maximum absorbance method has been used for estimating the formation constants of the charge transfer reactions (KCT). Job's method of continuous variation and photometric titration studies were used to detect the stoichiometric ratios of the formed complexes and they showed that 1:1 complexes were produced. The molar extinction coefficient (ε), oscillator strength (f), dipole moment (μ), charge transfer energy (ECT), ionization potential (IP) and the dissociation energy (W) of the formed complexes were estimated, they reached acceptable values suggesting the stability of the formed CT-complexes. The solid CT-complexes were synthesized and characterized by elemental analyses, (1)H NMR and FTIR spectroscopies where the formed complexes included proton and electron transfer.

  4. Geometry and quadratic nonlinearity of charge transfer complexes in solution: a theoretical study.

    Science.gov (United States)

    Mukhopadhyay, S; Pandey, Ravindra; Das, Puspendu K; Ramasesha, S

    2011-01-28

    In this paper, we have computed the quadratic nonlinear optical (NLO) properties of a class of weak charge transfer (CT) complexes. These weak complexes are formed when the methyl substituted benzenes (donors) are added to strong acceptors like chloranil (CHL) or di-chloro-di-cyano benzoquinone (DDQ) in chloroform or in dichloromethane. The formation of such complexes is manifested by the presence of a broad absorption maximum in the visible range of the spectrum where neither the donor nor the acceptor absorbs. The appearance of this visible band is due to CT interactions, which result in strong NLO responses. We have employed the semiempirical intermediate neglect of differential overlap (INDO∕S) Hamiltonian to calculate the energy levels of these CT complexes using single and double configuration interaction (SDCI). The solvent effects are taken into account by using the self-consistent reaction field (SCRF) scheme. The geometry of the complex is obtained by exploring different relative molecular geometries by rotating the acceptor with respect to the fixed donor about three different axes. The theoretical geometry that best fits the experimental energy gaps, β(HRS) and macroscopic depolarization ratios is taken to be the most probable geometry of the complex. Our studies show that the most probable geometry of these complexes in solution is the parallel displaced structure with a significant twist in some cases.

  5. Fast ethylamine gas sensing based on intermolecular charge-transfer complexation

    Institute of Scientific and Technical Information of China (English)

    Eun Mi Lee; Seon Young Gwon; Young A Son; Sung Hoon Kim

    2012-01-01

    We have investigated the fast ethylamine gas sensing of 2-chloro-3,5-dinitrobenzotrifluoride (CDBF) loaded poly(acrylonitrile)nanofiber based on an intermolecular charge-transfer complexation.Reversible response and recovery were achieved using alternating gas exposure.This system shows a fast ethylamine gas sensing within 0.4 s.

  6. Photodissociation dynamics of the iodine-arene charge-transfer complex

    NARCIS (Netherlands)

    Lenderink, Egbert; Duppen, Koos; Everdij, Frank P.X.; Mavri, Janez; Torre, Renato; Wiersma, Douwe A.

    1996-01-01

    The photodissociation reaction of the molecular iodine:arene charge-transfer (CT) complex into an iodine atom and an iodine atom-arene fragment has been investigated using femtosecond pump-probe, resonance Raman, and molecular dynamics simulations. In the condensed phase the reaction proceeds on a t

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

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

    Science.gov (United States)

    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.

  10. Semilocal and Hybrid Density Embedding Calculations of Ground-State Charge-Transfer Complexes

    CERN Document Server

    Laricchia, S; Della Sala, F; 10.1063/1.4795825

    2013-01-01

    We apply the frozen density embedding method, using a full relaxation of embedded densities through a freeze-and-thaw procedure, to study the electronic structure of several benchmark ground-state charge-transfer complexes, in order to assess the merits and limitations of the approach for this class of systems. The calculations are performed using both semilocal and hybrid exchange-correlation (XC) functionals. The results show that embedding calculations using semilocal XC functionals yield rather large deviations with respect to the corresponding supermolecular calculations. Due to a large error cancellation effect, however, they can often provide a relatively good description of the electronic structure of charge-transfer complexes, in contrast to supermolecular calculations performed at the same level of theory. On the contrary, when hybrid XC functionals are employed, both embedding and supermolecular calculations agree very well with each other and with the reference benchmark results. In conclusion, fo...

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

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

    2016-02-01

    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.

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

    Directory of Open Access Journals (Sweden)

    K. B. Vinay

    2012-01-01

    Full Text Available 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.

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

    Science.gov (United States)

    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.

  16. Lock-arm supramolecular ordering: a molecular construction set for cocrystallizing organic charge transfer complexes.

    Science.gov (United States)

    Blackburn, Anthea K; Sue, Andrew C-H; Shveyd, Alexander K; Cao, Dennis; Tayi, Alok; Narayanan, Ashwin; Rolczynski, Brian S; Szarko, Jodi M; Bozdemir, Ozgur A; Wakabayashi, Rie; Lehrman, Jessica A; Kahr, Bart; Chen, Lin X; Nassar, Majed S; Stupp, Samuel I; Stoddart, J Fraser

    2014-12-10

    Organic charge transfer cocrystals are inexpensive, modular, and solution-processable materials that are able, in some instances, to exhibit properties such as optical nonlinearity, (semi)conductivity, ferroelectricity, and magnetism. Although the properties of these cocrystals have been investigated for decades, the principal challenge that researchers face currently is to devise an efficient approach which allows for the growth of high-quality crystalline materials, in anticipation of a host of different technological applications. The research reported here introduces an innovative design, termed LASO-lock-arm supramolecular ordering-in the form of a modular approach for the development of responsive organic cocrystals. The strategy relies on the use of aromatic electronic donor and acceptor building blocks, carrying complementary rigid and flexible arms, capable of forming hydrogen bonds to amplify the cocrystallization processes. The cooperativity of charge transfer and hydrogen-bonding interactions between the building blocks leads to binary cocrystals that have alternating donors and acceptors extending in one and two dimensions sustained by an intricate network of hydrogen bonds. A variety of air-stable, mechanically robust, centimeter-long, organic charge transfer cocrystals have been grown by liquid-liquid diffusion under ambient conditions inside 72 h. These cocrystals are of considerable interest because of their remarkable size and stability and the promise they hold when it comes to fabricating the next generation of innovative electronic and photonic devices.

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

    DEFF Research Database (Denmark)

    Chabera, Pavel; Liu, Yizhu; Prakash, Om

    2017-01-01

    of innovative molecular designs(6,8-10), it remains a formidable scientific challenge(11) to access Earth-abundant transition-metal complexes with long-lived charge-transfer excited states. No known iron complexes are considered(12) photoluminescent at room temperature, and their rapid excited...... sufficiently to realize a long charge-transfer lifetime of 100 picoseconds (ps) and room-temperature photoluminescence. This species is a low-spin Fe(III) d(5) complex, and emission occurs from a long-lived doublet ligand-to-metal charge-transfer ((LMCT)-L-2) state that is rarely seen for transition...

  18. Spectrophotometric determination of nizatidine and ranitidine through charge transfer complex formation.

    Science.gov (United States)

    Walash, M; Sharaf-El Din, M; Metwalli, M E-S; RedaShabana, M

    2004-07-01

    Two Spectrophotometric procedures are presented for the determination of two commonly used H2-receptor antagonists, nizatidine (I) and ranitidine hydrochloride (II). The methods are based mainly on charge transfer complexation reaction of these drugs with either p-chloranilic acid (rho-CA) or 2, 3 dichloro-5, 6-dicyanoquinone (DDQ). The produced colored products are quantified spectrophotometrically at 515 and 467 nm in chloranilic acid and DDQ methods, respectively. The molar ratios for the reaction products and the optimum assay conditions were studied. The methods determine the cited drugs in concentration ranges of 20-200 and 20-160 microg/mL for nizatidine and ranges of 20-240 and 20-140 microg/mL for ranitidine with chloranilic acid and DDQ methods, respectively. A more detailed investigation of the complexes formed was made with respect to their composition, association constant, molar absorptivity and free energy change. The proposed procedures were successfully utilized in the determination of the drugs in pharmaceutical preparations. The standard addition method was applied by adding nizatidine and ranitidine to the previously analyzed tablets or capsules. The recovery of each drug was calculated by comparing the concentration obtained from the spiked mixtures with those of the pure drug. The results of analysis of commercial tablets and the recovery study (standard addition method) of the cited drugs suggested that there is no interference from any excipients, which are present in tablets or capsules. Statistical comparison of the results was performed with regard to accuracy and precision using student's t-test and F-ratio at 95% confidence level. There is no significant difference between the reported and proposed methods with regard to accuracy and precision.

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

    Directory of Open Access Journals (Sweden)

    Nourah Z. Alzoman

    2013-07-01

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

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

    Science.gov (United States)

    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.

  1. Semiconduction properties of some polyene-iodine charge-transfer complexes and their application in solid-state batteries

    Energy Technology Data Exchange (ETDEWEB)

    Sen, S.; Pal, P.; Misra, T.N. (Indian Association for the Cultivation of Science, Calcutta (India). Dept. of Spectroscopy)

    1993-03-01

    The conjugated polyenes [beta]-carotene, lutein, retinoic acid and [beta]-apo-8'-carotenal are shown to form charge-transfer (CT) complexes with the electron acceptor iodine. The conductivity increases by several orders of magnitude and the activation energy decreases on CT complex formation. Using these complexes as cathodic material, batteries with the configuration Mg/(polyene-iodine CT complex)/graphite are developed. Different battery parameters are evaluated. The effects of ambient temperature and humidity on battery performance are also studied. Results show that a [beta]-apo-8'-carotenal-1[sub 2] based battery has the maximum power density and longest self-life and is suitable for use as a micro-electronic gadget energizer. (author)

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

    Science.gov (United States)

    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.

  3. Ferroelectric phase transition, ionicity condensation, and multicriticality in charge-transfer organic complexes

    Science.gov (United States)

    Kishine, Jun-Ichiro; Luty, Tadeusz; Yonemitsu, Kenji

    2004-02-01

    To elucidate a pressure-temperature phase diagram of the quasi-one-dimensional mixed-stack charge-transfer complex tetrathiafulvalene-P-chloranil (TTF-CA), we study the quasi-one-dimensional spin-1 Blume-Emery-Griffiths model. In addition to the local charge-transfer energy (Δ) and the inter-stack polar (dipole-dipole) interaction (J⊥), we take account of the interstack electrostriction (Coulomb-lattice coupling). Using the self-consistent chain-mean-field theory, where the intra-stack degrees of freedom are exactly treated by the transfer-matrix method, we reproduce the gas-liquid-solid like phase diagram corresponding to the neutral (N), paraelectric ionic (Ipara), and ferroelectric ionic (Iferro) phases, respectively. Our classical model describes an essential point of the multicritical behavior of TTF-CA, i.e., the interchain electrostriction exclusively enhances the charge concentration (ionicity condensation), but does not affect the interchain ferroelectric coupling. This effect leads to appearance of the intermediate Ipara phase in between the N and Iferro phases on the Δ-T phase diagram.

  4. Impedance Spectroscopy Study of the AC Conductivity and Dielectric properties of 3, 5-Dimethylpyridine-Iodine Charge Transfer Complex

    Directory of Open Access Journals (Sweden)

    Uttam Mohan

    2016-05-01

    Full Text Available Solid charge transfer complex of n-donor 3, 5-dimethylpyridine (3, 5-Lutidine with σ acceptor iodine was prepared and characterised by using elemental analysis, UV-Vis, FTIR, 1H NMR spectroscopy and powder XRD techniques. The electrical parameters of the prepared complex in the pellet form were studied at various temperatures and at wide frequency range by employing AC complex impedance spectroscopic technique. The Nyquist (cole-cole plots have been successfully explained by employing (RC(RC(RC equivalent circuit corresponding to grain , grain boundary and electrode contributions. The radii of the semicircular arc decrease with increase in temperature which suggests that the material exhibits negative temperature coefficient of resistance (NTCR behaviour like semiconductors. Dielectric constant, ɛ′ and dielectric loss, ɛ″ seems to decrease sharply with increase in frequency. The ac conductivity obeys the power law of frequency.

  5. A schematic model for energy and charge transfer in the chlorophyll complex

    DEFF Research Database (Denmark)

    Bohr, Henrik; Malik, F.B.

    2011-01-01

    A theory for simultaneous charge and energy transfer in the carotenoid-chlorophyll-a complex is presented here and discussed. The observed charge transfer process in these chloroplast complexes is reasonably explained in terms of this theory. In addition, the process leads to a mechanism to drive...... an electron in a lower to a higher-energy state, thus providing a mechanism for the ejection of the electron to a nearby molecule (chlorophyll) or into the environment. The observed lifetimes of the electronically excited states are in accord/agreement with the investigations of Sundström et al....... and are in the range of pico-seconds and less. The change in electronic charge distribution in internuclear space as the system undergoes an electronic transition to a higher-energy state could, under appropriate physical conditions, lead to oscillating dipoles capable of transmitting energy from the carotenoid-chlorophylls...

  6. Optical studies of the charge transfer complex in polythiophene/fullerene blends for organic photovoltaic applications

    Science.gov (United States)

    Drori, T.; Holt, J.; Vardeny, Z. V.

    2010-08-01

    We studied the photophysics of regioregular polythiophene/ C61 (RR-P3HT/PCBM) blend films utilized for organic photovoltaic applications using the femtosecond transient and steady-state photomodulation techniques with above-gap and below-gap pump excitations and electroabsorption spectroscopy. We provide strong evidence for the existence of charge transfer complex (CTC) state in the blend that is formed deep inside the optical gap of the polymer and fullerene constituents, which is clearly revealed in the electroabsorption spectrum with an onset at 1.2 eV. We identify this “midgap” band as the lowest lying CTC state formed at the interfaces separating the polymer and fullerene phases. With above-gap pump excitation the primary photoexcitations in the blend are excitons and polarons in the polymer domains that are generated within the experimental time resolution (150 fs), having distinguishable photoinduced absorption (PA) bands in the mid-IR. The photogenerated excitons subsequently decay within ˜10ps , consistent with the polymer weak photoluminescence in the blend. In contrast, with below-gap pump excitation, a new PA band in the mid-IR is generated within our time resolution, which is associated with photogenerated species that decay into polarons at much later times; also no PA of excitons is observed. We interpret the photoexcitations as CT excitons, which with below-gap pump excitation are resonantly generated on the CTC states at the interfaces, as the first step for polaron generation, without involving intrachain excitons in the polymer phase. We found that the polarons generated with below-gap pump excitation are trapped at the interfaces with relatively long lifetime, and thus may generate polarons on the polymer chains and fullerene molecules with a different mechanism than with above-gap excitation. In any case the interfacial polarons generated with below-gap excitation do not substantially contribute to the photocurrent density in photovoltaic

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

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

    2017-02-01

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

  9. The origin of the strong interfacial charge-transfer absorption in the surface complex between TiO2 and dicyanomethylene compounds.

    Science.gov (United States)

    Jono, Ryota; Fujisawa, Jun-ichi; Segawa, Hiroshi; Yamashita, Koichi

    2013-11-14

    Interfacial charge transfer transitions between organic and inorganic materials are expected to be a potential photoinduced charge separation mechanism for photoenergy conversions. Recently, we reported that the hybrid material formed from TiO2 nanoparticles and an organic electron acceptor, 7,7,8,8-tetracyanoquinodimethane (TCNQ), shows strong interfacial charge transfer absorption in the visible region. In this work, we have theoretically studied the structure, and electronic and absorption properties in order to clarify the formation mechanism and the origin of the strong interfacial charge transfer absorption. Density functional theory (DFT) calculations employing an anatase Ti14O28H2(OH)2(H2O)2 nano-cluster unraveled that the surface complex is formed by a nucleophilic addition reaction between a surface hydroxyl group of TiO2 and the carbon atom of the methylene moiety in TCNQ with the drastic changes in the structure and electronic properties of TCNQ. In the formation process, owing to the high electron affinity of TCNQ, a negative charge of the surface oxygen atom is transferred to the TCNQ moiety. This leads to a significant electronic hybridization between TiO2 and TCNQ, which is the origin of interfacial charge transfer transitions.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-10-21

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

  13. Charge transfer complexes of fullerene[60] with porphyrins as molecular rectifiers. A theoretical study.

    Science.gov (United States)

    Montiel, Filiberto; Fomina, Lioudmila; Fomine, Serguei

    2015-01-01

    Molecular diodes based on charge transfer complexes of fullerene[60] with different metalloporphyrins have been modeled. Their current-voltage characteristics and the rectification ratios (RR) were calculated using direct ab initio method at PBE/def2-SVP level of theory with D3 dispersion correction, for voltages ranging from -2 to +2 V. The highest RR of 32.5 was determined for the complex of fullerene[60] with zinc tetraphenylporphyrin at 0.8 V. Other molecular diodes possessed lower RR, however, all complexes showed RR higher than 1 at all bias voltages. The asymmetric evolutions and alignment of the molecular orbitals with the applied bias were found to be essential for generating the molecular diode rectification behavior. Metal nature of metalloporphyrins and the interaction porphyrin-electrode significantly affect RR of molecular diode. Large metal ions like Cd(2+) and Ag(2+) in metalloporphyrins disfavor rectification creating conducting channels in two directions, while smaller ions Zn(2+) and Cu(2+) favor rectification increasing the interaction between gold electrode and porphyrin macrocycle.

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

    Science.gov (United States)

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

    2017-10-01

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

  15. Spectrophotometric determination of quetiapine fumarate in pharmaceuticals and human urine by two charge-transfer complexation reactions

    Directory of Open Access Journals (Sweden)

    Vinay K.B.

    2012-01-01

    Full Text Available Two simple, rapid and accurate spectrophotometric procedures are proposed for the determination of quetiapine fumarate (QTF in pharmaceuticals and in spiked human urine. The methods are based on charge transfer complexation reactions of free base form of the drug (quetiapine, QTP, as n-electron donor (D, with either p-chloranilic acid (p-CAA (method A or 2,3-dichloro-5,6-dicyanoquinone (DDQ (method B as π-acceptors (A. The coloured charge transfer complexes produced exhibit absorption maxima at 520 and 540 nm, in method A and method B, respectively. The experimental conditions such as reagent concentration, reaction solvent and time have been carefully optimized to achieve the maximum sensitivity. Beer’s law is obeyed over the concentration ranges of 8.0 - 160 and 4.0 - 80.0 μg ml-1, for method A and method B, respectively. The calculated molar absorptivity values are 1.77 × 103 and 4.59 × 103 l mol-1cm-1, respectively, for method A and method B. The Sandell sensitivity values, limits of detection (LOD and quantification (LOQ have also been reported. The stoichiometry of the reaction in both cases was accomplished adopting the limiting logarithmic method and was found to be 1: 2 (D: A. The accuracy and precision of the methods were evaluated on intra-day and inter-day basis. The proposed methods were successfully applied for the determination of QTF in pharmaceutical formulations and spiked human urine.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  19. Further evidence for charge transfer complexes in brown carbon aerosols from excitation-emission matrix fluorescence spectroscopy.

    Science.gov (United States)

    Phillips, Sabrina M; Smith, Geoffrey D

    2015-05-14

    The light-absorbing fraction of organic molecules in ambient aerosols, known as "brown carbon," is an important yet poorly characterized component. Despite the fact that brown carbon could alter the radiative forcing of aerosols significantly, identification of specific chromophores has remained challenging. We recently demonstrated that charge transfer (CT) complexes formed in organic molecules could be responsible for a large fraction of absorption observed in water-extracted ambient particulate matter.1 In the present study, we use excitation-emission matrix fluorescence spectroscopy to further corroborate the importance of CT complexes in defining aerosol optical properties. Monotonically increasing and decreasing quantum yields, decreasing Stokes shifts, and red-shifting emission maxima are observed from ambient particulate matter collected in Athens, Georgia, strongly suggesting that a superposition of independent chromophores is not sufficient to explain brown carbon absorption and fluorescence. Instead, we show that a model in which such chromophores are energetically coupled to a dense manifold of CT complexes is consistent with all of the observations. Further, we suggest that a significant fraction of the observed fluorescence originates from CT complexes and that their contribution to brown carbon absorption is likely greater than we reported previously.

  20. Geometry and quadratic nonlinearity of charge transfer complexes in solution using depolarized hyper-Rayleigh scattering.

    Science.gov (United States)

    Pandey, Ravindra; Ghosh, Sampa; Mukhopadhyay, S; Ramasesha, S; Das, Puspendu K

    2011-01-28

    We report large quadratic nonlinearity in a series of 1:1 molecular complexes between methyl substituted benzene donors and quinone acceptors in solution. The first hyperpolarizability, β(HRS), which is very small for the individual components, becomes large by intermolecular charge transfer (CT) interaction between the donor and the acceptor in the complex. In addition, we have investigated the geometry of these CT complexes in solution using polarization resolved hyper-Rayleigh scattering (HRS). Using linearly (electric field vector along X direction) and circularly polarized incident light, respectively, we have measured two macroscopic depolarization ratios D=I(2ω,X,X)/I(2ω,Z,X) and D(')=I(2ω,X,C)/I(2ω,Z,C) in the laboratory fixed XYZ frame by detecting the second harmonic scattered light in a polarization resolved fashion. The experimentally obtained first hyperpolarizability, β(HRS), and the value of macroscopic depolarization ratios, D and D('), are then matched with the theoretically deduced values from single and double configuration interaction calculations performed using the Zerner's intermediate neglect of differential overlap self-consistent reaction field technique. In solution, since several geometries are possible, we have carried out calculations by rotating the acceptor moiety around three different axes keeping the donor molecule fixed at an optimized geometry. These rotations give us the theoretical β(HRS), D and D(') values as a function of the geometry of the complex. The calculated β(HRS), D, and D(') values that closely match with the experimental values, give the dominant equilibrium geometry in solution. All the CT complexes between methyl benzenes and chloranil or 1,2-dichloro-4,5-dicyano-p-benzoquinone investigated here are found to have a slipped parallel stacking of the donors and the acceptors. Furthermore, the geometries are staggered and in some pairs, a twist angle as high as 30° is observed. Thus, we have demonstrated in

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

    DEFF Research Database (Denmark)

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

    2016-01-01

    , the quinol-protein interaction, which initiates the Q-cycle, has not yet been completely described. Furthermore, the initial charge transfer reactions of the Q-cycle lack a physical description. The present investigation utilizes classical molecular dynamics simulations in tandem with quantum density...

  2. Preparation and characterization of polymer composites based on charge-transfer complex of phenothiazine–iodine in polystyrene

    Indian Academy of Sciences (India)

    R A Singh; R K Gupta; S K Singh

    2005-08-01

    Polymer composites based on charge-transfer complex of phenothiazine and iodine with polystyrene have been prepared in different weight ratios and characterized by FTIR, XRD, mechanical, microstructure and electrical properties (d.c. as well as a.c.). These composites show semiconducting behaviour as the conductivity increases with increasing temperature. Low percolation threshold (10% wt CTC) has been found indicating that processable conducting polymers with improved mechanical properties can be prepared by this method.

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

    Energy Technology Data Exchange (ETDEWEB)

    Bradshaw, Rebecca; Sykes, Daniel; Faulkner, Stephen [University of Oxford, Chemistry Research Laboratory, Mansfield Road, Oxford (United Kingdom); Natrajan, Louise S; Livens, Francis R [Centre for Radiochemistry Research, School of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL (United Kingdom); Taylor, Robin J, E-mail: Stephen.Faulkner@chem.ox.ac.uk [Central Laboratory, National Nuclear Laboratory, Sellafield, Seascale, Cumbria, CA20 1PG (United Kingdom)

    2010-03-15

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

  4. Direct detection by atomic force microscopy of single bond forces associated with the rupture of discrete charge-transfer complexes.

    Science.gov (United States)

    Skulason, Hjalti; Frisbie, C Daniel

    2002-12-18

    Atomic force microscopy (AFM) was used to measure the chemical binding force of discrete electron donor-acceptor complexes formed at the interface between proximal self-assembled monolayers (SAMs). Derivatives of the well-known electron donor N,N,N',N'-tetramethylphenylenediamine (TMPD) and the electron acceptor 7,7,8,8-tetracyanoquinodimethane (TCNQ) were immobilized on Au-coated AFM tips and substrates by formation of SAMs of N,N,N'-trimethyl-N'-(10-thiodecyl)-1,4-phenylenediamine (I) and bis(10-(2-((2,5-cyclohexadiene-1,4-diylidene)dimalonitrile))decyl) disulfide (II), respectively. Pull-off forces between modified tips and substrates were measured under CHCl(3) solvent. The mean pull-off forces associated with TMPD/TCNQ microcontacts were more than an order of magnitude larger than the pull-off forces for TMPD/TMPD and TCNQ/TCNQ microcontacts, consistent with the presence of specific charge-transfer interactions between proximal TMPD donors and TCNQ acceptors. Furthermore, histograms of pull-off forces for TMPD/TCNQ contacts displayed 70 +/- 15 pN periodicity, assigned to the rupture of individual TMPD-TCNQ donor-acceptor (charge-transfer) complexes. Both the mean pull-off force and the 70 pN force quantum compare favorably with a contact mechanics model that incorporates the effects of discrete chemical bonds, solvent surface tensions, and random contact area variations in consecutive pull-offs. From the 70 pN force quantum, we estimate the single bond energy to be approximately 4-5 kJ/mol, in reasonable agreement with thermodynamic data. These experiments establish that binding forces due to discrete chemical bonds can be detected directly in AFM pull-off measurements employing SAM modified probes and substrates. Because SAMs can be prepared with a wide range of exposed functional groups, pull-off measurements between SAM-coated tips and substrates may provide a general strategy for directly measuring binding forces associated with a variety of simple

  5. 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.

    Science.gov (United States)

    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.

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

    Science.gov (United States)

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

    2013-04-21

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

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

    Science.gov (United States)

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

    Science.gov (United States)

    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.

  9. Charge transfer adducts of metal complexes of π-donor ligands with I 2 and TCNQ

    Science.gov (United States)

    Bera, T. R.; Sen, D.; Ghosh, R.

    1989-01-01

    Copper(II) and nickel(II) biguanides and O-alkyl-1-amidinourea can act as donors for the formation of charge transfer (CT) adducts with I 2 and tetracyanoquinodimethane (TNCQ) as acceptors. Iodine adducts are characterized both in solid and solution states whereas TCNQ adducts obtain only in solution. Appearance of a broad band at 355 nm for iodine adducts and at 335 nm for TNCQ adducts and shifting of i.r. frequencies support the formation of donor acceptor associates. Elemental analysis establishes 1:1 stoichiometry of the solid adducts. The K and ɛ values determined by modified Benesi—Hildebrand, Scott and Rose—Drago equations are found to be of the order of 10 4 and 10 3 respectively at 298 K in methanol. The solvent effect on the K values is discussed in terms of coupled solute-solute and solute-solvent equilibria.

  10. Charge Transfer Complexes of Polymers%高分子电荷转移复合物

    Institute of Scientific and Technical Information of China (English)

    赵扬; 邱家白

    1986-01-01

    @@ 电荷转移复合物(charge transfer complex, CTC)的研究,始于本世纪二十年代。然而对CTC理论的阐述,及其实际应用方面,长期未取得实质性进展。1952年R. S. Mulliken在J. H. Hildebrand的实验基础上首创共振模型,引入电荷转移(charge transfer,CT)这一术语,奠定了CTO的理论基础。从此,对CT现象的研究不断深入,开拓的领域日益广阔,已成为世界性的研究课题。

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

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

    2011-03-01

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

  13. 碳纳米管-苯胺电荷转移复合物中的胺荧光淬灭效应%Quenching Effects of Amine on Fluorescence of Carbon Nanotube-Aniline Charge Transfer Complex

    Institute of Scientific and Technical Information of China (English)

    SUN Xu-feng; WANG Yu; JIN Wei-jun

    2005-01-01

    Under refluxing, carbon nanotube (CNT) and aniline (An) can form the charge transfer complex (CTC) of CNT-An.The corresponding fluorescence emission peaks lied at 564nm and 606nm, respectively, with the excitation wavelength of 516nm in the acetone solution. The quenching effects of various amines on CNT- An CTC fluorescence were investigated in detail.

  14. Visualization of Metal-to-Ligand and Ligand-to-Ligand Charge Transfer in Metal-Ligand Complexes

    Institute of Scientific and Technical Information of China (English)

    Yong Ding; Jian-xiu Guo; Xiang-si Wang; Sha-sha Liu; Feng-cai Ma

    2009-01-01

    Three methods including the atomic resolved density of state, charge difference density, and the transition density matrix are used to visualize metal to ligand charge transfer (MLCT) in ruthenium(Ⅱ) ammine complex. The atomic resolved density of state shows that there is density of Ru on the HOMOs. All the density is localized on the ammine, which reveals that the excited electrons in the Ru complex are delocalized over the ammine ligand. The charge difference density shows that all the holes are localized on the Ru and the electrons on the ammine. The localization explains the MLCT on excitation. The transition density matrix shows that there is electron-hole coherence between Ru and ammine. These methods are also used to examine the MLCT in Os(bpy)(p0p)Cl ("Osp0p"; bpy=2,2'-bipyridyl; p0p=4,4'-bipyridyl) and the ligand-to-ligand charge transfer (LLCT) in Alq3. The calculated results show that these methods are powerful to examine MLCT and LLCT in the metal-ligand system.

  15. Spectrophotometric Determination of Some Fluoroquinolone Antibacterials through Charge-transfer and Ion-pair Complexation Reactions

    Energy Technology Data Exchange (ETDEWEB)

    El-Brashy, Amina Mohamed; El-Sayed Metwally Mohamed; El-Sepai, Fawzi Abdallah [University of Mansoura, Mansoura (Egypt)

    2004-03-15

    Two simple, rapid and sensitive spectrophotometric methods for the determination of three fluoroquinolones, namely levofloxacin, norfloxacin and ciprofloxacin have been performed either in pure form or in their tablets. In the first method, levofloxacin and norfloxacin are directly treated with bromocresol green (BCG) in dichloromethane while ciprofloxacin is allowed to react with the same dye in aqueous acidic buffer. Highly yellow colored complex species were formed instantaneously in case of levofloxacin and norfloxacin or after extraction into dichloromethane for ciprofloxacin. The formed complexes are quantified spectrophotometrically at their absorption maxima at 411 nm for levofloxacin and 412 nm for norfloxacin and ciprofloxacin. The second method involves the reaction of levofloxacin with {rho}-chloranilic acid ({rho}-CA) and norfloxacin with tetracyanoethylene (TCNE) in acetonitrile to give complexes with maximum absorbance at 521 and 333 nm for the two drugs, respectively. Adopting the first procedure, calibration graphs were linear over the range 1- 20 {mu}g mL{sup .1} with mean percentage recoveries of 100.41 {+-} 0.72, 99.99 {+-} 0.54 and 100.23 {+-} 0.91 for the three drugs, respectively. For the second procedure, the concentration ranges were 15-250 {mu}g mL{sup .1} for levofloxacin using {rho}-CA and 0.8-16 {mu}g mL{sup .1} for norfloxacin using TCNE with mean percentage recoveries of 99.88 {+-} 0.45 and 100.26 {+-} 0.68 for the two drugs, respectively. The proposed methods were successfully applied to determine these drugs in their tablet formulations and the results compared favorably to that of reference methods. The proposed methods are recommended for quality control and routine analysis

  16. Carotenoid to chlorophyll energy transfer in the peridinin–chlorophyll-a–protein complex involves an intramolecular charge transfer state

    Science.gov (United States)

    Zigmantas, Donatas; Hiller, Roger G.; Sundström, Villy; Polívka, Tomáš

    2002-01-01

    Carotenoids are, along with chlorophylls, crucial pigments involved in light-harvesting processes in photosynthetic organisms. Details of carotenoid to chlorophyll energy transfer mechanisms and their dependence on structural variability of carotenoids are as yet poorly understood. Here, we employ femtosecond transient absorption spectroscopy to reveal energy transfer pathways in the peridinin–chlorophyll-a–protein (PCP) complex containing the highly substituted carotenoid peridinin, which includes an intramolecular charge transfer (ICT) state in its excited state manifold. Extending the transient absorption spectra toward near-infrared region (600–1800 nm) allowed us to separate contributions from different low-lying excited states of peridinin. The results demonstrate a special light-harvesting strategy in the PCP complex that uses the ICT state of peridinin to enhance energy transfer efficiency. PMID:12486228

  17. Nuclear magnetic resonance study of charge transfer complex formation between Silver Nitrate and Benzylcyanide in Solvent Ethylene Glycol

    CERN Document Server

    Modarress, H

    2003-01-01

    The formation constant for charge transfer complexes between electron acceptor (AgNo sub 3) and electron donor benzylcyanide (C sub 6 H sub 5 -CH sub 2 -C ident to N) in solvent ethyleneglycol [(CH sub 2 OH) sub 2] has been evaluated by using the nuclear magnetic resonance chemical shifts of aromatic group of benzylcyanide measured against external references, tetramethylsilane, hexamethyldisilane and cyclohexane at 20 sup d ig sup C. The external referencing procedure eliminated the interference of internal reference in the course of complexation. The necessary bulk magnetic susceptibility corrections on the measured chemical shifts have been made. The solution nationalised and their effects on the formation constant have been considered and a new equation has been suggested to obtain the main ionic activity coefficient of AgNO sub 3 from nuclear magnetic resonance results. The mean ionic activity coefficient has been taken into account in the formation constant calculations. The results indicated that the a...

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

    Science.gov (United States)

    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.

  19. Spectrophotometric determination and thermodynamic studies of the charge transfer complexation of emedastine difumarate with some π-acceptors

    Directory of Open Access Journals (Sweden)

    Abdel-Raeq A. Sawsan

    2017-05-01

    Full Text Available Spectrophotometric procedures were presented for the determination of antihistaminic drug, emedastine difumarate. The methods are based on the charge transfer complexation reaction of the drug with π-acceptors; 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ, chloranilic acid (CA and 7,7,8,8-tetracyanoquinodimethane (TCNQ. Different charge-transfer complexes and colored radical anions were obtained. The formations of the colored complexes were utilized in the development of simple, rapid and accurate spectrophotometric methods for the analysis of emedastine in drug substance and products. Under the optimum reaction conditions, linear relationships with good correlation coefficients (0.9996–0.9999 were found between the absorbance at the relevant maxima and the concentrations of emedastine in the range of 0.8–200 μg mL−1. The limits of detection ranged from 0.06 to 0.76 μg mL−1. The molar absorptivities and association constants for the colored complexes were evaluated using the Benesi–Hildebrand equation. The free energy change (ΔG° and the enthalpy of formation (ΔH° as well as the entropy (ΔS° were also determined. The methods were successfully applied to analyze the drug formulation with mean recovery percentages ± RSD% of 100.04 ± 0.59–100.22 ± 0.72. The results were compared favorably with the official and reported methods.

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

    Science.gov (United States)

    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.

  1. Identification of a (H2O)8 cluster in a supramolecular host of a charge transfer platinum(II) complex

    Indian Academy of Sciences (India)

    Sutanuva Mandal; Ipsita Chatterjee; Alfonso Castiñeirs; Sreebrata Goswami

    2014-09-01

    The chemical reaction of PtII(L1)Cl2 [L1 = 2-(phenylazo)pyridine] with a bidentate N,S-donor atom ligand, 2-phenylthioaniline, (HL2) in alkaline acetonitrile yielded a mixed ligand donor acceptor complex, [PtII(L1)(L2)−]Cl, [1]Cl. The complex has been characterized by using a host of physical methods: X-ray crystallography, nuclear magnetic resonance, cyclic voltammetry, absorption spectroscopy, electron paramagnetic resonance. The complex showed intense interligand charge transfer (ILCT) transition in the long wavelength region of UV-vis spectrum at 785 nm. The single-crystal X-ray structure of complex, [1]Cl·2.6H2O is reported. The cationic complex upon crystallization from aqueous methanol solvent produces an assembly of three dimensional (H2O)8 guest moiety within the host lattice of reference Pt-complex. The water assembly showed a unique type of aggregation of two trigonal pyramids hydrogen bonded with three chloride anions. The complex displayed two reversible responses at −0.34 and −1.05 V along with one irreversible anodic response at 0.91 V versus Ag/AgCl reference electrode. The redox processes are characterized by examination of EPR spectra of the electrogenerated complexes.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    Shahdousti, Parvin; Aghamohammadi, Mohammad; Alizadeh, Naader

    2008-04-01

    The charge-transfer (CT) complexes of methamphetamine (MPA) as a n-donor with several acceptors including bromocresolgreen (BCG), bromocresolpurple (BCP), chlorophenolred (CPR), picric acid (PIC), and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) have been studied spectrophotometrically in chloroform solutions in order to obtain some information about their stoichiometry and stability of complexation. The oscillator strengths, transition dipole moments and resonance energy of the complex in the ground state for all complexes have been calculated. Vertical ionization potential of MPA and electron affinity of acceptors were determined by ab initio calculation. The acceptors were also used to utilize a simple and sensitive extraction-spectrophotometric method for the determination of MPA. The method is based on the formation of 1:1 ion-pair association complexes of MPA with BCG, BCP and PIC in chloroform medium. Beer's plots were obeyed in a general concentration range of 0.24-22 μg ml -1 for the investigated drug with different acceptors. The proposed methods were applied successfully for the determination of MAP in pure and abuse drug with good accuracy and precision.

  5. Spectrophotometric Determination of Kinetic Constants of Fe (Iii-Amines’s Charge Transfere Complexes

    Directory of Open Access Journals (Sweden)

    Kamel Bentayeb

    2016-05-01

    Full Text Available Using UV-visible spectrophotometric data of (1:1, electron donor-acceptor complexes (AD1, AD2 and AD3 have been investigated. The complexes concerned are n-butyl amine (D1 and cyclohexyl amine (D2 and phenyl hydrazine (D3 as electron donors with iron (III ion as an electron acceptor (A in methanol at 25°C. The values of formation constant (KAD, molar extinction coefficient (εAD, and absorption band energy of complexes were estimated. The ionization potential of the donors ID, were calculated from the complex band energies. The kinetics of the above association and reverse reactions were studied and some kinetic parameters have been estimated.

  6. Spectrophotometric and thermal studies on the charge--transfer complexes of 4-(aminomethyl) piperidine as donor with σ- and π-electron acceptors.

    Science.gov (United States)

    Mostafa, Adel; El-Ghossein, Nada; Alqaradawi, Siham Y

    2014-01-24

    The spectroscopic characteristics of the solid charge-transfer molecular complexes (CT) formed in the reaction of the electron donor 4-(aminomethyl) piperidine (4AMP) with the σ-acceptor iodine and the π-acceptors 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), 2,4,4,6-tetrabromo-2,5-cyclohexadienone (TBCHD) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) have been studied in chloroform at 25°C. These were investigated through electronic, infrared spectra and thermal analysis as well as elemental analysis. The results show that the formed solid CT-complexes have the formulas [(4AMP)I](+)I3(-), [(4AMP)(DDQ)2] and [(4AMP)(TBCHD)] while in the case of 4AMP-TCNQ reaction, a short-lived CT complex is formed followed by rapid N-substitution by TCNQ forming the final reaction product 7,7,8-tricyano-8-aminomethylpiperidinylquinodimethane [TCAMPQDM] in full agreement with the known reaction stoichiometries in solution as well as the elemental measurements and the thermal analysis confirmed the structure of the obtained compounds. The formation constant kCT, molar extinction coefficient εCT, free energy change ΔG(0) and CT energy ECT have been calculated for the CT-complexes [(4AMP)I](+)I3(-), [(4AMP)(DDQ)2] and [(4AMP)(TBCHD)].

  7. Highly luminescent Sm(III) complexes with intraligand charge-transfer sensitization and the effect of solvent polarity on their luminescent properties.

    Science.gov (United States)

    Lo, Wai-Sum; Zhang, Junhui; Wong, Wing-Tak; Law, Ga-Lai

    2015-04-20

    Samarium complexes with the highest quantum yields to date have been synthesized, and their luminescence properties were studied in 12 solvents. Sensitization via a nontriplet intraligand charge-transfer pathway was also successfully demonstrated in solution states with good quantum yields.

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

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Shin, H.-C.; Ahn, S. J.; Kim, H. W.; Moon, Y.; Rai, K. B. [Department of Physics, Sungkyunkwan University, Suwon 440-746 (Korea, Republic of); Woo, S. H. [College of Pharmacy, Chungnam National University, Daejeon 305–764 (Korea, Republic of); Ahn, J. R., E-mail: jrahn@skku.edu [Department of Physics, Sungkyunkwan University, Suwon 440-746 (Korea, Republic of); SAINT, Sungkyunkwan University, Suwon 440-746 (Korea, Republic of)

    2016-08-22

    Atom (or molecule) intercalations and deintercalations have been used to control the electronic properties of graphene. In general, finite energies above room temperature (RT) thermal energy are required for the intercalations and deintercalations. Here, we demonstrate that alkali metal atoms can be deintercalated from epitaxial graphene on a SiC substrate at RT, resulting in the reduction in density of states at the Fermi level. The change in density of states at the Fermi level at RT can be applied to a highly sensitive graphene sensor operating at RT. Na atoms, which were intercalated at a temperature of 80 °C, were deintercalated at a high temperature above 1000 °C when only a thermal treatment was used. In contrast to the thermal treatment, the intercalated Na atoms were deintercalated at RT when tetrafluorotetracyanoquinodimethane (F4-TCNQ) molecules were adsorbed on the surface. The RT deintercalation occurred via the formation of charge-transfer complexes between Na atoms and F4-TCNQ molecules.

  10. Spectrophotometric study of the charge transfer complexation of some amino acid derivative drugs as electron donors with 7,7,8,8-tetracyanoquinodimethane

    Directory of Open Access Journals (Sweden)

    Sheng Yun Li

    2010-04-01

    Full Text Available Charge transfer (CT complexes of some drugs of amino acid derivatives, such as carbocysteine, aminobutyric acid, and levodopa, as electron donors with 7,7,8,8-tetracyanoquinodimethane (TCNQ as electron acceptor have been studied. The spectra obtained for carbocysteine/TCNQ, aminobutyric acid/TCNQ, and levodopa/TCNQ systems show the maximum absorption bands at wavelengths of 422, 415, and 417 nm, respectively. The formation of such complexes was also confirmed by infrared measurements. The stoichiometry of the complexes was found to be 1:1 between the donor and the acceptor. The possible reaction mechanisms were explored. The thermodynamic standard reaction quantities of the complexes between donors and acceptor were estimated. Different variables affecting the reaction were carefully studied and optimized. At the optimum reaction conditions, Beer’s law was obeyed in a concentration limit of 1–30, 1–10, and 2–50 μg mL−1 for carbocysteine, aminobutyric acid, and levodopa, respectively. The limits of detection ranged from 0.3 to 0.8 μg mL−1. The developed methods could be applied successfully for the determination of the studied compounds in their pharmaceutical dosage forms with a good precision and accuracy compared to official and reported methods as revealed by t- and F-tests.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  13. 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.

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  15. Charge transfer interactions of a Ru(II) dye complex and related ligand molecules adsorbed on Au(111)

    Energy Technology Data Exchange (ETDEWEB)

    Britton, Andrew J.; Weston, Matthew; O' Shea, James N. [School of Physics and Astronomy, University of Nottingham, Nottingham NG7 2RD (United Kingdom); Nottingham Nanotechnology and Nanoscience Centre (NNNC), University of Nottingham, Nottingham NG7 2RD (United Kingdom); Taylor, J. Ben; Rienzo, Anna; Mayor, Louise C. [School of Physics and Astronomy, University of Nottingham, Nottingham NG7 2RD (United Kingdom)

    2011-10-28

    The interaction of the dye molecule, N3 (cis-bis(isothiocyanato)bis(2,2{sup '}-bipyridyl-4,4{sup '}-dicarboxylato) -ruthenium(II)), and related ligand molecules with a Au(111) surface has been studied using synchrotron radiation-based electron spectroscopy. Resonant photoemission spectroscopy (RPES) and autoionization of the adsorbed molecules have been used to probe the coupling between the molecules and the substrate. Evidence of charge transfer from the states near the Fermi level of the gold substrate into the lowest unoccupied molecular orbital (LUMO) of the molecules is found in the monolayer RPES spectra of both isonicotinic acid and bi-isonicotinic acid (a ligand of N3), but not for the N3 molecule itself. Calibrated x-ray absorption spectroscopy and valence band spectra of the monolayers reveals that the LUMO crosses the Fermi level of the surface in all cases, showing that charge transfer is energetically possible both from and to the molecule. A core-hole clock analysis of the resonant photoemission reveals a charge transfer time of around 4 fs from the LUMO of the N3 dye molecule to the surface. The lack of charge transfer in the opposite direction is understood in terms of the lack of spatial overlap between the {pi}*-orbitals in the aromatic rings of the bi-isonicotinic acid ligands of N3 and the gold surface.

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

    Science.gov (United States)

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

    2015-10-15

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

  17. On the nature of stabilization in weak, medium, and strong charge-transfer complexes: CCSD(T)/CBS and SAPT calculations.

    Science.gov (United States)

    Karthikeyan, S; Sedlak, Robert; Hobza, Pavel

    2011-09-01

    Weak, medium, and strong charge-transfer (CT) complexes containing various electron donors (C(2)H(4), C(2)H(2), NH(3), NMe(3), HCN, H(2)O) and acceptors (F(2), Cl(2), BH(3), SO(2)) were investigated at the CCSD(T)/complete basis set (CBS) limit. The nature of the stabilization for these CT complexes was evaluated on the basis of perturbative NBO calculations and DFT-SAPT/CBS calculations. The structure of all of the complexes was determined by the counterpoise-corrected gradient optimization performed at the MP2/cc-pVTZ level, and most of complexes possess a linear-like contact structure. The total stabilization energies lie between 1 and 55 kcal/mol and the strongest complexes contain BH(3) as an electron acceptor. When ordering the electron donors and electron acceptors on the basis of these energies, we obtain the same order as that based on the perturbative E2 charge-transfer energies, which provides evidence that the charge-transfer term is the dominant energy contribution. The CCSD(T) correction term, defined as the difference between the CCSD(T) and MP2 interaction energies, is mostly small, which allows the investigation of the CT complexes of this type at the "cheap" MP2/CBS level. In the case of weak and medium CT complexes (with stabilization energy smaller than about 15 kcal/mol), the dominant stabilization originates in the electrostatic term; the dispersion as well as induction and δ(HF) terms covering the CT energy contribution are, however, important as well. For strong CT complexes, induction energy is the second (after electrostatic) most important energy term. The role of the induction and δ(HF) terms is unique and characteristic for CT complexes. For all CT complexes, the CCSD(T)/CBS and DFT-SAPT/CBS stabilization energies are comparable, and surprisingly, it is true even for very strong CT complexes with stabilization energy close to 50 kcal/mol characteristic by substantial charge transfer (more than 0.3 e). It is thus possible to conclude

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

    Directory of Open Access Journals (Sweden)

    Sara J. Krivickas

    2015-09-01

    , θ21 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.

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

    Science.gov (United States)

    Zulkarnain; Khan, Ishaat M.; Ahmad, Afaq; Miyan, Lal; Ahmad, Musheer; Azizc, Nafe

    2017-08-01

    The charge transfer interaction between p-nitroaniline (PNA) and chloranilic (CAA) acid was studied spectrophotometrically in methanol at different temperatures within the range 298-328 K. This experimental work explores the nature of charge-transfer interactions that play a significant role in chemistry and biology. Structure of synthesized charge transfer (CT) complex was investigated by different technique such as X-ray crystallography, FTIR, 1HNMR, UV-visible spectroscopy, XRD and TGA-DTA, which indicates the presence of N+sbnd Hrbd2bd O- bond between donor and acceptor moieties. Spectrophotometric studies of CT complexes were carried out in methanol at different temperatures to estimate thermodynamic parameters such as formation constant (KCT), molar absorptivity (εCT), free energy change (ΔG), enthalpy change (ΔH), resonance energy (RN), oscillator strength (f), transition dipole moment (μEN) and interaction energy (ECT) were also calculated. The effect of temperatures on all the parameters was studied in methanol. 1:1 stoichiometric of CT-complex was ascertained by Benesi-Hildebrand plots giving straight line, which are good agreement with other analysis. Synthesized CT complex was screened for its antimicrobial activity such as antibacterial activity against two gram-positive bacteria, Staphylococcus aureus and bacillus subtilis and two gram negative bacteria Escherichia coli and pseudomonas aeruginosa, and antifungal activity against fungi Fusarium oxysporum, and Aspergillus flavus.

  20. Charge-transfer character of the low-energy Chl a Q(y) absorption band in aggregated light harvesting complexes II.

    Science.gov (United States)

    Kell, Adam; Feng, Ximao; Lin, Chen; Yang, Yiqun; Li, Jun; Reus, Michael; Holzwarth, Alfred R; Jankowiak, Ryszard

    2014-06-12

    One of the key functions of the major light harvesting complex II (LHCII) of higher plants is to protect Photosystem II from photodamage at excessive light conditions in a process called "non-photochemical quenching" (NPQ). Using hole-burning (HB) spectroscopy, we investigated the nature of the low-energy absorption band in aggregated LHCII complexes - which are highly quenched and have been established as a good in vitro model for NPQ. Nonresonant holes reveal that the lowest energy state (located near 683.3 nm) is red-shifted by ~4 nm and significantly broader (by a factor of 4) as compared to nonaggregated trimeric LHCII. Resonant holes burned in the low-energy wing of the absorption spectrum (685-710 nm) showed a high electron-phonon (el-ph) coupling strength with a Huang-Rhys factor S of 3-4. This finding combined with the very low HB efficiency in the long-wavelength absorption tail is consistent with a dominant charge-transfer (CT) character of the lowest energy transition(s) in aggregated LHCII. The value of S decreases at shorter wavelengths (energy excitonic state is strongly mixed with the CT states. Our findings support the mechanistic model in which Chl-Chl CT states formed in aggregated LHCII are intermediates in the efficient excited state quenching process (M. G. Müller et al., Chem. Phys. Chem. 2010, 11, 1289-1296; Y. Miloslavina et al., FEBS Lett. 2008, 582, 3625-3631).

  1. Conformational control of benzophenone-sensitized charge transfer in dinucleotides.

    Science.gov (United States)

    Merz, Thomas; Wenninger, Matthias; Weinberger, Michael; Riedle, Eberhard; Wagenknecht, Hans-Achim; Schütz, Martin

    2013-11-14

    Charge transfer in DNA cannot be understood without addressing the complex conformational flexibility, which occurs on a wide range of timescales. In order to reduce this complexity four dinucleotide models 1X consisting of benzophenone linked by a phosphodiester to one of the natural nucleosides X = A, G, T, C were studied in water and methanol. The theoretical work focuses on the dynamics and electronic structure of 1G. Predominant conformations in the two solvents were obtained by molecular dynamics simulations. 1G in MeOH adopts mainly an open geometry with a distance of 12–16 Å between the two aromatic parts. In H2O the two parts of 1G form primarily a stacked conformation yielding a distance of 5–6 Å. The low-lying excited states were investigated by electronic structure theory in a QM/MM environment for representative snapshots of the trajectories. Photo-induced intramolecular charge transfer in the S1 state occurs exclusively in the stacked conformation. Ultrafast transient absorption spectroscopy with 1X reveals fast charge transfer from S1 in both solvents with varying yields. Significant charge transfer from the T1 state is only found for the nucleobases with the lowest oxidation potential: in H2O, charge transfer occurs with 3.2 × 10(9) s(-1) for 1A and 6.0 × 10(9) s(-1) for 1G. The reorganization energy remains nearly unchanged going from MeOH to the more polar H2O. The electronic coupling is rather low even for the stacked conformation with H(AB) = 3 meV and explains the moderate charge transfer rates. The solvent controls the conformational distribution and therefore gates the charge transfer due to differences in distance and stacking.

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

    Science.gov (United States)

    Baumeier, Björn; Andrienko, Denis; Rohlfing, Michael

    2012-08-14

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

  3. Charge transfer driven emergent phenomena in oxide heterostructures

    Science.gov (United States)

    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.

  4. Spectrophotometric study of the charge transfer complexes of 4'-nitrobenzo-15-crown-5 and benzo-15-crown-5 with iodine in nonaqueous solvents

    Institute of Scientific and Technical Information of China (English)

    Nina Alizadeh; Sadegh Dehghanikhah

    2011-01-01

    The formation of charge transfer complex between iodine with 4'-nitrobenzo-15-crown-5 (NB15C5) and benzo-15-crown-5 (B15C5) is investigated spectrophotometrically in chloroform and dichloromethane (DCM) solutions at 25℃. The pseudo-first-order rate constants for the transformation process were evaluated from the absorbance-time data and found to vary in the order of DCM > CHCl3. The values of the formation constant, Kf, for each complex are evaluated from Benesi-Hilebrand equation. Stability of the resulting complex in two solvents was also found to vary in the order of DCM > CHC13.

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

    Science.gov (United States)

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

    2015-01-01

    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.

  6. Interplay of Charge Transfer, Dimensionality, and Amide Hydrogen Bond Network Adaptability in TCNQF 4 Complexes of EDO-TTF-CONH 2 and EDT-TTF-CONH 2

    Science.gov (United States)

    Baudron, Stéphane A.; Mézière, Cécile; Heuzé, Karine; Fourmigué, Marc; Batail, Patrick; Molinié, Philippe; Auban-Senzier, Pascale

    2002-11-01

    [EDO-TTF-CONH 2][TCNQF 4], triclinic system, space group P-1, a=8.2479(12) Å, b=12.282(2) Å, c=12.6842(18) Å, α=113.850(17)°, β=106.420(17)°, γ=90.284(19)°, V=1116.8(4) Å 3; and [EDT-TTF-CONH 2] 2[TCNQF 4], triclinic system, space group P-1, a=6.5858(9) Å, b=11.699(2) Å, c=12.2281(18) Å, α=104.000(19)°, β=93.611(17)°, γ=98.279(19)°, V=899.9(3) Å 3, whose π-donor molecules, (ethylenedioxo)-carbamoyltetrathiafulvalene and (ethylenedithio)-carbamoyltetrathiafulvalene, respectively, differ solely by the nature of the chalcogen atoms in their outer ethylene dichalcogeno bridge, yet form very different charge-transfer complexes with the same π-acceptor. [EDO-TTF-CONH 2•+] 2 [TCNQF 4•-] 2 is a diamagnetic insulating ionic salt with a three-dimensional rock-salt-type structure based on discrete dimers while in the semi-conducting mixed-valence complex, [EDT-TTF-CONH 2] 2•+[TCNQF 4•-], the mixed-valence dimers aggregate into infinite chains interspersed within parallel rows of non-interacting radical anions. It is shown how the robust and adaptable supramolecular amide hydrogen bond tweezers-like motifs common to the two solids simply comply to the 3-to-1 dimensionality reduction upon substitution of O for S.

  7. Synthesis, growth, spectral, and thermal studies of a new organic molecular charge transfer complex crystal: 3-nitroaniline 4-methyl benzene sulfonate.

    Science.gov (United States)

    Selvakumar, E; Anandha babu, G; Ramasamy, P; Chandramohan, A

    2014-03-25

    A new organic intermolecular charge transfer complex 3-nitroaniline 4-methyl benzene sulfonate (NATS) has been successfully synthesized and good optical quality single crystals grown by slow solvent evaporation solution growth technique at room temperature using methanol as the solvent. The (1)H and (13)C NMR spectra were recorded to establish the molecular structure of the title complex. The crystal structure of NATS has been determined by single crystal XRD analysis and it belongs to orthorhombic crystal system with space group Pbca. Fourier transform infrared (FT-IR) spectral study has been carried out to confirm the presence of various functional groups present in the complex. Electronic absorption spectrum was recorded to find the prevalent charge transfer activity in the complex. The UV-Vis-NIR transmission spectrum was recorded in the range 200-2500 nm, to find the optical transmittance window and lower cut off wavelength of the title crystal. The thermal stability of the title complex crystal was studied by using thermo-gravimetric and differential thermal analyses and found that the compound is stable up to 215 °C.

  8. Backward Charge Transfer in Conjugated Polymers

    Institute of Scientific and Technical Information of China (English)

    CHENG Meng-Xing; LI Guang-Qi; Thomas F. George; SUN Xin

    2005-01-01

    It has been known that the static polarizability of a polymer chain with a biexciton is negative. In order to understand this peculiar fact, this paper studies the dynamical process of the charge transfer in the polymer chain induced by an external electric field E during forming the biexciton. The time dependence of the charge distribution in the chain reveals that the charge transfer is backward: the positive charge shifts in the opposite direction of the external electric field. Such a backward charge transfer (BCT) produces an opposite dipole, which makes the polarization negative. The effect of electron interaction on the BCT is illustrated.

  9. Shape similarity of charge-transfer (CT) excitation energy curves in a series of donor-acceptor complexes and its description with a transferable energy of CT orbital

    Science.gov (United States)

    Gritsenko, O. V.

    2017-08-01

    A simple nature of charge-transfer (CT) in the prototype complexes Dp -F2 (Dp =NH3 , H2O) manifests itself in a very close shape of their CT excitation energy curves ωCT (R) along the donor-acceptor separation R. It affords a simple orbital description in terms of the CT orbitals (CTOs) obtained with a transformation of the virtual orbitals of the standard local density approximation (LDA). The transferable energy of the relevant CTO as a function of R closely approximates the common shape of ωCT (R) , while the height of the individual curve is determined with the ionization potential of Dp .

  10. Intervalence charge transfer transition in mixed valence complexes synthesised from RuIII(edta)- and FeII(CN)5-cores

    Indian Academy of Sciences (India)

    H C Bajaj; Atindra D Shukla; Amitava Das

    2002-08-01

    Intervalence charge transfer properties were studied for a set of mixed valence complexes incorporating Ru(III) and Fe(II)-centres linked by various saturated and unsaturated bridging ligands (BL). Studies reveal that degree of ground state electronic interaction and coupling between Ru(III) and Fe(II)-centres can be attenuated by changing the nature of the bridging ligand. Further, inclusion of the bridging ligand with interrupted -electron system in a -CD cavity initiate an optical electron transfer from Fe(II) to Ru(III) which is otherwise not observed.

  11. Organic Metals. Mono- and 2,5-Di-substituted 7,7,8,8-Tetracyano-p-quinodimethanes and Conductivities of their Charge-Transfer Complexes

    DEFF Research Database (Denmark)

    Andersen, Jan Rud; Jørgensen, Ole

    1979-01-01

    procedures utilizing multiple recrystallizations from CH3CN, followed by gradient sublimation, yield high quality materials for the preparation of conducting organic charge-transfer complexes based on these acceptors. Field-ionization mass spectrometry was found to be a convenient means of monitoring...... the impurity contents during purification. Roomtemperature conductivity data for selected donor–acceptor combinations are reported, together with the electrochemical reduction potentials of the acceptors. The latter indicate that these have slightly poorer electron-accepting properties than unsubstituted TCNQ....

  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

    Science.gov (United States)

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

    2017-03-01

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

  13. Spectrophotometric and spectroscopic studies of charge transfer complexes of p-toluidine as an electron donor with picric acid as an electron acceptor in different solvents.

    Science.gov (United States)

    Singh, Neeti; Khan, Ishaat M; Ahmad, Afaq

    2010-04-01

    The charge transfer complexes of the donor p-toluidine with pi-acceptor picric acid have been studied spectrophotometrically in various solvents such as carbon tetrachloride, chloroform, dichloromethane acetone, ethanol, and methanol at room temperature using absorption spectrophotometer. The results indicate that formation of CTC in non-polar solvent is high. The stoichiometry of the complex was found to be 1:1 ratio by straight-line method between donor and acceptor with maximum absorption bands. The data are discussed in terms of formation constant (K(CT)), molar extinction coefficient (epsilon(CT)), standard free energy (DeltaG(o)), oscillator strength (f), transition dipole moment (mu(EN)), resonance energy (R(N)) and ionization potential (I(D)). The results indicate that the formation constant (K(CT)) for the complex was shown to be dependent upon the nature of electron acceptor, donor and polarity of solvents that were used.

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

    Science.gov (United States)

    Shehab, Ola R.; Mansour, Ahmed M.

    2015-08-01

    A simple, sensitive and rapid method was developed for the quantitative analysis of sparfloxacin in its pharmaceutical formulations through the formation of charge transfer complexes with π-acceptor systems. The Lambert-Beer's law was obeyed in the concentration ranges of 7-70 and 10-50 μg/mL sparfloxacin for 2,3-dichloro-5,6-dicyano-1,4-benzoquinone and tetracyanoquinodimethane. Structural characterization of the isolated solid CT complexes was carried out by IR, 1H NMR, UV-Vis. and MS. The experimental studies were complemented by quantum chemical calculations at DFT level of theory. The electronic structures were investigated by TD-DFT calculations. Natural bond orbital analysis and molecular electrostatic potential maps were helpful in assigning the CT route. The formation constant, molar extinction coefficient, oscillator strength, dipole moment, standard free energy and ionization potential were calculated.

  15. Spectrophotometric determination of repaglinide in tablets based on charge-transfer complexation reaction with chloranilic acid and dichloro-dicyano benzoquinone

    Directory of Open Access Journals (Sweden)

    Cijo Madathil X.

    2011-01-01

    Full Text Available Two simple, accurate, precise, inexpensive, selective and sensitive spectrophotometric methods are described for the determination of repaglinide (RPG in bulk drug and its tablets. The methods were based on the charge- transfer complex reaction between RPG in acetonitrile with p-chloranilic acid (CAA or 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ in dioxane and subsequent formation of intensely colored radical anions of the reagents which were measured at 520 nm (CAA or 590 nm (DDQ. Several experimental variables affecting the complex formation, stability of the colored species and sensitivity of the reaction were optimized. Under the optimized conditions, Beer’s law was obeyed over the concentration ranges of 20-400 and 5-80 μg ml-1 RPG for CAA and DDQ methods, respectively, and the corresponding correlation coefficients were 0.9995 and 0.9998. The apparent molar absorptivity values were 1.02x103 and 4.60x103 for CAA and DDQ methods respectively, with corresponding Sandell sensitivity values of 0.4438 and 0.0984 μg cm-2. Limits of detection (LOD were calculated to be 7.07 and 2.42 μg ml-1 and the limits of quantification (LOQ were 21.43 and 7.33 μg ml-1 RPG, for CAA method and DDQ method, respectively. Validation results demonstrated that the inter day and intra day accuracy were up to 97.56%. The precision determined did not exceed 2.5% of RSD. The methods were successfully used for the determination of RPG in tablet form and the results were in good agreement with the label claims as shown by the recoveries which were in the range of 99.22- 102.8% with standard deviation values < 2%. The accuracy of the method was confirmed by recovery studies via standardaddition procedure with excellent recovery 98.24-104.0 ± 1.08-3.35.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  17. Nonlinear lattice relaxation of photogenerated charge-transfer excitation in halogen-bridged mixed-valence metal complexes. II. Polaron channel

    Science.gov (United States)

    Mishima, A.; Nasu, K.

    1989-03-01

    The one-dimensional extended Peierls-Hubbard model with half-filled-band electrons is studied in order to clarify the lattice relaxation path of the photogenerated charge-transfer excitation in halogen-bridged mixed-valence metal complexes. The ground and excited states are calculated within mean-field theory for electrons and the adiabatic approximation for phonons. It is concluded that the main origin of the photoinduced absorption is a distant pair of the hole-polaron and the electron-polaron. This distant pair is created not from the ground state of the self-trapped exciton (STE), but from the excited states of the STE through their autodissociation. This is consistent with the experiment on the excitation energy dependence of the photoinduced absorption yield.

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

    Science.gov (United States)

    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.

  19. Highly Efficient Visible-to-NIR Luminescence of Lanthanide(III) Complexes with Zwitterionic Ligands Bearing Charge-Transfer Character: Beyond Triplet Sensitization.

    Science.gov (United States)

    Pan, Mei; Du, Bin-Bin; Zhu, Yi-Xuan; Yue, Mei-Qin; Wei, Zhang-Wen; Su, Cheng-Yong

    2016-02-12

    Two zwitterionic-type ligands featuring π-π* and intraligand charge-transfer (ILCT) excited states, namely 1,1'-(2,3,5,6-tetramethyl-1,4-phenylene)bis(methylene)dipyridinium-4-olate (TMPBPO) and 1-dodecylpyridin-4(1 H)-one (DOPO), have been prepared and applied to the assembly of lanthanide coordination complexes in an effort to understand the ligand-direction effect on the structure of the Ln complexes and the ligand sensitization effect on the luminescence of the Ln complexes. Due to the wide-band triplet states plus additional ILCT excitation states extending into lower energy levels, broadly and strongly sensitized photoluminescence of f→f transitions from various Ln(3+) ions were observed to cover the visible to near-infrared (NIR) regions. Among which, the Pr, Sm, Dy, and Tm complexes simultaneously display both strong visible and NIR emissions. Based on the isostructural feature of the Ln complexes, color tuning and single-component white light was achieved by preparation of solid solutions of the ternary systems Gd-Eu-Tb (for TMPBPO) and La-Eu-Tb and La-Dy-Sm (for DOPO). Moreover, the visible and NIR luminescence lifetimes of the Ln complexes with the TMPBPO ligand were investigated from 77 to 298 K, revealing a strong temperature dependence of the Tm(3+) ((3) H4 ) and Yb(3+) ((2) F5/2 ) decay dynamics, which has not been explored before for their coordination complexes.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  3. 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

    Science.gov (United States)

    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.

  4. Evaluating the Performance of DFT Functionals in Assessing the Interaction Energy and Ground-State Charge Transfer of Donor/Acceptor Complexes: Tetrathiafulvalene−Tetracyanoquinodimethane (TTF−TCNQ) as a Model Case

    KAUST Repository

    Sini, Gjergji

    2011-03-08

    We have evaluated the performance of several density functional theory (DFT) functionals for the description of the ground-state electronic structure and charge transfer in donor/acceptor complexes. The tetrathiafulvalene- tetracyanoquinodimethane (TTF-TCNQ) complex has been considered as a model test case. Hybrid functionals have been chosen together with recently proposed long-range corrected functionals (ωB97X, ωB97X-D, LRC-ωPBEh, and LC-ωPBE) in order to assess the sensitivity of the results to the treatment and magnitude of exact exchange. The results show an approximately linear dependence of the ground-state charge transfer with the HOMO TTF-LUMOTCNQ energy gap, which in turn depends linearly on the percentage of exact exchange in the functional. The reliability of ground-state charge transfer values calculated in the framework of a monodeterminantal DFT approach was also examined. © 2011 American Chemical Society.

  5. 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

    Science.gov (United States)

    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.

  6. Charge Transfer at the Qo-Site of the Cytochrome bc1 Complex Leads to Superoxide Production

    DEFF Research Database (Denmark)

    Salo, Adrian Bøgh; Husen, Peter; Solov'yov, Ilia A

    2017-01-01

    to influence the normal operation of the bc1 complex and acquire an extra electron, thus becoming superoxide, a biologically toxic free radical. The process is modeled by applying quantum chemical calculations to previously performed classical molecular dynamics simulations. Investigations reveal several...

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

    Energy Technology Data Exchange (ETDEWEB)

    Bartocci, Alessio; Cappelletti, David; Pirani, Fernando [Dipartimento di Chimica, Biologia e Biotecnologie, Università di Perugia, Perugia 06123 (Italy); Belpassi, Leonardo [Istituto di Scienze e Tecnologie Molecolari del CNR, Perugia 06123 (Italy); Falcinelli, Stefano [Dipartimento di Ingegneria Civile ed Ambientale, Università degli Studi di Perugia, 06125 Perugia (Italy); Grandinetti, Felice [Dipartimento per la Innovazione nei sistemi Biologici, Agroalimentari e Forestali (DIBAF), Università della Tuscia, 01100 Viterbo (Italy); Tarantelli, Francesco [Dipartimento di Chimica, Biologia e Biotecnologie, Università di Perugia, Perugia 06123 (Italy); Istituto di Scienze e Tecnologie Molecolari del CNR, Perugia 06123 (Italy)

    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

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

    Science.gov (United States)

    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.

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

    Directory of Open Access Journals (Sweden)

    Shinichi Yamabe

    2013-01-01

    Full Text Available 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−(H2O16 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(H2–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−(H2On, 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.

  10. Critical analysis of spectral solvent shifts calculated by the contemporary PCM approaches of a representative series of charge-transfer complexes between tetracyanoethylene and methylated benzenes.

    Science.gov (United States)

    Budzák, Šimon; Mach, Pavel; Medved', Miroslav; Kysel', Ondrej

    2015-07-21

    Applications of contemporary polarisable continuum model (PCM) quantum chemical approaches to account for the solvent shifts of UV-Vis absorption charge transfer (CT) transitions in electron donor-acceptor (EDA) complexes (as well as to account for their stability and other properties in solvents) have been rather rare until now. In this study, we systematically applied different - mainly state-specific - PCM approaches to examine excited state properties, namely, solvatochromic excitation energy shifts in a series of EDA complexes of a tetracyanoethylene (TCNE) acceptor with methyl substituted benzenes with different degrees of methylation N (NMB). For these complexes, representative and reliable experimental data exist both for the gas phase and in solution (dichloromethane). We have found that the linear response (LR) solvent shifts are too small compared to the experimental values, while self-consistent SS approaches give values that are too large. The best agreement with experimental values was obtained by corrected LR (cLR). The transition energies were calculated by means of TD-DFT methodology with PBE0, CAM-B3LYP and M06-2X functionals as well as the wave function CC2 method for the gas phase, and the PCM solvent shifts were added to account for the solvent effects. The best results for transition energies in solvents were obtained using the CC2 method complemented by CAM-B3LYP/cLR for the gas phase transition energy red solvent shift, while all three TD-DFT approaches used gave insufficient values (ca. 50%) of the slope of the dependence of the transition energies on N compared to experimental values.

  11. A charge-transfer surface enhanced Raman scattering model from time-dependent density functional theory calculations on a Ag10-pyridine complex.

    Science.gov (United States)

    Birke, Ronald L; Znamenskiy, Vasiliy; Lombardi, John R

    2010-06-07

    Vibrational frequency calculations were made for a Ag(10)-pyridine vertex complex with density functional theory (DFT) for static simulated spectra and with time-dependent DFT (TD-DFT) for preresonance and resonance simulated spectra using both B3LYP/LANL2DZ and BP86/TZP methodologies. In addition, 40 excited states of the complex were calculated and assigned symmetry based on a C(2v) symmetry of the optimized complex found with B3LYP/LANL2DZ. Molecular orbital isosurfaces show that the excited states involve both Ag(10) intercluster excitations and charge-transfer (CT) excitations between the Ag nanocluster and the pyridine molecule. An excitation around 500 nm involving CT from the Ag cluster to pyridine was found in both calculations. For free pyridine, the relative average deviations between unscaled calculated and experimental results were 1.5 cm(-1) for BP86 and 3.1 cm(-1) for the B3LYP calculations. For the complex, simulated spectra at a variety of excitation wavelengths were calculated. In the case of 514 nm excitation, the simulated Raman cross section from the TD-DFT calculations (near the CT resonance) was plotted versus Raman shift frequency and compared with an experimental surface enhanced Raman scattering (SERS) spectrum obtained on an oxidation-reduction cycle, ORC roughened Ag electrode. The BP86 TD-DFT calculation with finite damping term showed a better fit to experimental spectrum with respect to both relative intensities and frequencies. The average deviation of the unscaled BP86 calculations for 16 bands in the experimental spectrum was 13.0 cm(-1). The calculated spectrum in both cases shows many contributions from nontotally symmetric as well as totally symmetric modes, indicating the contribution of Herzberg-Teller (HT) scattering. The simulated intensities of the Raman modes of different symmetry from Ag(10)-pyridine can be correlated with HT intensity borrowing from excited states of given symmetry and decent oscillator strength. These

  12. 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

    Science.gov (United States)

    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.

  13. CHARGE-TRANSFER AND ENERGY-TRANSFER IN THE PHOTO-INDUCED COPOLYMERIZATION OF 2-VINYLNAPHTHALENE WITH MALEIC ANHYDRIDE

    Institute of Scientific and Technical Information of China (English)

    LI Tong; LUO Bin; LI Shanjun; CHU Guobei

    1990-01-01

    The initiation mechanism of the copolymerization of 2-vinylnaphthalene with maleic anhydride was studied under irradiation of 365 nm. The excited complex was formed from ( 1 ) the local excitation of 2-vinylnaphthalene followed by the charge-transfer interaction with maleic anhydride and ( 2 ) the excitation of the ground state charge-transfer complex, and then it collapsed to 1,4-tetramethylene biradical for initiation. A 1:1 alternating copolymer was formed in different monomer feeds. Addition of benzophenone could greatly enhance the rate of copolymerization through energy-transfer mechanism.

  14. Intramolecular Charge Transfer in Arylpyrazolines

    Institute of Scientific and Technical Information of China (English)

    WANG Ming-Liang; LIU Ju-Zheng; XU Chun-Xiang

    2006-01-01

    @@ Arylpyrazoline microparticles dispersed in water are synthesized and their absorption spectra are compared with those in solution. It is found that the absorbance of pyrazoline group in solution of 5-aryl arylpyrazoline is far greater than that in solution of arylpyrazolines with no 5-aryl group. This hyperchromic effect is intensified in 5-aryl arylpyrazoline microparticles. It is indicated that intramolecular charge transfer exists between pyrazoline group and 5-aryl group and this kind of interaction is increased in their microparticles.

  15. The Complex Core Level Spectra of CeO2: An Analysis in Terms of Atomic and Charge Transfer Effects

    Energy Technology Data Exchange (ETDEWEB)

    Bagus, Paul S; Nelin, Constance J; Ilton, Eugene S; Baron, Martin; Abbott, Heather; Primorac, Elena; Kuhlenbeck, Helmut; Shaikhutdinov, Shamil; Freund, Hans-Joachim

    2010-03-05

    We present a rigorous parameter-free theoretical treatment of the Ce 4s and 5s photoelectron spectra of CeO2. In the currently accepted model the satellite structure in the photoelectron spectra is explained in terms of a mixed valence (Ce 4f0 O 2p6, Ce 4f1 O 2p5, and Ce 4f2 O 2p4) configurations. We show that charge transfer (CT) into Ce 5d as well as configurations involving intra-atomic movement of charge must be considered in addition and compute their contributions to the spectra.

  16. CNDO/SCF molecular orbital structural studies and charge transfer complex formation between 4,4’-dimethoxydiquinone and uracil

    Directory of Open Access Journals (Sweden)

    Anwar S. El-Shahawy

    2004-12-01

    Full Text Available Through CNDO/SCF molecular orbital calculations, the structure of 4,4’-dimethoxy- diquinone (DQ has been discussed and compared with some related compounds. The electron transfer between DQ and uracil was studied in ethanol as an interaction medium. The ionization potentials and the electron affinities of the studied molecules have been calculated in addition to their charge densities giving the columbic potential energy of the donor and acceptor. The experimental charge transfer band lies at 500 nm. The electronic transitions have been calculated for the singlet and triplet transitions in uracil and DQ molecules using the SCF eigenvectors of the two HOMO’s, ψn-1 and ψ n, and the two LUMO’s, ψ n+1 and ψ n+2, using CI theory. The calculated electronic transitions are compared with those of the experimental data to verify the non-planar structure of the DQ molecule.

  17. Charge-transfer with graphene and nanotubes

    Directory of Open Access Journals (Sweden)

    C.N.R. Rao

    2010-09-01

    Full Text Available Charge-transfer between electron–donor and –acceptor molecules is a widely studied subject of great chemical interest. Some of the charge-transfer compounds in solid state exhibit novel electronic properties. In the last two to three years, occurrence of molecular charge-transfer involving single-walled carbon nanotubes (SWNTs and graphene has been demonstrated. This interaction gives rise to significant changes in the electronic properties of these nanocarbons. We examine charge-transfer phenomenon in graphene and SWNTs in this article in view of its potential utility in device applications.

  18. Intermolecular-charge-transfer-induced fluorescence quenching in protic solvent

    Science.gov (United States)

    Lin, Tao; Liu, Xiaojun; Lou, Zhidong; Hou, Yanbing; Teng, Feng

    2016-11-01

    The fluorescence quenching of fluorenone in protic solvent has been extensively investigated, and the intermolecular hydrogen bond was found to play a crucial role. Unfortunately, the mechanism at atomic level is still not clear. In the present work, we theoretically put forward the charge transfer along the hydrogen bond in the excited states. The vertical excitation energies of the fluorenone-methanol complex as well as the potential energy profiles and surfaces of the vertical excited states and charge transfer states were calculated by using the ab initio electronic-structure methods. The photochemical reactions occurring in the diverse charge transfer states were compared and their decisiveness to the fluorescence quenching was discussed in the paper.

  19. Resonant charge transfer at dielectric surfaces

    CERN Document Server

    Marbach, Johannes; Fehske, Holger

    2012-01-01

    We report on the theoretical description of secondary electron emission due to resonant charge transfer occurring during the collision of metastable nitrogen molecules with dielectric surfaces. The emission is described as a two step process consisting of electron capture to form an intermediate shape resonance and subsequent electron emission by decay of this ion, either due to its natural life time or its interaction with the surface. The electron capture is modeled using the Keldysh Green's function technique and the negative ion decay is described by a combination of the Keldysh technique and a rate equation approach. We find the resonant capture of electrons to be very efficient and the natural decay to be clearly dominating over the surface-induced decay. Secondary electron emission coefficients are calculated for aluminum oxide, magnesium oxide, silicon oxide, and diamond at several kinetic energies of the projectile. With the exception of magnesium oxide the coefficients turn out to be of the order of...

  20. 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

    Science.gov (United States)

    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.

  1. Correlating electronic and vibrational motions in charge transfer systems

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-06-27

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

  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.

    Science.gov (United States)

    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. Comparative study of Green's function matrix elements and charge transfers obtained from different partitioning schemes of molecular charge in hydrogen-bonded complexes

    Directory of Open Access Journals (Sweden)

    Parnaíba-da Silva Antenor J.

    2006-01-01

    Full Text Available RHF and MP2 ab initio molecular orbital calculations using the 4-31G**, 6-311G** and cc-pVTZ basis sets have revealed that the Green's function matrix element (G D,A values show a good correlation with the amount of intermolecular transferred charges obtained from different charge partitioning schemes for the CNH?CNH, NCH?CNH, CNH?NCH and NCH?NCH hydrogen bonded complexes. This is evident specially when the hydrogen bond distance is progressively increased from the equilibrium position until 4.5 Å. However, G D,A values show a better linear correlation with deltaQ values using corrected Mülliken charges, which are obtained from the charge-charge flux-overlap (CCFO model for infrared intensities. In this case, both G D,A and deltaQcorr form two practically superposed exponential curves. On the other hand, G D,A values show a smaller agreement with deltaQ values obtained from atomic charges derived from natural bonding orbitals. This is clearly verified when considering the first order exponential decay rate of G D,A versus deltaQ obtained from different charge partitioning schemes.

  4. Conformational control of benzophenone-sensitized charge transfer in dinucleotides

    OpenAIRE

    Merz, Thomas; Wenninger, Matthias; Weinberger, Michael; Riedle, Eberhard; Wagenknecht, Hans-Achim; Schuetz, Martin

    2013-01-01

    Charge transfer in DNA cannot be understood without addressing the complex conformational flexibility, which occurs on a wide range of timescales. In order to reduce this complexity four dinucleotide models 1X consisting of benzophenone linked by a phosphodiester to one of the natural nucleosides X = A, G, T, C were studied in water and methanol. The theoretical work focuses on the dynamics and electronic structure of 1G. Predominant conformations in the two solvents were obtained by molecula...

  5. Altering intra- to inter-molecular hydrogen bonding by dimethylsulfoxide: A TDDFT study of charge transfer for coumarin 343

    Science.gov (United States)

    Liu, Xiaochun; Yin, Hang; Li, Hui; Shi, Ying

    2017-04-01

    DFT and TDDFT methods were carried out to investigate the influences of intramolecular and intermolecular hydrogen bonding on excited state charge transfer for coumarin 343 (C343). Intramolecular hydrogen bonding is formed between carboxylic acid group and carbonyl group in C343 monomer. However, in dimethylsulfoxide (DMSO) solution, DMSO 'opens up' the intramolecular hydrogen bonding and forms solute-solvent intermolecular hydrogen bonded C343-DMSO complex. Analysis of frontier molecular orbitals reveals that intramolecular charge transfer (ICT) occurs in the first excited state both for C343 monomer and complex. The results of optimized geometric structures indicate that the intramolecular hydrogen bonding interaction is strengthened while the intermolecular hydrogen bonding is weakened in excited state, which is confirmed again by monitoring the shifts of characteristic peaks of infrared spectra. We demonstrated that DMSO solvent can not only break the intramolecular hydrogen bonding to form intermolecular hydrogen bonding with C343 but also alter the mechanism of excited state hydrogen bonding strengthening.

  6. 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

    Science.gov (United States)

    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.

  7. Charge-transfer interactions of metoclopramide nausea drug against six kind of π-acceptors: spectral and thermal discussions.

    Science.gov (United States)

    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(-)).

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-04-02

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

  10. Architecture of a charge-transfer state regulating light harvesting in a plant antenna protein.

    Science.gov (United States)

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

    2008-05-01

    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). We found 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 delocalized 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 chlorophyll-zeaxanthin charge-transfer state and switching on and off the charge-transfer quenching during qE.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  12. Molecular Orbital and Density Functional Study of the Formation, Charge Transfer, Bonding and the Conformational Isomerism of the Boron Trifluoride (BF3 and Ammonia (NH3 Donor-Acceptor Complex

    Directory of Open Access Journals (Sweden)

    Dulal C. Ghosh

    2004-09-01

    Full Text Available The formation of the F3B–NH3 supermolecule by chemical interaction of its fragment parts, BF3 and NH3, and the dynamics of internal rotation about the ‘B–N’ bond have been studied in terms of parameters provided by the molecular orbital and density functional theories. It is found that the pairs of frontier orbitals of the interacting fragments have matching symmetry and are involved in the charge transfer interaction. The donation process stems from the HOMO of the donor into the LUMO of the acceptor and simultaneously, back donation stems from the HOMO of acceptor into the LUMO of the donor. The density functional computation of chemical activation in the donor and acceptor fragments, associated with the physical process of structural reorganization just prior to the event of chemical reaction, indicates that BF3 becomes more acidic and NH3 becomes more basic, compared to their separate equilibrium states. Theoretically it is observed that the chemical reaction event of the formation of the supermolecule from its fragment parts is in accordance with the chemical potential equalization principle of the density functional theory and the electronegativity equalization principle of Sanderson. The energetics of the chemical reaction, the magnitude of the net charge transfer and the energy of the newly formed bond are quite consistent, both internally and with the principle of maximum hardness, PMH. The dynamics of the internal rotation of one part with respect to the other part of the supermolecule about the ‘B–N’ bond mimics the pattern of the conformational isomerism of the isostructural ethane molecule. It is also observed that the dynamics and evolution of molecular conformations as a function of dihedral angles is also in accordance with the principle of maximum hardness, PMH. Quite consistent with spectroscopic predictions, the height of the molecule

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

    Energy Technology Data Exchange (ETDEWEB)

    Weiss, Emily A. [Northwestern Univ., Evanston, IL (United States)

    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.

  14. Intramolecular charge transfer effects on 3-aminobenzoic acid

    Energy Technology Data Exchange (ETDEWEB)

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

    2006-03-20

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

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

    African Journals Online (AJOL)

    stock solutions of drugs are stable for a period of at least one week when kept .... Linearity was assessed by analysing a set of six calibration standards. ... sample analysis in the absence of the analyte and k is the slope of the calibration graph.

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

    Science.gov (United States)

    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}.

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

    CERN Document Server

    Babb, James F

    2016-01-01

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

  18. Opposites Attract: Organic Charge Transfer Salts

    Science.gov (United States)

    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…

  19. Optics of Chromites and Charge-Transfer Transitions

    Directory of Open Access Journals (Sweden)

    Andrei V. Zenkov

    2008-01-01

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

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

    KAUST Repository

    Zheng, Zilong

    2017-05-08

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

  1. Charge Transfer in Nanocrystalline Semiconductor Electrodes

    Directory of Open Access Journals (Sweden)

    M. Bouroushian

    2013-01-01

    Full Text Available Nanocrystalline electrodes in liquid junction devices possess a number of unique properties arising from their convoluted structure and the dimensions of their building units. The light-induced charge separation and transport in photoelectrochemical systems using nanocrystalline/nanoporous semiconductor electrodes is discussed here in connection with the basic principles of the (Schottky barrier theory. Recent models for charge transfer kinetics in normal and unipolar (dye-sensitized cells are reviewed, and novel concepts and materials are considered.

  2. PHOTOINDUCED CHARGE TRANSFER POLYMERIZATION OF STYRENE INITIATED BY ELECTRON ACCEPTOR

    Institute of Scientific and Technical Information of China (English)

    CAO Weixiao; ZHANG Peng; FENG Xinde

    1995-01-01

    Photoinduced charge transfer polymerization of styrene(St) with electron acceptor as initiator was investigated. In case of fumaronitrile (FN) or maleic anhydride (MA) as initiator the polymerization takes place regularly, whereas the tetrachloro-1, 4-benzenequinone (TCQ), 2, 3-dichloro-5, 6-dicyano-1, 4-benzenequinone (DDQ) . or tetracyano ethylene (TCNE) as initiator the polymerization proceeds reluctantly only after the photoaddition reaction. A mechanism was proposed that free radicals would be formed following the charge and proton transfer in the exciplex formed between St and electron acceptors.

  3. Charge Transfer Based Colorimetric Detection of Silver Ion

    Energy Technology Data Exchange (ETDEWEB)

    Han, Seung Choul; Kim, Kwang Seob; Choi, Soon Kyu; Oh, Jinho; Lee, Jae Wook [Dong-A Univ., Busan (Korea, Republic of)

    2014-05-15

    We have demonstrated the colorimetric chemosensor for detection of Ag{sup +} via formation of nanoparticles which is based on the intramolecular CT interaction between the electron-rich (2,6-dialkoxynaphthalene; Np) moiety and the electron-deficient (methyl viologen; MV{sup 2+}) moiety of a single sensor molecule. Under irradiation of light, Ag{sup +} was reduced to very small silver nanoparticle by CT interaction in the presence of OEGs as flexible recognition moiety of Ag{sup +} and stabilizer for Ag nanoparticles, thus Ag nanoparticles resulted to reddish brown in the color change of sensor solution, gradually. Therefore, the charge-transfer interaction between an electron-deficient and an electron-rich units existing at a sensor molecule can be regarded as a new and efficient method to construct various colorimetric chemosensors. Donor.acceptor interactions or charge transfer (CT) interactions are an important class of non-covalent interactions and have been widely exploited in self-assembling systems. Beyond molecular chemistry, supramolecular chemistry aims at constituting highly complex, functional chemical systems from components held together by intermolecular forces. Chemosensors are the molecules of abiotic origin that bind selectively and reversibly with the analyte with concomitant change in one or more properties of the system. The recognition and signaling of ionic and neutral species of varying complexity is one of the most intensively studied areas of contemporary supramolecular chemistry.

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

    Science.gov (United States)

    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.

  5. Computational Approach to Electron Charge Transfer Reactions

    DEFF Research Database (Denmark)

    Jónsson, Elvar Örn

    -molecular mechanics scheme, and tools to analyse statistical data and generate relative free energies and free energy surfaces. The methodology is applied to several charge transfer species and reactions in chemical environments - chemical in the sense that solvent, counter ions and substrate surfaces are taken...... in to account - which directly influence the reactants and resulting reaction through both physical and chemical interactions. All methods are though general and can be applied to different types of chemistry. First, the basis of the various theoretical tools is presented and applied to several test systems...... to show general (or expected) properties. Properties such as in the physical and (semi-)chemical interface between classical and quantum systems and the effects of molecular bond length constraints on the temperature during simulations. As a second step the methodology is applied to the symmetric...

  6. Charge-transfer processes in semiconductor colloids

    Science.gov (United States)

    Kamat, Prashant V.; Gopidas, K. R.

    1990-04-01

    A picosecond transient absorption spectroscopy technique has been employed to probe the charge transfer processes in Ti02 semiconductor colloids. The trapping of electrons at the TiO surface (Ti4+ sitesY was characterized from the appearance of a broad absorption in the region of 550-750 nm following the 355-nm laser pulse excitation of Ti02 colloids. The lifetime of these trapped charge carriers increased upon incorporation of a hole scavenger in the colloidal semiconductor system. The mechanistic and kinetic details of the charge injection from excited CdS into a large bandgap semiconductor such as AgI and Ti02 have also been inves-' t i ga ted.

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

    Institute of Scientific and Technical Information of China (English)

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

    2012-01-01

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

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

    KAUST Repository

    Gruenewald, Marco

    2015-02-11

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

  9. Charge transfer between sensing and targeted metal nanoparticles in indirect nanoplasmonic sensors

    Science.gov (United States)

    Zhdanov, Vladimir P.; Langhammer, Christoph

    2017-03-01

    In indirect nanoplasmonic sensors, the plasmonic metal nanoparticles are adjacent to the material of interest, and the material-related changes of their optical properties are used to probe that material. If the latter itself represents another metal in the form of nanoparticles, its deposition is accompanied by charge transfer to or from the plasmonic nanoparticles in order to equalize the Fermi levels. We estimate the value of the transferred charge and show on the two examples, nanoparticle sintering and hydride formation, that the charge transfer has negligible influence on the probed processes, because the effect of charge transfer is less important than that of nanoparticle surface energy. This further corroborates the non-invasive nature of nanoplasmonic sensors.

  10. Elementary charge-transfer processes in mesoscopic conductors

    NARCIS (Netherlands)

    Vanević, M.; Nazarov, Y.V.; Belzig, W.

    2008-01-01

    We determine charge-transfer statistics in a quantum conductor driven by a time-dependent voltage and identify the elementary transport processes. At zero temperature unidirectional and bidirectional single-charge transfers occur. The unidirectional processes involve electrons injected from the sour

  11. Charge-transfer spectra of tetravalent lanthanide ions in oxides

    NARCIS (Netherlands)

    Hoefdraad, H.E.

    1975-01-01

    The charge-transfer spectra of Ce4+, Pr4+ and Tb4+ in a number of oxides are reported. It is noted that the position of the first charge-transfer band is fixed for the metal ion in an oxygen coordination of VI, but varies in VIII coordination as a function of the host lattice. It is argued that this

  12. Photoinduced charge transfer within polyaniline-encapsulated quantum dots decorated on graphene.

    Science.gov (United States)

    Nguyen, Kim Truc; Li, Dehui; Borah, Parijat; Ma, Xing; Liu, Zhaona; Zhu, Liangliang; Grüner, George; Xiong, Qihua; Zhao, Yanli

    2013-08-28

    A new method to enhance the stability of quantum dots (QDs) in aqueous solution by encapsulating them with conducting polymer polyaniline was reported. The polyaniline-encapsulated QDs were then decorated onto graphene through π-π interactions between graphene and conjugated polymer shell of QDs, forming stable polyaniline/QD/graphene hybrid. A testing electronic device was fabricated using the hybrid in order to investigate the photoinduced charge transfer between graphene and encapsulated QDs within the hybrid. The charge transfer mechanism was explored through cyclic voltammetry and spectroscopic studies. The hybrid shows a clear response to the laser irradiation, presenting a great advantage for further applications in optoelectronic devices.

  13. Near-resonant versus nonresonant chemiluminescent charge-transfer reactions of atomic ions with HCl

    Science.gov (United States)

    Glenewinkel-Meyer, Th.; Ottinger, Ch.

    1994-01-01

    Charge-transfer reactions of C+, O+, F+, Ar+ and some other atomic ions with hydrogen chloride were investigated at collision energies between eVc.m.. This may be due to formation of a long-lived collision complex (Ar-HCl)+.

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

    Science.gov (United States)

    Dyakonov, Vladimir

    2013-03-01

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

  15. Graphene Charge Transfer, Spectroscopy, and Photochemical Reactions

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-01-31

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

  16. Study of fluorescence characteristics of the charge-transfer reaction of quinolone agents with bromanil

    Science.gov (United States)

    Li, Wen-Ying; Chen, Xiao-Fang; Xuan, Chun-Sheng

    2009-01-01

    A spectrofluorimetric method was discussed for the determination of three antibacterial quinolone derivatives, ofloxacin (OFL), norfloxacin (NOR) and ciprofloxacin (CIP) through charge-transfer complexation (CTC) with 2,3,5,6-tetrabromo-1,4-benzoquinone (bromanil, TBBQ). The method was based on the reaction of these drugs as n-electron donors with the π-acceptor TBBQ. TBBQ was found to react with these drugs to produce a kind of yellow complexes and the fluorescence intensities of the complexes were enhanced by 29-36 times more than those of the corresponding monomers. UV-vis, 1H NMR and XPS techniques were used to study the complexes formed. The various experimental parameters affecting the fluorescence intensity were studied and optimized. Under optimal reaction conditions, the rectilinear calibration graphs were obtained in the concentration range of 0.021-2.42 μg mL -1, 0.017-2.63 μg mL -1 and 0.019-2.14 μg mL -1 for OFL, NOR and CIP, respectively. The methods developed were applied successfully to the determination of the subject drugs in their pharmaceutical dosage forms with good precision and accuracy compared to official and reported methods as revealed by t- and F-tests.

  17. Charge Transfer Fluctuations as a Signal for QGP

    OpenAIRE

    Shi, Lijun; Jeon, Sangyong

    2005-01-01

    In this work, the charge transfer fluctuation which was previously used for $pp$ collisions is proposed for relativistic heavy-ion collisions as a QGP probe. We propose the appearance of a local minimum at midrapidity for the charge transfer fluctuation as a signal for a QGP. Within a two-component neutral cluster model, we demonstrate that the charge transfer fluctuation can detect the presence of a QGP as well as the size of the QGP in the rapidity space. We also show that the forward-backw...

  18. Charge transfer and emergent phenomena of oxide heterostructures

    Science.gov (United States)

    Chen, Hanghui

    Charge transfer is a common phenomenon at oxide interfaces. We use first-principles calculations to show that via heterostructuring of transition metal oxides, the electronegativity difference between two dissimilar transition metal ions can lead to high level of charge transfer and induce substantial redistribution of electrons and ions. Notable examples include i) enhancing correlation effects and inducing a metal-insulator transition; ii) tailoring magnetic structures and inducing interfacial ferromagnetism; iii) engineering orbital splitting and inducing a non-cuprate single-orbital Fermi surface. Utilizing charge transfer to induce emergent electronic/magnetic/orbital properties at oxide interfaces is a robust approach. Combining charge transfer with quantum confinement and expitaxial strain provides an appealing prospect of engineering electronic structure of artificial oxide heterostructures. This research was supported by National Science Foundation under Grant No. DMR-1120296.

  19. Charge transfer in time-dependent density functional theory

    Science.gov (United States)

    Maitra, Neepa T.

    2017-10-01

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

  20. Charge-transfer pipi* excited state in the 7-azaindole dimer. A hybrid configuration interactions singles/time-dependent density functional theory description.

    Science.gov (United States)

    Gelabert, Ricard; Moreno, Miquel; Lluch, José M

    2006-01-26

    The hybrid configuration interaction singles/time dependent density functional theory approach of Dreuw and Head-Gordon [Dreuw, A.; Head-Gordon, M. J. Am. Chem. Soc. 2004, 126, 4007] has been applied to study the potential energy landscape and accessibility of the charge-transfer pipi* excited state in the dimer of 7-azaindole, which has been traditionally considered a model for DNA base pairing. It is found that the charge-transfer pipi* excited state preferentially stabilizes the product of a single proton transfer. In this situation, the crossing between this state and the photoactive electronic state of the dimer is accessible. It is found that the charge-transfer pipi* excited state has a very steep potential energy profile with respect to any single proton-transfer coordinate and, in contrast, an extremely flat potential energy profile with respect to the stretch of the single proton-transfer complex. This is predicted to bring about a pair of rare fragments of the 7-azaindole dimer, physically separated and hence having very long lifetimes. This could have implications in the DNA base pairs of which the system is an analogue, in the form of replication errors.

  1. Towards first-principles prediction of valence instabilities in mixed stack charge-transfer crystals

    Science.gov (United States)

    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.

  2. Charge Transfer Dynamics from Photoexcited Semiconductor Quantum Dots

    Science.gov (United States)

    Zhu, Haiming; Yang, Ye; Wu, Kaifeng; Lian, Tianquan

    2016-05-01

    Understanding photoinduced charge transfer from nanomaterials is essential to the many applications of these materials. This review summarizes recent progress in understanding charge transfer from quantum dots (QDs), an ideal model system for investigating fundamental charge transfer properties of low-dimensional quantum-confined nanomaterials. We first discuss charge transfer from QDs to weakly coupled acceptors within the framework of Marcus nonadiabatic electron transfer (ET) theory, focusing on the dependence of ET rates on reorganization energy, electronic coupling, and driving force. Because of the strong electron-hole interaction, we show that ET from QDs should be described by the Auger-assisted ET model, which is significantly different from ET between molecules or from bulk semiconductor electrodes. For strongly quantum-confined QDs on semiconductor surfaces, the coupling can fall within the strong coupling limit, in which case the donor-acceptor interaction and ET properties can be described by the Newns-Anderson model of chemisorption. We also briefly discuss recent progress in controlling charge transfer properties in quantum-confined nanoheterostructures through wavefunction engineering and multiple exciton dissociation. Finally, we identify a few key areas for further research.

  3. Charge transfer in the cold Yb$^+$ + Rb collisions

    CERN Document Server

    Sayfutyarova, Elvira R; Yakovleva, Svetlana A; Belyaev, Andrey K

    2013-01-01

    Charge-transfer cold Yb$^+$ + Rb collision dynamics is investigated theoretically using high-level {\\it ab initio} potential energy curves, dipole moment functions and nonadiabatic coupling matrix elements. Within the scalar-relativistic approximation, the radiative transitions from the entrance $A^1\\Sigma^+$ to the ground $X^1\\Sigma^+$ state are found to be the only efficient charge-transfer pathway. The spin-orbit coupling does not open other efficient pathways, but alters the potential energy curves and the transition dipole moment for the $A-X$ pair of states. The radiative, as well as the nonradiative, charge-transfer cross sections calculated within the $10^{-3}-10$ cm$^{-1}$ collision energy range exhibit all features of the Langevin ion-atom collision regime, including a rich structure associated with centrifugal barrier tunneling (orbiting) resonances. Theoretical rate coefficients for two Yb isotopes agree well with those measured by immersing Yb$^+$ ion in an ultracold Rb ensemble in a hybrid trap....

  4. Dynamics of Charge Transfer in Ordered and Chaotic Nucleotide Sequences

    CERN Document Server

    Fialko, N S

    2013-01-01

    Charge transfer is considered in systems composed of a donor, an acceptor and bridge sites of (AT) nucleotide pairs. For a bridge consisting of 180 (AT) pairs, three cases are dealt with: a uniform case, when all the nucleotides in each strand are identical; an ordered case, when nucleotides in each DNA strand are arranged in an orderly fashion; a chaotic case, when (AT) and (TA) pairs are arranged randomly. It is shown that in all the cases a charge transfer from a donor to an acceptor can take place. All other factors being equal, the transfer is the most efficient in the uniform case, the ordered and chaotic cases are less and the least efficient, accordingly. The results obtained are in agreement with experimental data on long-range charge transfer in DNA.

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

    Science.gov (United States)

    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.

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

    KAUST Repository

    Alsam, Amani Abdu

    2017-03-14

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

  7. Charge Transfer in Multiple Site Chemical Systems.

    Science.gov (United States)

    2014-09-26

    as catalysis , photoredox systems, and studies of the fundamental properties of film-coated electrodes. 8 One method of attachment of metal complexes...reduction ot Ru(bpy)33+ by released ocalate, the photocurrent in the heterogeneous system remained fairly stable over the period of 2-3 hours if

  8. Surface-enhanced photoinduced charge transfer processes in metal-molecule nanoclusters

    OpenAIRE

    Centeno, Silvia P.; Ruano, Cristina; Román-Pérez, Jéssica; López-Tocón, Isabel; Soto, Juan; Otero, Juan Carlos

    2013-01-01

    This work deals with the unexplained efficiency of the electrode potential (EV) in tuning the energy of Charge Transfer (ECT) electronic states of hybrid systems formed by molecules and metal nanostructures. Huge energy gains (G) of up to 5 eV/V observed in electrochemical SERS experiences have been tentatively explained by a local increase of the electric potential at specific adsorption sites.[1] This gain, which is in conflict with the classical picture of the metal-adsorbate CT mechanism ...

  9. Charge transfer to a semi-esterified bifunctional phenol

    Energy Technology Data Exchange (ETDEWEB)

    Brede, O.; Hermann, R.; Orthner, H. [Leipzig Univ. (Germany)

    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-phenylac rylate (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. (author).

  10. Charge Transfer and Catalysis at the Metal Support Interface

    Energy Technology Data Exchange (ETDEWEB)

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

    2012-07-31

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

  11. Microgravity and Charge Transfer in the Neuronal Membrane: Implications for Computational Neurobiology

    Science.gov (United States)

    Wallace, Ron

    1995-01-01

    Evidence from natural and artificial membranes indicates that the neural membrane is a liquid crystal. A liquid-to-gel phase transition caused by the application of superposed electromagnetic fields to the outer membrane surface releases spin-correlated electron pairs which propagate through a charge transfer complex. The propagation generates Rydberg atoms in the lipid bilayer lattice. In the present model, charge density configurations in promoted orbitals interact as cellular automata and perform computations in Hilbert space. Due to the small binding energies of promoted orbitals, their automata are highly sensitive to microgravitational perturbations. It is proposed that spacetime is classical on the Rydberg scale, but formed of contiguous moving segments, each of which displays topological equivalence. This stochasticity is reflected in randomized Riemannian tensor values. Spacetime segments interact with charge automata as components of a computational process. At the termination of the algorithm, an orbital of high probability density is embedded in a more stabilized microscopic spacetime. This state permits the opening of an ion channel and the conversion of a quantum algorithm into a macroscopic frequency code.

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

    Science.gov (United States)

    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.

  13. Valence Topological Charge-Transfer Indices for Dipole Moments

    Directory of Open Access Journals (Sweden)

    Francisco Torrens

    2003-01-01

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

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

    NARCIS (Netherlands)

    Parisi, J; Dyakonov, [No Value; Pientka, M; Riedel, [No Value; Deibel, C; Brabec, CJ; Sariciftci, NS; Hummelen, JC

    2002-01-01

    The development of polymer-fullerene plastic solar cells has made significant progress in recent years. These devices excel by an efficient charge generation process as a consequence of a photoinduced charge transfer between the photo-excited conjugated polymer donor and acceptor-type fullerene

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

    Science.gov (United States)

    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

  16. Charge-Transfer Interactions in Organic Functional Materials

    Directory of Open Access Journals (Sweden)

    Bih-Yaw Jin

    2010-08-01

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

  17. The effect of solvent polarity on the balance between charge transfer and non-charge transfer pathways in the sensitization of singlet oxygen by pipi triplet states.

    Science.gov (United States)

    Schmidt, Reinhard

    2006-05-11

    A large set of literature kinetic data on triplet (T(1)) sensitization of singlet oxygen by two series of biphenyl and naphthalene sensitizers in solvents of strongly different polarity has been analyzed. The rate constants and the efficiencies of singlet oxygen formation are quantitatively reproduced by a model that assumes the competition of a non-charge transfer (nCT) and a CT deactivation channel. nCT deactivation occurs from a fully established spin-statistical equilibrium of (1)(T(1)(3)Sigma) and (3)(T(1)(3)Sigma) encounter complexes by internal conversion (IC) to lower excited complexes that dissociate to yield O(2)((1)Sigma(g)(+)), O(2)((1)Delta(g)), and O(2)((3)Sigma(g)(-)). IC of (1,3)(T(1)(3)Sigma) encounter complexes is controlled by an energy gap law that is generally valid for the transfer of electronic energy to and from O(2). (1,3)(T(1)(3)Sigma) nCT complexes form in competition to IC (1)(T(1)(3)Sigma) and (3)(T(1)(3)Sigma) exciplexes if CT interactions between T(1) and O(2) are important. The rate constants of exciplex formation depend via a Marcus type parabolic model on the corresponding free energy change DeltaG(CT), which varies with sensitizer triplet energy, oxidation potential, and solvent polarity. O(2)((1)Sigma(g)(+)), O(2)((1)Delta(g)), and O(2)((3)Sigma(g)(-)) are formed in the product ratio (1/6):(1/12):(3/4) in the CT deactivation channel. The balance between nCT and CT deactivation is described by the relative contribution p(CT) of CT induced deactivation calculated for a sensitizer of known triplet energy from its quenching rate constant. It is shown how the change of p(CT) influences the quenching rate constant and the efficiency of singlet oxygen formation in both series of sensitizers. p(CT) is sensitive to differences of solvent polarity and varies for the biphenyls and the naphthalenes as sigmoidal with DeltaG(CT). This quantitative model represents a realistic and general mechanism for the quenching of pipi triplet states by O

  18. 2,3-Dichloro-1,4-hydro-quinone 2,3-dichloro-1,4-benzoquinone monohydrate: a quinhydrone-type 1:1 donor-acceptor [D-A] charge-transfer complex.

    Science.gov (United States)

    Guégano, Xavier; Hauser, Jürg; Liu, Shi-Xia; Decurtins, Silvio

    2011-11-01

    IN THE CRYSTAL STRUCTURE OF THE TITLE COMPOUND (SYSTEMATIC NAME: 2,3-dichloro-benzene-1,4-diol 2,3-dichloro-cyclo-hexa-2,5-diene-1,4-dione monohydrate), C(6)H(4)Cl(2)O(2)·C(6)H(2)Cl(2)O(2)·H(2)O, the 2,3-dichloro-1,4-hydro-quinone donor (D) and the 2,3-dichloro-1,4-benzoquinone acceptor (A) mol-ecules form alternating stacks along [100]. Their mol-ecular planes [maximum deviations for non-H atoms: 0.0133 (14) (D) and 0.0763 (14) Å (A)] are inclined to one another by 1.45 (3)° and are thus almost parallel. There are π-π inter-actions involving the D and A mol-ecules, with centroid-centroid distances of 3.5043 (9) and 3.9548 (9) Å. Inter-molecular O-H⋯O hydrogen bonds involving the water mol-ecule and the hy-droxy and ketone groups lead to the formation of two-dimensional networks lying parallel to (001). These networks are linked by C-H⋯O inter-actions, forming a three-dimensional structure.

  19. 2,3-Dichloro-1,4-hydroquinone 2,3-dichloro-1,4-benzoquinone monohydrate: a quinhydrone-type 1:1 donor-acceptor [D—A] charge-transfer complex

    Directory of Open Access Journals (Sweden)

    Xavier Guégano

    2011-11-01

    Full Text Available In the crystal structure of the title compound (systematic name: 2,3-dichlorobenzene-1,4-diol 2,3-dichlorocyclohexa-2,5-diene-1,4-dione monohydrate, C6H4Cl2O2·C6H2Cl2O2·H2O, the 2,3-dichloro-1,4-hydroquinone donor (D and the 2,3-dichloro-1,4-benzoquinone acceptor (A molecules form alternating stacks along [100]. Their molecular planes [maximum deviations for non-H atoms: 0.0133 (14 (D and 0.0763 (14 Å (A] are inclined to one another by 1.45 (3° and are thus almost parallel. There are π–π interactions involving the D and A molecules, with centroid–centroid distances of 3.5043 (9 and 3.9548 (9 Å. Intermolecular O—H...O hydrogen bonds involving the water molecule and the hydroxy and ketone groups lead to the formation of two-dimensional networks lying parallel to (001. These networks are linked by C—H...O interactions, forming a three-dimensional structure.

  20. 2,3-Dichloro-1,4-hydro­quinone 2,3-dichloro-1,4-benzoquinone monohydrate: a quinhydrone-type 1:1 donor-acceptor [D—A] charge-transfer complex

    Science.gov (United States)

    Guégano, Xavier; Hauser, Jürg; Liu, Shi-Xia; Decurtins, Silvio

    2011-01-01

    In the crystal structure of the title compound (systematic name: 2,3-dichloro­benzene-1,4-diol 2,3-dichloro­cyclo­hexa-2,5-diene-1,4-dione monohydrate), C6H4Cl2O2·C6H2Cl2O2·H2O, the 2,3-dichloro-1,4-hydro­quinone donor (D) and the 2,3-dichloro-1,4-benzoquinone acceptor (A) mol­ecules form alternating stacks along [100]. Their mol­ecular planes [maximum deviations for non-H atoms: 0.0133 (14) (D) and 0.0763 (14) Å (A)] are inclined to one another by 1.45 (3)° and are thus almost parallel. There are π–π inter­actions involving the D and A mol­ecules, with centroid–centroid distances of 3.5043 (9) and 3.9548 (9) Å. Inter­molecular O—H⋯O hydrogen bonds involving the water mol­ecule and the hy­droxy and ketone groups lead to the formation of two-dimensional networks lying parallel to (001). These networks are linked by C—H⋯O inter­actions, forming a three-dimensional structure. PMID:22219991

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

    KAUST Repository

    Van Regemorter, Tanguy

    2012-09-15

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

  2. Charge-transfer states and optical transitions at the pentacene-TiO2 interface

    Science.gov (United States)

    Ljungberg, M. P.; Vänskä, O.; Koval, P.; Koch, S. W.; Kira, M.; Sánchez-Portal, D.

    2017-03-01

    Pentacene molecules have recently been observed to form a well-ordered monolayer on the (110) surface of rutile TiO2, with the molecules adsorbed lying flat, head to tail. With the geometry favorable for direct optical excitation and given its ordered character, this interface seems to provide an intriguing model to study charge-transfer excitations where the optically excited electrons and holes reside on different sides of the organic–inorganic interface. In this work, we theoretically investigate the structural and electronic properties of this system by means of ab initio calculations and compute its excitonic absorption spectrum. Molecular states appear in the band gap of the clean TiO2 surface, which enables charge-transfer excitations directly from the molecular HOMO to the TiO2 conduction band. The calculated optical spectrum shows a strong polarization dependence and displays excitonic resonances corresponding to the charge-transfer states, which could stimulate new experimental work on the optical response of this interface.

  3. Star-Forming Complexes in Galaxies

    CERN Document Server

    Elmegreen, B G

    2004-01-01

    Star complexes are the largest globular regions of star formation in galaxies. If there is a spiral density wave, nuclear ring, tidal arm, or other well-defined stellar structure, then gravitational instabilities in the gaseous component produce giant cloud complexes with a spacing of about three times the width. These gas complexes form star complexes, giving the familiar beads on a string of star formation along spiral arms, or nuclear hotspots in the case of a ring. Turbulence compression, supernovae, and self-gravitational contraction inside the giant clouds produce a nearly scale-free structure, including giant molecular clouds that form OB associations and molecular cloud cores that form clusters. Without stellar density waves or similar structures, random gravitational instabilities form flocculent spirals and these fragment into star complexes, OB associations and star clusters in the same way. The largest coherent star-forming regions are the flocculent arms themselves. At the core of the hierarchy a...

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

    Science.gov (United States)

    Bhattacharjee, Subham; Maiti, Bappa; Bhattacharya, Santanu

    2016-05-01

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

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

    DEFF Research Database (Denmark)

    Bohr, Henrik; Malik, F. Bary

    2013-01-01

    The observed multiple de-excitation pathways of photo-absorbed electronic excited state in the peridinin–chlorophyll complex, involving both energy and charge transfers among its constituents, are analyzed using the bio-Auger (B-A) theory. It is also shown that the usually used F¨orster–Dexter th...

  6. Implementing Metal-to-Ligand Charge Transfer in Organic Semiconductor for Improved Visible-Near-Infrared Photocatalysis.

    Science.gov (United States)

    Li, Yanrui; Wang, Zhaowu; Xia, Tong; Ju, Huanxin; Zhang, Ke; Long, Ran; Xu, Qian; Wang, Chengming; Song, Li; Zhu, Junfa; Jiang, Jun; Xiong, Yujie

    2016-08-01

    The coordination of organic semiconductors with metal cations can induce metal-to-ligand charge transfer, which broadens light absorption to cover the visible-near-infrared (vis-NIR) spectrum. As a proof-of-concept demonstration, the g-C3 N4 -based complex exhibits dramatically enhanced photocatalytic H2 production with excellent durability under vis-NIR irradiation.

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

    KAUST Repository

    Chen, Xian Kai

    2016-09-05

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

  8. Control over the charge transfer in dye-nanoparticle decorated graphene

    Science.gov (United States)

    Bongu, Sudhakara Reddy; Veluthandath, Aneesh V.; Nanda, B. R. K.; Ramaprabhu, Sundara; Bisht, Prem B.

    2016-01-01

    Charge transfer interaction between silver decorated graphene and three differently charged dyes, cationic (rhodamine 6G), neutral (rhodamine B) and anionic (fluorescein 27) has been studied. The ground state association constants have been evaluated and changes in the fluorescence intensity and lifetimes have been obtained in two solvents. Strength of complex-formation has been found to be higher with the cationic molecule in water. In a higher viscosity solvent, the ground state complex formation is restricted. Local field of localized surface plasmons of nanoparticles adsorbed on the graphene sheets leads to enhanced absorption and fluorescence of fluorescein 27.

  9. Spectroscopic Studies of Doping and Charge Transfer in Single Walled Carbon Nanotubes and Lead Sulfide Quantum Dots

    Science.gov (United States)

    Haugen, Neale O.

    The use of single wall carbon nanotubes (SW-CNTs) in solar photovoltaic (PV) devices is a relatively new, but quickly growing field. SW-CNTs have found application as transparent front contacts, and high work function back contacts in thin film solar PV. For the utility of SW-CNTs to be fully realized, however, controllable and stable doping as well as long term protection from doping must be achieved. Spectroscopic techniques facilitate detailed investigations of the intrinsic and variable properties of semiconductor materials without the issues of contact deposition and the possibility of sample contamination. Detailed spectroscopic analysis of the doping induced changes in the optical properties of SW-CNTs has revealed normally hidden excited state transitions in large diameter single walled carbon nanotubes for the first time. Spectroscopic monitoring of the degree of doping in SW-CNTs made possible studies of the dopant complex desorption and readsorption energies and kinetics. The long term protection from doping of SW-CNTs exposed to ambient laboratory conditions was achieved as a result of the more detailed understanding of the doping processes and mechanisms yielded by these spectroscopic studies. The application of SW-CNTs to other roles in solar PV devices was another goal of this research. Efficient collection of photogenerated charge carriers in semiconductor quantum dot (QD) based solar photovoltaic devices has been limited primarily by the poor transport properties and high density of recombination sites in the QD films. Coupling semiconductor QDs to nanomaterials with better transport properties is one potential solution to the poor transport within the QD films. This portion of the work investigated the possibility of charge transfer occurring in nano-heterostructures (NHSs) of PbS QDs and SW-CNTs produced through spontaneous self-assembly in solution. Electronic coupling in the form of charge transfer from the QDs to the SW-CNTs is unambiguously

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

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    N, Rekha T.; Rajkumar, Beulah J. M., E-mail: beulah-rajkumar@yahoo.co.in [PG & Research Department of Physics, Lady Doak College, Madurai 625002 (India)

    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.

  12. Charge transfer in conjugated oligomers encapsulated into carbon nanotubes

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-11-15

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

  13. Integrated Charge Transfer in Organic Ferroelectrics for Flexible Multisensing Materials.

    Science.gov (United States)

    Xu, Beibei; Ren, Shenqiang

    2016-09-01

    The ultimate or end point of functional materials development is the realization of strong coupling between all energy regimes (optical, electronic, magnetic, and elastic), enabling the same material to be utilized for multifunctionalities. However, the integration of multifunctionalities in soft materials with the existence of various coupling is still in its early stage. Here, the coupling between ferroelectricity and charge transfer by combining bis(ethylenedithio)tetrathiafulvalene-C60 charge-transfer crystals with ferroelectric polyvinylidene fluoride polymer matrix is reported, which enables external stimuli-controlled polarization, optoelectronic and magnetic field sensing properties. Such flexible composite films also display a superior strain-dependent capacitance and resistance change with a giant piezoresistance coefficient of 7.89 × 10(-6) Pa(-1) . This mutual coupled material with the realization of enhanced couplings across these energy domains opens up the potential for multisensing applications.

  14. Charge transfer in energetic Li^2+ - H collisions

    Science.gov (United States)

    Mancev, I.

    2008-07-01

    The total cross sections for charge transfer in Li^2+ - H collisions have been calculated, using the four-body first Born approximation with correct boundary conditions (CB1-4B) and four-body continuum distorted wave method (CDW-4B) in the energy range 10 - 5000 keV/amu. Present results call for additional experimental data at higher impact energies than presently available.

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

    Science.gov (United States)

    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.

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

    African Journals Online (AJOL)

    Pharmaceutical Chemistry Department, College of Pharmacy, King Saud University, P.O. Box 2457, ... International Pharmaceutical Abstract, Chemical Abstracts, Embase, Index Copernicus, EBSCO, African ..... Pharmacol 1982; 22: 137-142.

  17. Charge-transfer crystallites as molecular electrical dopants

    Science.gov (United States)

    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

    2015-10-01

    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.

  18. Orbital localization, charge transfer, and band gaps in semilocal density-functional theory.

    Science.gov (United States)

    Armiento, R; Kümmel, S

    2013-07-19

    We derive an exchange energy functional of generalized gradient form with a corresponding potential that changes discontinuously at integer particle numbers. The functional is semilocal, yet incorporates key features that are connected to the derivative discontinuity of Kohn-Sham density-functional theory. We validate our construction for several paradigm systems and explain how it addresses central well-known deficiencies of antecedent semilocal methods, i.e., the description of charge transfer, properly localized orbitals, and band gaps. We find, e.g., an improved shell structure for atoms, eigenvalues that more closely correspond to ionization energies, and an improved description of band structure where localized states are lowered in energy.

  19. Structure of Complex Verb Forms in Meiteilon

    Directory of Open Access Journals (Sweden)

    Lourembam Surjit Singh

    2016-12-01

    Full Text Available This piece of work proposes to descriptively investigate the structures of complex verbs in Meiteilon. The categorization of such verbs is based on the nature of semantic and syntactic functions of a lexeme or verbal lexeme. A lexeme or verbal lexeme in Meiteilon may have multifunctional properties in the nature of occurrence. Such lexical items can be co-occurred together in a phrase as single functional word. Specifically, in the co-occurrences of two lexical items, the first component of lexical items has different semantic and syntactic functions in comparison to semantic and syntactic functions of the second component of lexical items. Such co-occurrences of two lexical items are the forms of complex verb that are covered with the term complex predicate in this work. The investigation in constructing complex predicate is thoroughly presenting in this work. Keywords: Structures, complex verb, conjunct verb, compound verb, complex predicate

  20. Charge Transfer and Support Effects in Heterogeneous Catalysis

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-12-21

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

  1. Charge Transfer Fluorescence and 34 nm Exciton Diffusion Length in Polymers with Electron Acceptor End Traps.

    Science.gov (United States)

    Zaikowski, Lori; Mauro, Gina; Bird, Matthew; Karten, Brianne; Asaoka, Sadayuki; Wu, Qin; Cook, Andrew R; Miller, John R

    2015-06-18

    Photoexcitation of conjugated poly-2,7-(9,9-dihexylfluorene) polyfluorenes with naphthylimide (NI) and anthraquinone (AQ) electron-acceptor end traps produces excitons that form charge transfer states at the end traps. Intramolecular singlet exciton transport to end traps was examined by steady state fluorescence for polyfluorenes of 17-127 repeat units in chloroform, dimethylformamide (DMF), tetrahydrofuran (THF), and p-xylene. End traps capture excitons and form charge transfer (CT) states at all polymer lengths and in all solvents. The CT nature of the end-trapped states is confirmed by their fluorescence spectra, solvent and trap group dependence, and DFT descriptions. Quantum yields of CT fluorescence are as large as 46%. This strong CT emission is understood in terms of intensity borrowing. Energies of the CT states from onsets of the fluorescence spectra give the depths of the traps which vary with solvent polarity. For NI end traps, the trap depths are 0.06 (p-xylene), 0.13 (THF), and 0.19 eV (CHCl3). For AQ, CT fluorescence could be observed only in p-xylene where the trap depth is 0.27 eV. Quantum yields, emission energies, charge transfer energies, solvent reorganization, and vibrational energies were calculated. Fluorescence measurements on chains >100 repeat units indicate that end traps capture ∼50% of the excitons, and that the exciton diffusion length is LD = 34 nm, which is much larger than diffusion lengths reported in polymer films or than previously known for diffusion along isolated chains. The efficiency of exciton capture depends on chain length but not on trap depth, solvent polarity, or which trap group is present.

  2. Negative thermal expansion induced by intermetallic charge transfer.

    Science.gov (United States)

    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.

  3. Laser controlled charge-transfer reaction at low temperatures

    CERN Document Server

    Petrov, Alexander; Kotochigova, Svetlana

    2016-01-01

    We study the low-temperature charge transfer reaction between a neutral atom and an ion under the influence of near-resonant laser light. By setting up a multi-channel model with field-dressed states we demonstrate that the reaction rate coefficient can be enhanced by several orders of magnitude with laser intensities of $10^6$ W/cm$^2$ or larger. In addition, depending on laser frequency one can induce a significant enhancement or suppression of the charge-exchange rate coefficient. For our intensities multi-photon processes are not important.

  4. Simulation for signal charge transfer of charge coupled devices

    Institute of Scientific and Technical Information of China (English)

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

    2009-01-01

    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.

  5. Charge transfer and weak bonding between molecular oxygen and graphene zigzag edges at low temperatures

    CERN Document Server

    Boukhvalov, D W; Shames, A I; Takai, K; Hayashi, T; Enoki, T

    2016-01-01

    Electron paramagnetic resonance (EPR) study of air-physisorbed defective carbon nano-onions evidences in favor of microwave assisted formation of weakly-bound paramagnetic complexes comprising negatively-charged O2- ions and edge carbon atoms carrying pi-electronic spins. These complexes being located on the graphene edges are stable at low temperatures but irreversibly dissociate at temperatures above 50-60 K. These EPR findings are justified by density functional theory (DFT) calculations demonstrating transfer of an electron from the zigzag edge of graphene-like material to oxygen molecule physisorbed on the graphene sheet edge. This charge transfer causes changing the spin state of the adsorbed oxygen molecule from S = 1 to S = 1/2 one. DFT calculations show significant changes of adsorption energy of oxygen molecule and robustness of the charge transfer to variations of the graphene-like substrate morphology (flat and corrugated mono- and bi-layered graphene) as well as edges passivation. The presence of...

  6. Label-Free Acetylcholine Image Sensor Based on Charge Transfer Technology for Biological Phenomenon Tracking

    Science.gov (United States)

    Takenaga, Shoko; Tamai, Yui; Okumura, Koichi; Ishida, Makoto; Sawada, Kazuaki

    2012-02-01

    A 32 ×32 charge-transfer enzyme-type acetylcholine (ACh) image sensor array was produced for label-free tracking of images of ACh distribution and its performance in repeatable measurements without enzyme deactivation was examined. The proposed sensor was based on a charge-transfer-type pH image sensor, which was modified using an enzyme membrane (acetylcholine esterase, AChE) for each pixel. The ACh image sensor detected hydrogen ions generated by the ACh-AChE reaction. A polyion complex membrane composed of poly(L-lysine) and poly(4-styrenesulfonate) was used to immobilize the enzyme on the sensor. The improved uniformity and adhesion of the polyion complex membrane were evaluated in this study. As a result, temporal and spatial fluctuations of the ACh image sensor were successfully minimized using this approach. The sensitivity of the sensor was 4.2 mV/mM, and its detection limit was 20 µM. In five repeated measurements, the repeatability was 8.8%.

  7. Interface charge transfer process in ZnO:Mn/ZnS nanocomposites

    Science.gov (United States)

    Stefan, M.; Toloman, D.; Popa, A.; Mesaros, A.; Vasile, O. R.; Leostean, C.; Pana, O.

    2016-03-01

    ZnO:Mn/ZnS nanocomposites were prepared by seed-mediated growth of ZnS QDs onto the preformed ZnO:Mn nanoparticles. The formation of the nanocomposite structure has been evidenced by XRD, HRTEM, and XPS. The architecture of the nanocomposite with outer ZnS QDs around ZnO:Mn cores is sustained by the sulfur and oxygen depth profiles resulted from XPS. When the two components are brought together, the band gap of ZnS component decreases while that of ZnO:Mn increases. It is the result of interface charge transfer from ZnO:Mn to ZnS QDs. Here ZnO:Mn valence states are extended through the interface into unoccupied gap states of ZnS. The energy band setup is modified from a type II into a type I band alignment. The process is accompanied by enhancement of composite UV emission of PL spectra as compared to its counterparts. The charge transfer from valence band also determines the increase of the core-polarization effect of s shell electrons at Mn2+ nucleus, thus determining the increase of the hyperfine field through the reduction of the covalency degree of Zn(Mn)-O bonds. The quantum confinement in ZnS QDs promotes the ferromagnetic coupling of singly occupied states due to Zn vacancies determining a superparamagnetic behavior of the ensemble. When the nanocomposites are formed, due to interface charge transfer effects, an increased number of filled cation vacancies in ZnS QDs develop, thus disrupting the pre-existing ferromagnetic coupling between spins resulting in a significant reduction of the overall saturation magnetization. The possibility to modulate nanocomposite properties by controlling the interface interactions may be foreseen in these types of materials.

  8. Complex coacervates formed across liquid interfaces

    NARCIS (Netherlands)

    Monteillet, H.; Kleijn, J.M.; Sprakel, J.; Leermakers, F.A.M.

    2016-01-01

    The Scheutjens-Fleer self-consistent field (SF-SCF) theory is used to study complexation between two oppositely charged polyelectrolytes across an interface formed by two solvents, here called oil and water. The focus is on the composition and the lateral stability of such interfacial coacervate.

  9. Complex coacervates formed across liquid interfaces

    NARCIS (Netherlands)

    Monteillet, H.; Kleijn, J.M.; Sprakel, J.; Leermakers, F.A.M.

    2017-01-01

    The Scheutjens-Fleer self-consistent field (SF-SCF) theory is used to study complexation between two oppositely charged polyelectrolytes across an interface formed by two solvents, here called oil and water. The focus is on the composition and the lateral stability of such interfacial coacervate. On

  10. Super-iron Nanoparticles with Facile Cathodic Charge Transfer

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-12-31

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

  11. On the Possibility of Superfast Charge Transfer in DNA

    CERN Document Server

    Lakhno, V D

    2013-01-01

    Numerous experiments on charge transfer in DNA yield a contradictory picture of the transfer: on the one hand they suggest that it is a very slow process and the charge is almost completely localized on one Watson-Crick pair, but on the other hand they demonstrate that the charge can travel a very large distance. To explain this contradiction we propose that superfast charge transitions are possible between base pairs on individual DNA fragments resulting in the establishment of a quasi-equilibrium charge distribution during the time less than that of charge solvation. In other words, we hypothesize these states irrespective of the nature of a mechanism responsible for their establishment, whether it be a hopping mechanism, or a band mechanism, or superexchange, or polaron transport, etc., leaving aside the debates of which one is more advantageous. We discuss qualitative differences between the charge transfer in a dry DNA and that in a solution. In a solution, of great importance is the charge solvation whi...

  12. Ultrafast charge transfer via a conical intersection in dimethylaminobenzonitrile.

    Science.gov (United States)

    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.

  13. Energy and charge transfer in nanoscale hybrid materials.

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    Hendrickson, Heidi Phillips

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

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

    Science.gov (United States)

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

    2016-09-01

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

  16. Time-dependent quantum wave packet dynamics to study charge transfer in heavy particle collisions

    Science.gov (United States)

    Zhang, Song Bin; Wu, Yong; Wang, Jian Guo

    2016-12-01

    The method of time-dependent quantum wave packet dynamics has been successfully extended to study the charge transfer/exchange process in low energy two-body heavy particle collisions. The collision process is described by coupled-channel equations with diabatic potentials and (radial and rotational) couplings. The time-dependent coupled equations are propagated with the multiconfiguration time-dependent Hartree method and the modulo squares of S-matrix is extracted from the wave packet by the flux operator with complex absorbing potential (FCAP) method. The calculations of the charge transfer process 12Σ+ H-(1s2) +Li(1 s22 s ) →22Σ+ /32 Σ+ /12 Π H(1 s ) +Li-(1s 22 s 2 l ) (l =s ,p ) at the incident energy of about [0.3, 1.3] eV are illustrated as an example. It shows that the calculated reaction probabilities by the present FCAP reproduce that of quantum-mechanical molecular-orbital close-coupling very well, including the peak structures contributed by the resonances. Since time-dependent external interactions can be directly included in the present FCAP calculations, the successful implementation of FCAP provides us a powerful potential tool to study the quantum control of heavy particle collisions by lasers in the near future.

  17. Ultrafast dynamics of solvation and charge transfer in a DNA-based biomaterial.

    Science.gov (United States)

    Choudhury, Susobhan; Batabyal, Subrata; Mondol, Tanumoy; Sao, Dilip; Lemmens, Peter; Pal, Samir Kumar

    2014-05-01

    Charge migration along DNA molecules is a key factor for DNA-based devices in optoelectronics and biotechnology. The association of a significant amount of water molecules in DNA-based materials for the intactness of the DNA structure and their dynamic role in the charge-transfer (CT) dynamics is less documented in contemporary literature. In the present study, we have used a genomic DNA-cetyltrimethyl ammonium chloride (CTMA) complex, a technological important biomaterial, and Hoechest 33258 (H258), a well-known DNA minor groove binder, as fluorogenic probe for the dynamic solvation studies. The CT dynamics of CdSe/ZnS quantum dots (QDs; 5.2 nm) embedded in the as-prepared and swollen biomaterial have also been studied and correlated with that of the timescale of solvation. We have extended our studies on the temperature-dependent CT dynamics of QDs in a nanoenvironment of an anionic, sodium bis(2-ethylhexyl)sulfosuccinate reverse micelle (AOT RMs), whereby the number of water molecules and their dynamics can be tuned in a controlled manner. A direct correlation of the dynamics of solvation and that of the CT in the nanoenvironments clearly suggests that the hydration barrier within the Arrhenius framework essentially dictates the charge-transfer dynamics.

  18. Investigation of the contact charge transfer absorption of organic solvents with oxygen for use in oxygen determination.

    Science.gov (United States)

    Choi, M F; Hawkins, P

    1995-07-01

    The contact charge transfer (CCT) absorption spectra of dimethylsulphoxide (DMSO), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), ethanol, methanol, water, benzene (Bz), N,N'-diethylaniline (DEA), N,N'-dimethyl-p-toluidine (DMT) and N,N'-diethyl-p-toluidine with molecular oxygen have been investigated. These solvents form strong ultraviolet/visible CCT absorption spectra with intensities that are related to the partial pressure of the applied oxygen. DMSO, DMF, DMA, Bz, DEA and DMT are shown to form 1:1 molecular contact complexes with molecular oxygen. A simple oxygen sensing system is described using CCT absorption spectroscopy of DMT at a wavelength of 400 nm, with a gas flow rate of 60 cm(3) min(-1) through the solvent in a cuvette with a pathlength of 1 cm. Inexpensive plastic fibres are used to relay the light from a xenon lamp source to the cuvette and back to a photo-detector. The response of the sensing system to changes in oxygen concentration is reversible, non-linear and in good agreement with the Beer-Lambert law. The most sensitive response region is from 0 to 20% O(2) with a change in signal level of about 35%. The solvent used shows no deterioration in performance over a long period and can be used to determine gaseous oxygen concentrations from 0 to 100%. It does not respond to carbon dioxide.

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

    Directory of Open Access Journals (Sweden)

    Wendi Sapp

    2016-02-01

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

  20. Multivalence Charge Transfer in Doped and Codoped Photocatalytic TiO2.

    Science.gov (United States)

    Ren, Hangjuan; Koshy, Pramod; Cao, Fuyang; Sorrell, Charles Christopher

    2016-08-15

    The present work reports data for the mineralogical and chemical properties of anatase thin films individually doped or codoped with chromium and vanadium, fabricated by sol-gel spin coating on glass substrates and annealing at 450 °C for 2 h. X-ray photoelectron spectroscopy data indicated the presence of Ti(4+), Ti(3+), Cr(3+), and possibly Cr(4+) in the Cr-doped thin films; Ti(4+), Ti(3+), V(3+), V(4+), and possibly V(5+) in the V-doped thin films; and Ti(4+), Ti(3+), Cr(3+), Cr(4+), V(3+), V(4+), and possibly V(5+) in the codoped thin films. While the thermodynamically stable valences Ti(4+), Cr(3+), and V(5+) would be expected to have formed, the presence of the nonequilibrium valences Ti(3+), Cr(4+), V(3+), and V(4+) is considered to have resulted from intervalence charge transfer for the Cr-doped and V-doped systems but from multivalence charge transfer (MVCT) for the codoped system. The latter phenomenon, which is introduced as a new conceptual term, describes the nature of the mutual exchange of electrons during valence changes of both dopant (Cr, V) and matrix (Ti) ions during annealing. In the present case, MVCT appears to be a transient metastable condition that acts during annealing, but subsequent UV irradiation can alter its effects.

  1. Control of intrachain charge transfer in model systems for block copolymer photovoltaic materials.

    Science.gov (United States)

    Johnson, Kerr; Huang, Ya-Shih; Huettner, Sven; Sommer, Michael; Brinkmann, Martin; Mulherin, Rhiannon; Niedzialek, Dorota; Beljonne, David; Clark, Jenny; Huck, Wilhelm T S; Friend, Richard H

    2013-04-01

    We report the electronic properties of the conjugated coupling between a donor polymer and an acceptor segment serving as a model for the coupling in conjugated donor-acceptor block copolymers. These structures allow the study of possible intrachain photoinduced charge separation, in contrast to the interchain separation achieved in conventional donor-acceptor blends. Depending on the nature of the conjugated linkage, we observe varying degrees of modification of the excited states, including the formation of intrachain charge transfer excitons. The polymers comprise a block (typically 18 repeat units) of P3HT, poly(3-hexyl thiophene), coupled to a single unit of F8-TBT (where F8 is dioctylfluorene, and TBT is thiophene-benzothiadiazole-thiophene). When the P3HT chain is linked to the TBT unit, we observe formation of a localized charge transfer state, with red-shifted absorption and emission. Independent of the excitation energy, this state is formed very rapidly (<40 fs) and efficiently. Because there is only a single TBT unit present, there is little scope for long-range charge separation and it is relatively short-lived, <1 ns. In contrast, when the P3HT chain and TBT unit are separated by the wider bandgap F8 unit, there is little indication for modification of either ground or excited electronic states, and longer-lived charge separated states are observed.

  2. Charge transfer to a dielectric target by guided ionization waves using electric field measurements

    Science.gov (United States)

    Slikboer, Elmar; Garcia-Caurel, Enric; Guaitella, Olivier; Sobota, Ana

    2017-03-01

    A kHz-operated atmospheric pressure plasma jet is investigated by measuring charge transferred to a dielectric electro-optic surface (BSO crystal) allowing for the measurement of electric field by exploiting the Pockels effect. The electric field values, distribution of the surface discharge and amount of deposited charge are obtained for various parameters, including gas flow, applied voltage, target distance and the length of the capillary from ground to the end. A newly formed surface discharge emerges at the target when enough charge is deposited at the impact point and electric fields are high enough, i.e. 200 pC and 9 ± 2 kV cm‑1. The maximum amount of charge transferred by a single ionization wave (‘plasma bullet’) is 350 ± 40 pC. Due to the emerging new surface discharge behind the impact point, the total charge deposited on the surface of the dielectric target can increase up to 950 pC. The shape of the secondary discharge on the target is found to be mainly driven by gas flow, while the applied voltage allows us to utilize longer distances within the boundaries set by this gas mixing. Finally the ionization wave is found to lose charge along its propagation on the inner walls of the capillary. The loss is estimated to be approximately 7.5 pC mm‑1 of travel distance inside the capillary.

  3. Proton and charge transfer reactions dynamics of a hydroxyflavone derivative in a polar solvent and in a cyclodextrin nanocavity

    Energy Technology Data Exchange (ETDEWEB)

    Sanz, M.; Organero, J.A. [Departamento de Quimica Fisica, Seccion de Quimicas, Facultad de Ciencias del Medio Ambiente, Universidad de Castilla-La Mancha, Avda. Carlos III, S.N., 45071 Toledo (Spain); Douhal, A. [Departamento de Quimica Fisica, Seccion de Quimicas, Facultad de Ciencias del Medio Ambiente, Universidad de Castilla-La Mancha, Avda. Carlos III, S.N., 45071 Toledo (Spain)], E-mail: Abderrazzak.douhal@uclm.es

    2007-09-25

    In this work, we report on the observation of ultrafast intramolecular charge- and proton-transfer reactions of 4'-dimethylaminoflavonol (DMAF) in N,N-dimethyl formamide and in {gamma}-cyclodextrin ({gamma}-CD) solution. Upon femtosecond excitation an intramolecular charge transfer (ICT) reaction takes place to produce an ICT structure in {approx}200 fs. This structure may undergo a proton transfer reaction to generate a zwitterionic (Z) form in 2-3 ps, or relaxes in its potential energy well, to later equilibrate with that of Z in hundreds of ps. Addition of {gamma}-CD does not significantly affect the fast dynamics of the formed anion. The fs-emission signals of the parent molecule, 3-hydroxyflavone, indicate that the dimethyl amino group in DMAF enhances the rate constant of intermolecular proton-transfer and intramolecular charge-transfer reactions.

  4. Interfacial Charge Transfer States in Condensed Phase Systems

    Science.gov (United States)

    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.

  5. Tunable charge transfer properties in metal-phthalocyanine heterojunctions

    Science.gov (United States)

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

    2016-04-01

    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

  6. Extended Holstein polaron model for charge transfer in dry DNA

    Institute of Scientific and Technical Information of China (English)

    Liu Tao; Wang Yi; Wang Ke-Lin

    2007-01-01

    The variational method is applied to the study of charge transfer in dry DNA by using an extended Holstein small polaron model in two cases: the site-dependent finite-chain discrete case and the site-independent continuous one. The treatments in the two cases are proven to be consistent in theory and calculation. Discrete and continuous treatments of Holstein model both can yield a nonlinear equation to describe the charge migration in an actual long-range DNA chain.Our theoretical results of binding energy Eb, probability amplitude of charge carrier φ and the relation between energy and charge-lattice coupling strength are in accordance with the available experimental results and recent theoretical calculations.

  7. Self-interaction effects on charge-transfer collisions

    CERN Document Server

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

    2016-01-01

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

  8. Charge transfer excitons in C60-dimers and polymers

    CERN Document Server

    Harigaya, K

    1996-01-01

    Charge-transfer (CT) exciton effects are investigated for the optical absorption spectra of crosslinked C60 systems by using the intermediate exciton theory. We consider the C60-dimers, and the two (and three) molecule systems of the C60-polymers. We use a tight-binding model with long-range Coulomb interactions among electrons, and the model is treated by the Hartree-Fock approximation followed by the single-excitation configuration interaction method. We discuss the variations in the optical spectra by changing the conjugation parameter between molecules. We find that the total CT-component increases in smaller conjugations, and saturates at the intermediate conjugations. It decreases in the large conjugations. We also find that the CT-components of the doped systems are smaller than those of the neutral systems, indicating that the electron-hole distance becomes shorter in the doped C60-polymers.

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

    Science.gov (United States)

    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.

  10. Multiple-charge transfer and trapping in DNA dimers

    Science.gov (United States)

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

    2010-11-01

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

  11. Charge-Transfer Emitting Triarylborane π-Electron Systems.

    Science.gov (United States)

    Li, Sheng-Yong; Sun, Zuo-Bang; Zhao, Cui-Hua

    2017-08-07

    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.

  12. Charge Transfer and Ionization by Intermediate-Energy Heavy Ions

    Energy Technology Data Exchange (ETDEWEB)

    Toburen, L. H. [East Carolina University; McLawhorn, S. L. [East Carolina University; McLawhorn, R. A. [East Carolina University; Evans, N. L. [East Carolina University; Justiniano, E. L. B. [East Carolina University; Shinpaugh, J. L. [East Carolina University; Schultz, David Robert [ORNL; Reinhold, Carlos O [ORNL

    2006-11-01

    The use of heavy ion beams for microbeam studies of mammalian cell response leads to a need to better understand interaction cross sections for collisions of heavy ions with tissue constituents. For ion energies of a few MeV u-1 or less, ions capture electrons from the media in which they travel and undergo subsequent interactions as partially 'dressed' ions. For example, 16 MeV fluorine ions have an equilibrium charge of 7+, 32 MeV sulphur ions have an equilibrium charge of approx. 11+, and as the ion energies decrease the equilibrium charge decreases dramatically. Data for interactions of partially dressed ions are extremely rare, making it difficult to estimate microscopic patterns of energy deposition leading to damage to cellular components. Such estimates, normally obtained by Monte Carlo track structure simulations, require a comprehensive database of differential and total ionisation cross sections as well as charge transfer cross sections. To provide information for track simulation, measurement of total ionisation cross sections have been initiated at East Carolina University using the recoil ion time-of-flight method that also yields cross sections for multiple ionisation processes and charge transfer cross sections; multiple ionisation is prevalent for heavy ion interactions. In addition, measurements of differential ionisation cross sections needed for Monte Carlo simulation of detailed event-by-event particle tracks are under way. Differential, total and multiple ionisation cross sections and electron capture and loss cross sections measured for C+ ions with energies of 100 and 200 keV u-1 are described.

  13. Charge transfer and ionisation by intermediate-energy heavy ions.

    Science.gov (United States)

    Toburen, L H; McLawhorn, S L; McLawhorn, R A; Evans, N L; Justiniano, E L B; Shinpaugh, J L; Schultz, D R; Reinhold, C O

    2006-01-01

    The use of heavy ion beams for microbeam studies of mammalian cell response leads to a need to better understand interaction cross sections for collisions of heavy ions with tissue constituents. For ion energies of a few MeV u(-1) or less, ions capture electrons from the media in which they travel and undergo subsequent interactions as partially 'dressed' ions. For example, 16 MeV fluorine ions have an equilibrium charge of 7(+), 32 MeV sulphur ions have an equilibrium charge of approximately 11(+), and as the ion energies decrease the equilibrium charge decreases dramatically. Data for interactions of partially dressed ions are extremely rare, making it difficult to estimate microscopic patterns of energy deposition leading to damage to cellular components. Such estimates, normally obtained by Monte Carlo track structure simulations, require a comprehensive database of differential and total ionisation cross sections as well as charge transfer cross sections. To provide information for track simulation, measurement of total ionisation cross sections have been initiated at East Carolina University using the recoil ion time-of-flight method that also yields cross sections for multiple ionisation processes and charge transfer cross sections; multiple ionisation is prevalent for heavy ion interactions. In addition, measurements of differential ionisation cross sections needed for Monte Carlo simulation of detailed event-by-event particle tracks are under way. Differential, total and multiple ionisation cross sections and electron capture and loss cross sections measured for C(+) ions with energies of 100 and 200 keV u(-1) are described.

  14. Evaluating Electronic Couplings for Excited State Charge Transfer Based on Maximum Occupation Method ΔSCF Quasi-Adiabatic States.

    Science.gov (United States)

    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.

  15. Electron density characteristics and charge transfer effect of hydrogen bond O-H···Pt(II): atoms in molecules study and natural bond orbital analysis

    Science.gov (United States)

    Zhang, Guiqiu; Li, Xiwen; Li, Yan; Chen, Dezhan

    2013-11-01

    In this report, we extended the works of Rizzato et al. [Angew. Chem. Int. Ed. 49, 7440 (2010)] on the nature of O-H...Pt hydrogen bond in trans-[PtCl2(NH3)(N-glycine)].H2O(1.H2O) complex, by computational study of O-H...Pt interaction in [NBu4][Pt(C6F5)3(8-hydroxyquinaldine)], with emphasis on charge transfer effect in this interaction of platinum(II) and hydrogen atom. According to the crystallographic geometry reported by José María Casas et al., [NBu4][Pt(C6F5)3(8-hydroxyquinaldine)] possesses one O-H...Pt hydrogen bridging interaction, similar to the case in trans-[PtCl2(NH3)(N-glycine)].H2O(1.H2O) complex. On the basis of topological criteria of electron density, we characterised this O-H...Pt interaction. Charge transferred between platinum(II) and σ*O-H orbital in this complex was calculated by using NBO method. The stabilised energy associated to charge transfer was estimated using a direct proportionality, that is 2-3 eV per electron transferred. Charge transfer effects in O-H...Pt hydrogen bonds were studied for these two complexes. Our results indicate that the interaction of O-H...Pt is closed-shell in nature with significant charge transfer, and that charge transfer effect is not negligible in the interaction of O-H...Pt. The second conclusion is different from the result of Rizzato et al.

  16. Charge Transfer and Support Effects in Heterogeneous Catalysis

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-12-21

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

  17. Charge Transfer Modulated Self-Assembly in Poly(aryl ether) Dendron Derivatives with Improved Stability and Transport Characteristics.

    Science.gov (United States)

    Satapathy, Sitakanta; Prasad, Edamana

    2016-10-05

    Alteration of native gelation properties of anthracene and pyrene cored first generation poly(aryl ether) dendrons, G1-An and G1-Py, by introducing a common acceptor, 2,4,7-trinitro-9H-fluoren-9-one (TNF), results in forming charge transfer gels in long chain alcoholic solvents. This strategy leads to significant perturbation of optical and electronic properties within the gel matrix. Consequently, a noticeable increase of their electrical conductivities is observed, making these poly(aryl ether) dendron based gels potential candidates for organic electronics. While the dc-conductivity (σ) value for the native gel from G1-An is 2.8 × 10(-4) S m(-1), the value increased 3 times (σ = 8.7 × 10(-4) S m(-1)) for its corresponding charge transfer gel. Further, the dc-conductivity for the native gel self-assembled from G1-Py dramatically enhanced by approximately an order of magnitude from 4.9 × 10(-4) to 1.3 × 10(-3) S m(-1), under the influence of an acceptor. Apart from H-bonding and π···π interactions, charge transfer results in the formation of a robust 3D network of fibers, with improved aspect ratio, providing high thermo-mechanical stability to the gels compared to the native ones. The charge transfer gels self-assembled from G1-An/TNF (1:1) and G1-Py/TNF exhibit a 7.3- and 2.5-fold increase in their yield stress, respectively, compared to their native assemblies. A similar trend follows in the case of their thermal stabilities. This is attributed to the typical bilayer self-assembly of the former which is not present in the case of G1-Py/TNF charge transfer gel. Density functional calculations provide deeper insights accounting for the role of charge transfer interactions in the mode of self-assembly. The 1D potential energy surface for the G1-An/TNF dimer and G1-Py/TNF dimer is found to be 11.8 and 1.9 kcal mol(-1) more stable than their corresponding native gel dimers, G1-An/G1-An and G1-Py/G1-Py, respectively.

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

    Science.gov (United States)

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

    2017-09-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-11-15

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

  20. Charge Transfer Characteristics and Initiation Mechanisms of Long Delayed Sprites

    Science.gov (United States)

    Li, J.; Cummer, S. A.; Lyons, W. A.; Nelson, T. E.

    2007-12-01

    Simultaneous measurements of high altitude optical emissions and the magnetic field produced by sprite-associated lightning discharges enable a close examination of the link between low altitude lightning process and high altitude sprite process. In this work, we report results of the coordinated analysis of high speed (1000--10000 frames per second) sprite video and wideband (0.1 Hz to 30 kHz) magnetic field measurements made simultaneously at the Yucca Ridge Field Station and Duke University during the June through August 2005 campaign period. During the observation period, the high speed camera detected 83 sprite events in 67 TLE sequences, which are caused by the same number of +CGs. 46% of these sprite events are delayed more than 10 ms after the lightning return stroke. With the estimated lightning source current moment waveform, we computed the continuing current amplitude and total charge transfer characteristics of the long delayed sprites (>10 ms delay). Our calculation shows the total charge moment change of the long delayed sprites can vary from several hundred C km to more than ten thousand C km. All the long delayed sprites are related with intense continuing current bigger than 2 kA. This continuing current provides about 50% to 90% of the total charge transfer. However, a bigger continuing current does not necessarily mean a shorter time delay. This indicates that other processes also involved in the sprite initiation for long delayed sprites. In our observations, the sferic burst, a high frequency noise caused by intra-cloud activity, is always accompanied by a slow intensification in the lightning source current before the time of sprite initiation. Thus we used the lightning source current as an input and employed a 2-D FDTD model to numerically simulate the electric field at different altitudes and compare it with the breakdown field. Including the effect of the electron mobility dependence on electric field, the simulation results showed that

  1. Charge Transfer Channels in Formation of Exciplex in Polymer Blends

    Institute of Scientific and Technical Information of China (English)

    DOU Fei; ZHANG Xin-Ping

    2011-01-01

    The strong dependence of photoluminescence of charge transfer excited states or exciplex in a blend film of poly(9,9'-dioctylBuorene-co-benzothiadiazole) (F8BT) and poly(9,9'-dioctyl6uorene-co-bis-N,N'-(4-butylphenyl)-bis-N,N'-phenyl-l,4- phenylenediamine) (PFB) on the excitation wavelengths and morphology is investigated. The experimental results reveal that electron transfer in the LUMOs from PFB to F8BT is more efficient than hole transfer in the HOMOs from PFB to F8BT for the formation of exciplex at the interfacial junctions between these two types of molecules in the blend Sim. Furthermore, energy transfer from the blue-emitting PFB to the green-emitting F8BT at the interfaces introduces an additional two-step channel and thus enhances the formation of an exciplex. This is important for understanding of charge generation and separation in organic bulk heterojunctions and for design of optoelectronic devices.%@@ The strong dependence of photoluminescence of charge transfer excited states or exciplex in a blend film of poly(9,9'-dioctylfluorene-co-benzothiadiazole)(F8BT)and poly(9,9'-dioctylfluorene-co-bis-N,N'-(4-butylphenyl)-bis-N,N'-phenyl-1,4-phenylenediamine)(PFB)on the excitation wavelengths and morphology is investigated.The experimental results reveal that electron transfer in the LUMOs from PFB to F8BT is more efficient than hole transfer in the HOMOs from PFB to F8BT for the formation of exciplex at the interfacial junctions between these two types of molecules in the blend film.Furthermore,energy transfer from the blue-emitting PFB to the green-emitting F8BT at the interfaces introduces an additional two-step channel and thus enhances the formation of an exciplex.This is important for understanding of charge generation and separation in organic bulk heterojunctions and for design of optoelectronic devices.

  2. Solvent-mediated electron hopping: long-range charge transfer in IBr-(CO2) photodissociation.

    Science.gov (United States)

    Sheps, Leonid; Miller, Elisa M; Horvath, Samantha; Thompson, Matthew A; Parson, Robert; McCoy, Anne B; Lineberger, W Carl

    2010-04-09

    Chemical bond breaking involves coupled electronic and nuclear dynamics that can take place on multiple electronic surfaces. Here we report a time-resolved experimental and theoretical investigation of nonadiabatic dynamics during photodissociation of a complex of iodine monobromide anion with carbon dioxide [IBr-(CO2)] on the second excited (A') electronic state. Previous experimental work showed that the dissociation of bare IBr- yields only I- + Br products. However, in IBr-(CO2), time-resolved photoelectron spectroscopy reveals that a subset of the dissociating molecules undergoes an electron transfer from iodine to bromine 350 femtoseconds after the initial excitation. Ab initio calculations and molecular dynamics simulations elucidate the mechanism for this charge hop and highlight the crucial role of the carbon dioxide molecule. The charge transfer between two recoiling atoms, assisted by a single solvent-like molecule, provides a notable limiting case of solvent-driven electron transfer over a distance of 7 angstroms.

  3. Ultracold, radiative charge transfer in hybrid Yb ion - Rb atom traps

    CERN Document Server

    McLaughlin, B M; Lane, I C; McCann, J F

    2014-01-01

    Ultracold hybrid ion-atom traps offer the possibility of microscopic manipulation of quantum coherences in the gas using the ion as a probe. However, inelastic processes, particularly charge transfer can be a significant process of ion loss and has been measured experimentally for the Yb$^{+}$ ion immersed in a Rb vapour. We use first-principles quantum chemistry codes to obtain the potential energy curves and dipole moments for the lowest-lying energy states of this complex. Calculations for the radiative decay processes cross sections and rate coefficients are presented for the total decay processes. Comparing the semi-classical Langevin approximation with the quantum approach, we find it provides a very good estimate of the background at higher energies. The results demonstrate that radiative decay mechanisms are important over the energy and temperature region considered. In fact, the Langevin process of ion-atom collisions dominates cold ion-atom collisions. For spin dependent processes \\cite{kohl13} the...

  4. Effect of intramolecular charge transfer on fluorescence and singlet oxygen production of phthalocyanine analogues.

    Science.gov (United States)

    Vachova, Lenka; Novakova, Veronika; Kopecky, Kamil; Miletin, Miroslav; Zimcik, Petr

    2012-10-14

    Intramolecular charge transfer (ICT) was studied on a series of magnesium, metal-free and zinc complexes of unsymmetrical tetrapyrazinoporphyrazines and tribenzopyrazinoporphyrazines bearing two dialkylamino substituents (donors) and six alkylsulfanyl or aryloxy substituents (non-donors). The dialkylamino substituents were responsible for ICT that deactivated excited states and led to considerable decrease of fluorescence and singlet oxygen quantum yields. Photophysical and photochemical properties were compared to corresponding macrocycles that do not bear any donor centers. The data showed high feasibility of ICT in the tetrapyrazinoporphyrazine macrocycle and significantly lower efficiency of this deactivation process in the tribenzopyrazinoporphyrazine type molecules. Considerable effect of non-donor peripheral substituents on ICT was also described. The results imply that tetrapyrazinoporphyrazines may be more suitable for development of new molecules investigated in applications based on ICT.

  5. Charge-transfer interaction of drug quinidine with quinol, picric acid and DDQ:Spectroscopic characterization and biological activity studies towards understanding the drug-receptor mechanism

    Institute of Scientific and Technical Information of China (English)

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

    2014-01-01

    Investigation of charge-transfer (CT) complexes of drugs has been recognized as an important phenomenon in understanding of the drug-receptor binding mechanism. Structural, thermal, morpholo-gical and biological behavior of CT complexes formed between drug quinidine (Qui) as a donor and quinol (QL), picric acid (PA) or dichlorodicyanobenzoquinone (DDQ) as acceptors were reported. The newly synthesized CT complexes have been spectroscopically characterized via elemental analysis;infrared (IR), Raman, 1H NMR and electronic absorption spectroscopy; powder X-ray diffraction (PXRD);thermogravimetric (TG) analysis and scanning electron microscopy (SEM). It was found that the obtained complexes are nanoscale, semi-crystalline particles, thermally stable and spontaneous. The molecular composition of the obtained complexes was determined using spectrophotometric titration method and was found to be 1:1 ratios (donor:acceptor). Finally, the biological activities of the obtained CT complexes were tested for their antibacterial activities. The results obtained herein are satisfactory for estimation of drug Qui in the pharmaceutical form.

  6. Experimental verification of orbital engineering at the atomic scale: Charge transfer and symmetry breaking in nickelate heterostructures

    Science.gov (United States)

    Phillips, Patrick J.; Rui, Xue; Georgescu, Alexandru B.; Disa, Ankit S.; Longo, Paolo; Okunishi, Eiji; Walker, Fred; Ahn, Charles H.; Ismail-Beigi, Sohrab; Klie, Robert F.

    2017-05-01

    Epitaxial strain, layer confinement, and inversion symmetry breaking have emerged as powerful new approaches to control the electronic and atomic-scale structural properties of complex metal oxides. Trivalent rare-earth (RE) nickelate R E NiO3 heterostructures have been shown to be exemplars since the orbital occupancy, degeneracy, and, consequently, electronic/magnetic properties can be altered as a function of epitaxial strain, layer thickness, and superlattice structure. One recent example is the tricomponent LaTiO3-LaNiO3-LaAlO3 superlattice which exhibits charge transfer and orbital polarization as the result of its interfacial dipole electric field. A crucial step towards control of these parameters for future electronic and magnetic device applications is to develop an understanding of both the magnitude and range of the octahedral network's response towards interfacial strain and electric fields. An approach that provides atomic-scale resolution and sensitivity towards the local octahedral distortions and orbital occupancy is therefore required. Here, we employ atomic-resolution imaging coupled with electron spectroscopies and first-principles theory to examine the role of interfacial charge transfer and symmetry breaking in a tricomponent nickelate superlattice system. We find that nearly complete charge transfer occurs between the LaTiO3 and LaNiO3 layers, resulting in a mixed Ni2 +/Ni3 + valence state. We further demonstrate that this charge transfer is highly localized with a range of about 1 unit cell within the LaNiO3 layers. We also show how Wannier-function-based electron counting provides a simple physical picture of the electron distribution that connects directly with formal valence charges. The results presented here provide important feedback to synthesis efforts aimed at stabilizing new electronic phases that are not accessible by conventional bulk or epitaxial film approaches.

  7. Interaction and charge transfer between dielectric spheres: exact and approximate analytical solutions

    CERN Document Server

    Lindén, Fredrik; Zettergren, Henning

    2016-01-01

    We present exact analytical solutions for charge transfer reactions between two arbitrarily charged hard dielectric spheres. These solutions, and the corresponding exact ones for sphere-sphere interaction energies, include sums that describe polarization effects to infinite orders in the inverse of the distance between the sphere centers. In addition, we show that these exact solutions may be approximated by much simpler analytical expressions that are useful for many practical applications. This is exemplified through calculations of Langevin type cross sections for forming a compound system of two colliding spheres and through calculations of electron transfer cross sections. We find that it is important to account for dielectric properties and finite sphere sizes in such calculations, which for example may be useful for describing the evolution, growth, and dynamics of nanometer sized dielectric objects such as molecular clusters or dust grains in different environments including astrophysical ones.

  8. Intramolecular Charge-Transfer Interaction of Donor-Acceptor-Donor Arrays Based on Anthracene Bisimide.

    Science.gov (United States)

    Iwanaga, Tetsuo; Ogawa, Marina; Yamauchi, Tomokazu; Toyota, Shinji

    2016-05-20

    We designed anthracene bisimide (ABI) derivatives having two triphenylamine (TPA) groups as donor units at the 9,10-positions to form a novel π-conjugated donor-acceptor system. These compounds and their analogues with ethynylene linkers were synthesized by Suzuki-Miyaura and Sonogashira coupling reactions, respectively. In UV-vis spectra, the linker-free derivatives showed broad absorption bands arising from intramolecular charge-transfer interactions. Introducing ethynylene linkers resulted in a considerable red shift of the absorption bands. In fluorescence spectra, the ethynylene derivatives showed intense emission bands at 600-650 nm. Their photophysical and electrochemical properties were compared with those of the corresponding mono TPA derivatives on the basis of theoretical calculations and cyclic voltammetry to evaluate the intramolecular electronic interactions between the donor and acceptor units.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-10-01

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

  10. Thiolate versus Selenolate: Structure, Stability, and Charge Transfer Properties.

    Science.gov (United States)

    Ossowski, Jakub; Wächter, Tobias; Silies, Laura; Kind, Martin; Noworolska, Agnieszka; Blobner, Florian; Gnatek, Dominika; Rysz, Jakub; Bolte, Michael; Feulner, Peter; Terfort, Andreas; Cyganik, Piotr; Zharnikov, Michael

    2015-04-28

    Selenolate is considered as an alternative to thiolate to serve as a headgroup mediating the formation of self-assembled monolayers (SAMs) on coinage metal substrates. There are, however, ongoing vivid discussions regarding the advantages and disadvantages of these anchor groups, regarding, in particular, the energetics of the headgroup-substrate interface and their efficiency in terms of charge transport/transfer. Here we introduce a well-defined model system of 6-cyanonaphthalene-2-thiolate and -selenolate SAMs on Au(111) to resolve these controversies. The exact structural arrangements in both types of SAMs are somewhat different, suggesting a better SAM-building ability in the case of selenolates. At the same time, both types of SAMs have similar packing densities and molecular orientations. This permitted reliable competitive exchange and ion-beam-induced desorption experiments which provided unequivocal evidence for a stronger bonding of selenolates to the substrate as compared to the thiolates. Regardless of this difference, the dynamic charge transfer properties of the thiolate- and selenolate-based adsorbates were found to be nearly identical, as determined by the core-hole-clock approach, which is explained by a redistribution of electron density along the molecular framework, compensating the difference in the substrate-headgroup bond strength.

  11. Identifying interfacial charge transfer states in organic heterostructures (Conference Presentation)

    Science.gov (United States)

    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.

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

    Science.gov (United States)

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

    2017-08-01

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

  13. Doping graphene films via chemically mediated charge transfer

    Directory of Open Access Journals (Sweden)

    Ishikawa Ryousuke

    2011-01-01

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

  14. Satellite lines at the ionization threshold in charge transfer systems

    Science.gov (United States)

    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.

  15. Electronic structure, charge distribution, and charge transfer in α- and β-Si3N4 and at the Si(111)/Si3N4(001) interface

    Science.gov (United States)

    Zhao, G. L.; Bachlechner, M. E.

    1997-02-01

    The electronic structure, charge distribution, and charge transfer in α- and β- Si3N4 and at the Si(111)/Si3N4(001) interface have been studied using a self-consistent first-principles LCAO method. The calculated charge transfer suggests that both in α- and β-phases, the ionic formula may be written as Si3+1.24N4-0.93. For the Si(111)/Si3N4(001) interface, the silicon atoms from the Si(111) side give some electrons to the N atoms of Si3N4 forming the Si-N bonds at the interface. One Si-N bond is associated with a charge transfer of about 0.31 electrons.

  16. Theory for electrochemical impedance spectroscopy of heterogeneous electrode with distributed capacitance and charge transfer resistance

    Indian Academy of Sciences (India)

    SHWETA DHILLON; RAMA KANT

    2017-08-01

    Randles-Ershler admittance model is extensively used in the modeling of batteries, fuel cells, sensors etc. It is also used in understanding response of the fundamental systems with coupled processes like charge transfer, diffusion, electric double layer charging and uncompensated solution resistance. Wegeneralize phenomenological theory for the Randles-Ershler admittance at the electrode with double layer capacitance and charge transfer heterogeneity, viz., non-uniform double layer capacitance and charge transfer resistance (c d and R CT). Electrode heterogeneity is modeled through distribution functions of R CT and c d, viz., log-normal distribution function. High frequency region captures influence of electric double layer while intermediate frequency region captures influence from the charge transfer resistance of heterogeneous electrode. A heterogeneous electrode with mean charge transfer resistance $\\bar{R CT}$ shows faster charge transfer kinetics over a electrode with uniform charge transfer resistance ($\\bar{R CT}$). It is also observed that a heterogeneous electrode having high mean with large variance in the R CT and c d can behave same as an electrode having low mean with small variance in the R CT and c d. The origin of coupling of uncompensated solution resistance (between working and reference electrode) with the charge transfer kinetics is explained. Finally, our model provides a simple route to understand the effect of spatial heterogeneity.

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

    Directory of Open Access Journals (Sweden)

    Parul Chawla

    2014-08-01

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

  18. Influence of Coherent Tunneling and Incoherent Hopping on the Charge Transfer Mechanism in Linear Donor-Bridge-Acceptor Systems.

    Science.gov (United States)

    Li, Guangqi; Govind, Niranjan; Ratner, Mark A; Cramer, Christopher J; Gagliardi, Laura

    2015-12-17

    The mechanism of charge transfer has been observed to change from tunneling to hopping with increasing numbers of DNA base pairs in polynucleotides and with the length of molecular wires. The aim of this paper is to investigate this transition by examining the population dynamics using a tight-binding Hamiltonian with model parameters to describe a linear donor-bridge-acceptor (D-B-A) system. The model includes a primary vibration and an electron-vibration coupling at each site. A further coupling of the primary vibration with a secondary phonon bath allows the system to dissipate energy to the environment and reach a steady state. We apply the quantum master equation (QME) approach, based on second-order perturbation theory in a quantum dissipative system, to examine the dynamical processes involved in charge-transfer and follow the population transfer rate at the acceptor, ka, to shed light on the transition from tunneling to hopping. With a small tunneling parameter, V, the on-site population tends to localize and form polarons, and the hopping mechanism dominates the transfer process. With increasing V, the population tends to be delocalized and the tunneling mechanism dominates. The competition between incoherent hopping and coherent tunneling governs the mechanism of charge transfer. By varying V and the total number of sites, we also examine the onset of the transition from tunneling to hopping with increasing length.

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

    Science.gov (United States)

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

    2014-01-01

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

  20. UV-induced self-assembly of the inclusion complexes formed between a long-chain photochromic spiropyran and cyclodextrins

    Institute of Scientific and Technical Information of China (English)

    隋强; 周金渭; 何炜; 李仲杰; 王艳乔

    1999-01-01

    Photochromic spiropyran with a long chain alkyl substitute can form axial complexes with α-, β-, and γ-cyclodextrin, respectively. The complexes show normal photochromism. The novel property of the colored forms of the inclusion complexes is that they can assemble into dimers at relatively low concentration or J-aggregates at relatively high concentration. For α-, β-, and γ-cyclodextrin, λmax of the J-aggregates appear at 700 650, and 630 nm, respectively. The sizes of the cavities of cyclodextrins have very little effect on the spectra and decoloration kinetics of the dimers, but have great effects on the spectra of the J-aggregates. Unlike the charge transfer complex of Krongauz, the decoloration process of the dimers or J-aggregates cannot be described by an exponential or a two-exponential kinetics, but obey half-order kinetics very well. Another result that can be deduced from the kinetic analysis is that unlike the dimers formed in apolar solvents or in polymers, which consist of a color

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-09-01

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

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

    Science.gov (United States)

    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.

  3. Crystal Growth of new charge-transfer salts based on $\\pi$-conjugated molecules

    CERN Document Server

    Morherr, Antonia; Chernenkaya, Alisa; Bäcker, Jan-Peter; Schönhense, Gerd; Bolte, Michael; Krellner, Cornelius

    2016-01-01

    New charge transfer crystals of $\\pi$-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 is reported for charge transfer salts with (fluorinated) tetracyanoquinodimethane (TCNQ-F$_x$, x=0, 2, 4), which was used as acceptor material. The crystal structures were determined by single-crystal X-ray diffraction. Growth conditions for different vapor pressures in closed ampules were applied and the effect of these starting conditions for crystal size and quality is reported. The process of charge transfer was investigated by geometrical analysis of the crystal structure and by infrared spectroscopy on single crystals. With these three different acceptor strengths and the two sets of donor materials, it is possible to investigate the distribution of the charge transfer systematically. This helps to understand the charge transfer process in this class of materials with $\\pi$-conjug...

  4. Cooperative coupling of the Li cation and groups to amplify the charge transfer between C60 and corannulene

    Science.gov (United States)

    Sun, Gang; Xu, Jing; Chen, Zhi-Yuan; Lei, E.; Liu, Xiang-Shuai; Liu, Chun-Guang

    2017-02-01

    In present work, four complexes have been designed to investigate the effect of Li+ cation and substituent on the geometric structures and a series of electronic properties using density functional theory. The calculated results indicate that the charge decomposition (CDA) analysis and extend charge decomposition analysis (ECDA) of four complexes have the same sequence. The average d values defined the distances between C60 and corannulene display the inverse sequence. Consequently, the cooperative coupling of the Li+ cation and appropriate substituent is predicted to be an effective way to enhance the charge transfer between the C60 and corannulene derivatives.

  5. Flavin Charge Transfer Transitions Assist DNA Photolyase Electron Transfer

    Science.gov (United States)

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

    2007-12-01

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

  6. Flavin Charge Transfer Transitions Assist DNA Photolyase Electron Transfer

    Science.gov (United States)

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

    2012-01-01

    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. PMID:23226907

  7. Self-interaction and charge transfer in organic semiconductors

    Energy Technology Data Exchange (ETDEWEB)

    Koerzdoerfer, Thomas

    2009-12-18

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

  8. Theoretical description of photo-doping in Mott and charge-transfer insulators

    Science.gov (United States)

    Eckstein, Martin

    2012-02-01

    Many aspects of photo-excited insulator-to-metal transitions in Mott and charge-transfer systems are theoretically not well understood: How is the photo-doped state related to a chemically doped state? On what timescale do we expect the formation of quasiparticles? To describe the electronic dynamics of Mott insulators, we have used nonequilibrium dynamical mean-field theory (DMFT) in combination with Quantum Monte Carlo and various weak and strong-coupling [1] techniques. In the talk, I will briefly present the current status of this approach and of related cluster approaches for nonequilibrium. I will then discuss results for the photo-doping in the Hubbard model, and in a in a p-d model for charge-transfer insulators. When the onsite Coulomb repulsion U is much larger than the hopping, rapid thermalization of the pump-excited Mott insulator is inhibited by the energetic stabilization of doublon-hole pairs [2], and various types of non-thermal states can arise. Immediately after the excitation process, the system of doublons and holes is too hot to form quasiparticle states, but coupling to a heat-bath of phonons can drive the system into a metallic state with well developed doublon and hole bands. Close to the metal-insulator transition, on the other hand, when U is of the order as the hopping, doublons and holes rapidly thermalize due to the electron-electron interaction, which makes the system a bad metal rather than a Fermi liquid. [4pt] [1] M. Eckstein and Ph. Werner, Phys. Rev. B 82, 115115 (2010).[0pt] [2] M. Eckstein and Ph. Werner, Phys. Rev. B 84, 035122 (2011).

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

    Science.gov (United States)

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

    2014-06-28

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

  10. Flexible Organic Phototransistor Array with Enhanced Responsivity via Metal-Ligand Charge Transfer.

    Science.gov (United States)

    Liu, Xien; Lee, Eun Kwang; Kim, Dong Yeong; Yu, Hojeong; Oh, Joon Hak

    2016-03-23

    Phototransistors based on organic photoactive materials combine tunable light absorption in the spectral region from ultraviolet to near-infrared with low-temperature processability over large areas on flexible substrates. However, they often exhibit low photoresponsivity because of low molar extinction coefficient of photoactive components. We report a simple, yet highly efficient solution method for enhancing the performance of organic phototransistors using ruthenium complex 1 (Ru-complex 1). An air-stable n-type organic semiconductor, N,N'-bis(2-phenylethyl)-perylene-3,4:9,10-tetracarboxylic diimide (BPE-PTCDI), has been deposited on a silicon wafer and a transparent polyimide (PI) substrate via thermal evaporation under vacuum. The BPE-PTCDI phototransistors functionalized with Ru-complex 1 exhibit ∼5000 times higher external quantum efficiency (EQE) than that of pristine BPE-PTCDI phototransistors, owing to the metal-ligand charge transfer (MLCT) from Ru-complex 1 to the active component of the device. In addition, a large 10 × 10 phototransistor array (2.5 × 2.5 cm(2)) has been prepared on a transparent PI substrate, showing distinct light mapping. The fabricated phototransistor array is highly flexible and twistable and works well under tensile and compressive strains. We believe that our simple method will pave a viable way for improvements in the photoresponsivity of organic semiconductors for applications in wearable organic optoelectronic devices.

  11. Reaction dynamics and proton coupled electron transfer: studies of tyrosine-based charge transfer in natural and biomimetic systems.

    Science.gov (United States)

    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.

  12. Direct electrochemical detection of PCR product based on charge transfer through DNA

    Institute of Scientific and Technical Information of China (English)

    ZHAO Hongtao; ZHANG Zhijie; JU Huangxian

    2005-01-01

    @@ Human genome project and genetic identification for inherited diseases will definitely have a profound impact on the diagnosis of diseases[1], which calls for rapid and accurate assays of DNA. Among different types of sensors, electrochemical DNA biosensors offer a promising alternative means[2,3]. Recent efforts to elucidate the mechanism of charge transfer in DNA have demonstrated that the charge transfer is sensitive to the perturbation in base stack[4,5]. Long-range charge transfer in DNA therefore has been showing great potential application in the development of DNA-based biosensors, especially in the study of single nucleotide polymorphs[7―10].

  13. Twisted intra-molecular charge transfer investigations of semiorganic triglycine phosphate single crystal for non linear optical applications

    Science.gov (United States)

    Meera, M. R.; Joselin Beaula, T.; Rayar, S. L.; Bena Jothy, V.

    2017-09-01

    NLO materials are gaining importance in technologies such as optical communication, optical computing and dynamic image processing. Many NLO crystals grown by mixing amino acids with various organic and inorganic acids have been reported in the literature. Hence, glycine mixed semi-organic material will be of special interest as a fundamental building block to develop many complex crystals with improved NLO properties. A semi organic Single crystal of Triglycine Phosphate (TGP) which was grown and spectral analysis have been using FTIR and Raman spectral analysis. Natural Bond Orbital Analysis and the atomic natural charges are also predicted. HOMO LUMO energy gap value suggests the possibility of charge transfer within the molecule.

  14. Real Hypersurfaces of a Complex Space Form

    Indian Academy of Sciences (India)

    Sharief Deshmukh

    2012-11-01

    In this paper we are interested in obtaining a condition under which a compact real hypersurface of a complex projective space $CP^n$ is a geodesic sphere. We also study the question as to whether the characteristic vector field of a real hypersurface of the complex projective space $CP^n$ is harmonic, and show that the answer is in negative.

  15. Light-induced copper(II) coordination by a bicyclic tetraaza chelator through a ligand-to-metal charge-transfer reaction.

    Science.gov (United States)

    Holm-Jørgensen, Jacob R; Jensen, Mikael; Bjerrum, Morten J

    2011-12-19

    To enable utilization of the broad potential of copper isotopes in nuclear medicine, rapid and robust chelation of the copper is required. Bowl adamanzanes (bicyclic tetraaza ligands) can form kinetically stable copper complexes, but they are usually formed at low rates unless high pH values and high temperatures are applied. We have investigated the effects of the variation in the pH, different anions, and UV irradiation on the chelation rate. UV spectra of mixtures of Cu(2+) and [2(4).3(1)]adz in water show the existence of a long-lived two-coordinated copper(II) intermediate (only counting coordinated amine groups) at pH above 6. These findings are supported by pH titrations of mixtures of Cu(2+) and [2(4).3(1)]adz in water. Irradiation of this complex in the ligand-to-metal charge-transfer (LMCT) band by a diode-array spectrophotometer leads to photodeprotonation and subsequently to formation of the four-coordinated copper(II) complex at a rate up to 7800-fold higher at 25 °C than in the dark. Anions in the solution were found to have three major effects: competitive inhibition due to Cu(II) binding anions, inhibition of the photoinduced transchelation from UV-absorbing anions, and photoredox inhibition from acido ligands capable of acting as electron donors in LMCT reactions. Dissolved O(2) was also found to result in photoredox inhibition.

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

    Science.gov (United States)

    Chakraverty, B. K.

    1990-01-01

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

  17. Electronic properties of the charge transfer material MnPc/F4TCNQ

    Science.gov (United States)

    Rückerl, Florian; Mahns, Benjamin; Dodbiba, Eni; Nikolis, Vasileios; Herzig, Melanie; Büchner, Bernd; Knupfer, Martin; Hahn, Torsten; Kortus, Jens

    2016-09-01

    We present electronic properties of a charge transfer material consisting of Manganese(ii)Phthalocyanine (MnPc) and 2,3,5,6-Tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ), investigated by means of photoemission spectroscopy and electron energy-loss spectroscopy, as well as supporting density functional theory calculations. We report the successful formation of a bulk material characterized by a strong interaction of the molecular compounds which affects the optical properties significantly. Our investigations reveal a significant charge transfer, whereas the MnPc molecule is oxidized and F4TCNQ is reduced. The valence band data indicate a full charge transfer between the two partners. The electronic excitation spectrum reveals a relatively small energy gap of MnPc/F4TCNQ of about 0.7 eV, which is related to a charge transfer excitation.

  18. Charge-Transfer Reaction of Cediranib with 2,3-Dichloro- 3,5 ...

    African Journals Online (AJOL)

    Abstract. Purpose: To investigate the charge-transfer (CT) reaction between cediranib (CRB) and 2, 3 - dichloro- ... Conclusion: The developed assay has high throughput and consumed minimum volume of organic solvent ..... radical ions…

  19. Synergizing Noncovalent Bonding Interactions in the Self-Assembly of Organic Charge-Transfer Ferroelectrics and Metal-Organic Frameworks

    Science.gov (United States)

    Cao, Dennis

    Contemporary supramolecular chemistry---chemistry beyond the molecule---seeks to leverage noncovalent bonding interactions to generate emergent properties and complexity. These aims extend beyond the solution phase and into the solid state, where crystalline organic materials have attracted much attention for their ability to imitate the physical properties of inorganic crystals. This Thesis outlines my efforts to understand the properties of the solid-state materials that are self-assembled with noncovalent bonding motifs which I have helped to realize. In the first five Chapters, I chronicle the development of the lock-arm supramolecular ordering (LASO) paradigm, which is a general molecular design strategy for amplifying the crystallization of charge transfer complexes that revolves around the synergistic action of hydrogen bonding and charge transfer interactions. In an effort to expand upon the LASO paradigm, I identify a two-point halogen-bonding motif which appears to operate orthogonally from the hydrogen bonding and charge transfer interactions. Since some of these single crystalline materials are ferroelectric at room temperature, I discuss the implications of these experimental observations and reconcile them with the centrosymmetric space groups assigned after X-ray crystallographic refinements. I conclude in the final two Chapters by recording my endeavors to control the assembly of metal-organic frameworks (MOFs) with noncovalent bonding interactions between [2]catenane-bearing struts. First of all, I describe the formation of syndiotactic pi-stacked 2D MOF layers before highlighting a two-component MOF that assembles with a magic number ratio of components that is independent of the molar proportions present in the crystallization medium.

  20. Migraine genetics : from monogenic to complex forms

    NARCIS (Netherlands)

    Vanmolkot, Kaate Raymond Josepha

    2008-01-01

    Migraine has a strong genetic component, but the identification of these factors has proven difficult mainly because of the complex interaction of multiple loci and environmental factors. Unraveling its molecular basis and deciphering pathways leading to migraine attacks will help identifying novel

  1. Migraine genetics : from monogenic to complex forms

    NARCIS (Netherlands)

    Vanmolkot, Kaate Raymond Josepha

    2008-01-01

    Migraine has a strong genetic component, but the identification of these factors has proven difficult mainly because of the complex interaction of multiple loci and environmental factors. Unraveling its molecular basis and deciphering pathways leading to migraine attacks will help identifying novel

  2. Study of the contact charge transfer behavior between cryptophanes (A and E) and fullerene by absorption, fluorescence and {sup 1}H NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Zhang Caihong; Shen Weili; Fan Ruying; Zhang Guomei; Shangguan Lingzhi; Chao Jianbin; Shuang Shaomin [Research Center of Environmental Science and Engineering, School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006 (China); Dong Chuan, E-mail: dc@sxu.edu.cn [Research Center of Environmental Science and Engineering, School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006 (China); Choi, Martin M.F., E-mail: mfchoi@hkbu.edu.hk [Department of Chemistry, Hong Kong Baptist University, Kowloon Tong (Hong Kong)

    2009-09-14

    A group of novel cage-like compounds cryptophanes A and E were synthesized from vanillin by a three-step method. The intermolecular interaction between cryptophanes (A and E) and fullerene (C{sub 60}) was investigated in detail by absorption, fluorescence and {sup 1}H NMR spectroscopy. The absorption of C{sub 60} at 410-650 nm decreased in the presence of cryptophanes A or E. The decrease in absorption intensity was proportional to the concentration of cryptophanes A or E. On the other hand, the fluorescence intensity of cryptophanes A or E decreased and the emission maxima were blue-shifted with the increase in C{sub 60} concentration. These results suggest that contact charge transfer (CCT) complexes can be formed from C{sub 60} with cryptophanes A or E. In addition, the electrochemical behavior of cryptophanes (A and E) and C{sub 60} was studied by cyclic voltammetry. The redox currents of cryptophanes (A and E) decreased and the peak potentials were shifted on addition of C{sub 60}. The changes in the chemical shifts ({Delta}{delta}) of aromatic protons of cryptophanes (A and E) in their NMR spectra further support that CCT complexes were formed with cryptophanes as the electron donors and C{sub 60} as the electron acceptor.

  3. Formation of Nanoscale Composites of Compound Semiconductors Driven by Charge Transfer.

    Science.gov (United States)

    Gao, Weiwei; Dos Reis, Roberto; Schelhas, Laura T; Pool, Vanessa L; Toney, Michael F; Yu, Kin Man; Walukiewicz, Wladek

    2016-08-10

    Composites are a class of materials that are formed by mixing two or more components. These materials often have new functional properties compared to their constituent materials. Traditionally composites are formed by self-assembly due to structural dissimilarities or by engineering different layers or structures in the material. Here we report the synthesis of a uniform and stoichiometric composite of CdO and SnTe with a novel nanocomposite structure stabilized by the dissimilarity of the electronic band structure of the constituent materials. The composite has interesting electronic properties which range from highly n-type in CdO to semi-insulating in the intermediate composition range to highly p-type in SnTe. This can be explained by the overlap of the conduction and valence band of the constituent compounds. Ultimately, our work identifies a new class of composite semiconductors in which nanoscale self-organization is driven and stabilized by charge transfer between constituent materials.

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

    Science.gov (United States)

    Bazant, Martin Z

    2013-05-21

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

  5. Self-assembly of intramolecular charge-transfer compounds into functional molecular systems.

    Science.gov (United States)

    Li, Yongjun; Liu, Taifeng; Liu, Huibiao; Tian, Mao-Zhong; Li, Yuliang

    2014-04-15

    Highly polarized compounds exhibiting intramolecular charge transfer (ICT) are used widely as nonlinear optical (NLO) materials and red emitters and in organic light emitting diodes. Low-molecular-weight donor/acceptor (D/A)-substituted ICT compounds are ideal candidates for use as the building blocks of hierarchically structured, multifunctional self-assembled supramolecular systems. This Account describes our recent studies into the development of functional molecular systems with well-defined self-assembled structures based on charge-transfer (CT) interactions. From solution (sensors) to the solid state (assembled structures), we have fully utilized intrinsic and stimulus-induced CT interactions to construct these functional molecular systems. We have designed some organic molecules capable of ICT, with diversity and tailorability, that can be used to develop novel self-assembled materials. These ICT organic molecules are based on a variety of simple structures such as perylene bisimide, benzothiadiazole, tetracyanobutadiene, fluorenone, isoxazolone, BODIPY, and their derivatives. The degree of ICT is influenced by the nature of both the bridge and the substituents. We have developed new methods to synthesize ICT compounds through the introduction of heterocycles or heteroatoms to the π-conjugated systems or through extending the conjugation of diverse aromatic systems via another aromatic ring. Combining these ICT compounds featuring different D/A units and different degrees of conjugation with phase transfer methodologies and solvent-vapor techniques, we have self-assembled various organic nanostructures, including hollow nanospheres, wires, tubes, and ribbonlike architectures, with controllable morphologies and sizes. For example, we obtained a noncentrosymmetric microfiber structure that possessed a permanent dipole along its fibers' long axis and a transition dipole perpendicular to it; the independent NLO responses of this material can be separated and

  6. Symmetry-Breaking Charge Transfer in a Zinc Chlorodipyrrin Acceptor for High Open Circuit Voltage Organic Photovoltaics

    KAUST Repository

    Bartynski, Andrew N.

    2015-04-29

    © 2015 American Chemical Society. Low open-circuit voltages significantly limit the power conversion efficiency of organic photovoltaic devices. Typical strategies to enhance the open-circuit voltage involve tuning the HOMO and LUMO positions of the donor (D) and acceptor (A), respectively, to increase the interfacial energy gap or to tailor the donor or acceptor structure at the D/A interface. Here, we present an alternative approach to improve the open-circuit voltage through the use of a zinc chlorodipyrrin, ZCl [bis(dodecachloro-5-mesityldipyrrinato)zinc], as an acceptor, which undergoes symmetry-breaking charge transfer (CT) at the donor/acceptor interface. DBP/ZCl cells exhibit open-circuit voltages of 1.33 V compared to 0.88 V for analogous tetraphenyldibenzoperyflanthrene (DBP)/C60-based devices. Charge transfer state energies measured by Fourier-transform photocurrent spectroscopy and electroluminescence show that C60 forms a CT state of 1.45 ± 0.05 eV in a DBP/C60-based organic photovoltaic device, while ZCl as acceptor gives a CT state energy of 1.70 ± 0.05 eV in the corresponding device structure. In the ZCl device this results in an energetic loss between ECT and qVOC of 0.37 eV, substantially less than the 0.6 eV typically observed for organic systems and equal to the recombination losses seen in high-efficiency Si and GaAs devices. The substantial increase in open-circuit voltage and reduction in recombination losses for devices utilizing ZCl demonstrate the great promise of symmetry-breaking charge transfer in organic photovoltaic devices.

  7. Charge transfer interaction of 4-acetamidophenol (paracetamol) with 2,3-dichloro-1,4-naphthoquinone: A study in aqueous ethanol medium by UV-vis spectroscopic and DFT methods

    Science.gov (United States)

    Saha, Avijit; Tiwary, Amit S.; Mukherjee, Asok K.

    2008-12-01

    4-Acetamidophenol (paracetamol) is shown to form charge transfer complex with 2,3-dichloro1,4-naphthoquinone in aqueous ethanol media exhibiting the unusual 2:1 (paracetamol:quinone) stoichiometry. The complexation enthalpy and entropy have been estimated from the formation constant ( K) determined spectrophotometrically at five different temperatures. In aqueous ethanol mixtures of varying composition K increases with increasing dielectric constant of the medium. This has been rationalized by calculating the electronic charge distribution in paracetamol molecule and its conjugate base at the DFT/B3LYP/6-31++G(d,p) level. The theoretically calculated vertical ionization potential of paracetamol also agrees with reported experimental value.

  8. Charge transfer at organic-organic heterojunctions, and remote doping of a pentacene transistor

    Science.gov (United States)

    Zhao, Wei

    Organic-organic heterojunctions (OOHs) are the fundamental building blocks of organic devices, such as organic light-emitting diodes, organic photovoltaic cells, and photo detectors. Transport of free electrons and holes, exciton formation, recombination or dissociation, and various other physical processes all take place in OOHs. Understanding the electronic structures of OOH is critical for studying device physics and further improving the performance of organic devices. This work focuses on the electronic structure, i.e., the energy level alignment, at OOHs, investigated by ultraviolet and inverse photoemission spectroscopy (UPS and IPES). The weak interaction that generally prevails at OOH interfaces leads to small interface dipoles of 0˜0.5eV. The experimental observations on the majority of OOHs studied can be semi-quantitatively predicted by the model derived from the induced density of interface states and charge neutrality level (IDIS/CNL). However, we also find that the electronic structure of interfaces between two small-band-gap semiconductors, e.g., using copper phthalocyanine (CuPc) as the donor and a tris(thieno)-hexaazatriphenylene derivative (THAP) as the acceptor, is strongly influenced by changes in the substrate work function. In these cases, the charge transfer that takes place at the interface is governed by thermodynamic equilibrium, dominating any subtle interaction due to IDIS/CNL. The impact of doping on the energy level alignment of OOHs is also studied. The charges donated by the dopant molecules transfer from the parent doped layer to the adjacent undoped layer, taking advantage of the molecular level offset, and are then spatially separated from the dopant molecules. Remote doping, based on this charge transfer mechanism, is demonstrated with the heterojunction formed between pentacene and N,N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'bisphenyl-4,4'diazine (alpha-NPD) p-doped with tris[1,2-bis(trifluoromethyl) ethane-1,2-dithiolene] (Mo

  9. Platinum/Palladium hollow nanofibers as high-efficiency counter electrodes for enhanced charge transfer

    Science.gov (United States)

    Navarro Pardo, F.; Benetti, D.; Zhao, H. G.; Castaño, V. M.; Vomiero, A.; Rosei, F.

    2016-12-01

    Pt/Pd hollow nanofibers were obtained by sputtering a Pt/Pd alloy (80/20 wt%) onto polymer nanofibers (used as sacrificial template) and were used as counter-electrodes (CEs) in dye-sensitized solar cells (DSSCs). We demonstrate that optimization of nanofiber density and Pt/Pd sputtering thickness can increase the short circuit current density and consequently lead to a ∼15% enhancement in power conversion efficiency (PCE), when compared to the commonly used flat Pt/Pd CEs with the same thickness. The processes that contribute to such PCE improvement are: (i) increased surface area provided by the high aspect ratio hollow nanofibers and (ii) improved electro-catalytic performance, as validated by electrochemical impedance spectroscopy (EIS) measurements. The latter showed a two-fold decrease in the charge-transfer resistance of the nanostructured-CE, compared to the flat CE. The contribution of the Pt/Pd hollow nanofiber to light scattering was negligible as shown by reflectance measurements. These results suggest a simple and straightforward strategy to increase PCE in DSSCs, to minimize the use of precious metals used in this kind of devices and, more generally, to tailor the CE structure in photoelectrochemical systems to boost their functional properties, thanks to the advantages afforded by this complex morphology.

  10. Femtosecond Heterodyne Transient Grating Spectroscopic Studies of Intramolecular Charge Transfer Character of Peridinin and Peridinin Analogs

    Science.gov (United States)

    Bishop, Michael; Khosravi, Soroush; Obaid, Razib; Whitelock, Hope; Carroll, Ann Marie; Lafountain, Amy; Frank, Harry; Beck, Warren; Gibson, George; Berrah, Nora

    2016-05-01

    The peridinin chlorophyll-a protein is a light harvesting complex found in several species of dinoflagellates. Peridinin absorbs strongly in the mid-visible spectral region and, despite the lack of a strong permanent dipole moment in its lowest energy excited state, is able to transfer excitation energy quickly and efficiently to chlorophyll-a. It is believed that the high efficiency arises from the development of intramolecular charge-transfer (ICT) character upon photoexcitation. Recently, heterodyne transient grating spectroscopy has been used to study the ultrafast (<50 fs) dynamics of β carotene and peridinin. The studies show evidence for a structurally displaced intermediate in both cases and strong ICT character in the case of peridinin, but up to now the work has not provided appropriate control experiments. The present experiments examine peridinin and two peridinin analogs, S1-peridinin and S2-peridinin. S1-peridinin is reported to have greatly diminished ICT character, and S2-peridinin is reported to have little-or-no ICT character. Heterodyne transient grating data will be presented and provide a more unambiguous characterization spectral and kinetic properties associated with the peridinin ICT state. Funded by the DoE-BES, Grant No. DE-SC0012376.

  11. Magneto-photocurrent in organic photovoltaic cells; the effect of short-lived charge transfer states

    Science.gov (United States)

    Ehrenfreund, Eitan; Devir-Wolfman, A.; Khachatryan, B.; Gautam, B.; Tessler, N.; Vardeny, Z. V.

    2014-03-01

    The spin degrees of freedom are responsible for the magnetic field effects in organic devices at low magnetic fields. The MFE is formed via a variety of spin-mixing mechanisms, such as the hyperfine (typical strength: Bhf<0.003 T), triplet-polaron or triplet-triplet (Btrip<0.1 T) interactions, that limit the response by their respective strength. We report on magneto-photocurrent (MPC) response of bulk hetero-junction organic photovoltaic cells in an extended field range B =0.00005 - 8 Tesla, and found that spin mixing mechanisms are still operative even at the highest fields. In fact, the response MPC(B) can be divided into three main regions, each with a different sign: sharp response that increases with B up to B1 ~ 0.04 T; broad response that decreases with B in the range from B1 to B2 ~ 0.3-0.7 T; and even broader response that increases above B2; this response does not saturate even at 8.5 T. We attribute the latter MPC component to short-lived charge transfer excitons (CTE) where spin-mixing is caused by the difference of the donor/acceptor g factors; a mechanism that is increasingly more effective at high magnetic field. Supported by the US-Israel BSF.

  12. Probing of Charge Transfer States at Buried Organic Interfaces with Even-Order Spectroscopy

    Science.gov (United States)

    Pandey, Ravindra; Moon, Aaron; Roberts, Sean

    Organic thin film photovoltaics (OPV) are an emerging economically competitive technology that combines manufacturing adaptability, low-cost processing and a lightweight, flexible device end-product. At junctions formed between organic electron-donating and electron-accepting materials, the abrupt change in the dielectric properties can strongly perturb the density of states of the OPV. This can substantially alter the driving force for charge transfer between these materials. Electronic Sum Frequency Generation (ESFG), owing to its inherent interfacial sensitivity, is ideally suited to probe buried interfaces. Here, we report the ESFG spectra of Copper Phthalocyanine (CuPc) films, deposited on SiO2 measured for both reflection and transmission geometries. Three peaks are observed that roughly correlate with resonances that comprise CuPc's Q-band absorption but display slight shifts and amplitude changes with respect to CuPc's bulk absorption spectrum. Experimental results are compared with calculations based on a thin film interference model that accounts for ESFG emitted from both the CuPc:Air and CuPc:SiO2 interface as well as contributions to the signal from higher order source terms from the bulk. The model reveals a difference in the density of states between the two interfaces and suggests that by combining experimental transmission and reflection data it is possible to separate bulk and interfacial contributions to ESFG spectra.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-10-15

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

  14. Origin and impact of recombination via charge transfer excitons in polymer/fullerene solar cells

    Science.gov (United States)

    Hallermann, Markus; da Como, Enrico; Feldmann, Jochen

    2010-03-01

    To further advance the performances of organic photovoltaic cells a thorough understanding of loss mechanisms in polymer/fullerene blends is mandatory. Recombination via charge transfer excitons (CTEs) appears to be a fundamental loss, potentially impacting the open circuit voltage (VOC) and the short circuit current (ISC) of cells. We unravel the origin of CTEs forming in polymer/fullerene blends and discuss their importance in recombination processes considering binding energy [1], polymer conformation [2], and energetic position. CTE photoluminescence (PL) is observed in material combinations such as P3HT and PPV blended with fullerene acceptors. By combining electron microscopy and PL spectroscopy, we show that CTE recombination is only slightly influenced by the mesoscopic morphology, whereas strongly by the polymer chain conformation [2]. By shifting the orbital energies of the fullerene, we tune the CTE PL characteristics. High energy CTE emission results in cells with a beneficial increase in VOC. On the other hand, high energy CTE emission leads to a more efficient recombination impacting directly the ISC. The results highlight a fundamental limit in the efficiency of organic solar cells with CTE recombination. [1] Hallermann et al. APL 2008 [2] Hallermann et al. AFM 2009

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-10-17

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

  16. Charge transfer bands in optical materials and related defect level location

    Science.gov (United States)

    Dorenbos, Pieter

    2017-07-01

    Charge transfer (CT)-bands, electron trapping, hole trapping, electron release, hole release, metal-to-metal-charge transfer, CT-luminescence, anomalous emission, impurity trapped exciton emission, inter-valence charge transfer, pair-emission, tunneling, photo-electron spectroscopy, redox potentials, photo-ionization, thermal-ionization. All these phenomena deal with the transfer of an electron from one atom in a compound to either another atom in the compound or to the ambient, i.e., outside the compound. The energy needed for, or released in, such transfer carries information on the electron binding energy in the defect levels with respect to the host band levels or the levels in the ambient. First the different types of charge transfer between a lanthanide and the host bands, and how they can be used to construct a host referred binding energy (HRBE) diagram, are reviewed. Then briefly the chemical shift model is introduced in order to convert the HRBE diagram into a vacuum referred binding energy diagram (VRBE). Next charge transfer between transition metal elements and host bands and between Bi3+ and host bands are treated, and finally electron transfer from one defect to another and to the ambient. Illustrating examples are provided.

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

    Science.gov (United States)

    Lazić, Predrag; Štefančić, Hrvoje; Abraham, Hrvoje

    2006-03-01

    We introduce a novel numerical method, named the Robin Hood method, of solving electrostatic problems. The approach of the method is closest to the boundary element methods, although significant conceptual differences exist with respect to this class of methods. The method achieves equipotentiality of conducting surfaces by iterative non-local charge transfer. For each of the conducting surfaces, non-local charge transfers are performed between surface elements, which differ the most from the targeted equipotentiality of the surface. The method is tested against analytical solutions and its wide range of application is demonstrated. The method has appealing technical characteristics. For the problem with N surface elements, the computational complexity of the method essentially scales with Nα, where α < 2, the required computer memory scales with N, while the error of the potential decreases exponentially with the number of iterations for many orders of magnitude of the error, without the presence of the Critical Slowing Down. The Robin Hood method could prove useful in other classical or even quantum problems. Some future development ideas for possible applications outside electrostatics are addressed.

  18. Intermolecular electron transfer from intramolecular excitation and coherent acoustic phonon generation in a hydrogen-bonded charge-transfer solid

    Science.gov (United States)

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

    2016-03-01

    Organic materials that produce coherent lattice phonon excitations in response to external stimuli may provide next generation solutions in a wide range of applications. However, for these materials to lead to functional devices in technology, a full understanding of the possible driving forces of coherent lattice phonon generation must be attained. To facilitate the achievement of this goal, we have undertaken an optical spectroscopic study of an organic charge-transfer material formed from the ubiquitous reduction-oxidation pair hydroquinone and p-benzoquinone. Upon pumping this material, known as quinhydrone, on its intermolecular charge transfer resonance as well as an intramolecular resonance of p-benzoquinone, we find sub-cm-1 oscillations whose dispersion with probe energy resembles that of a coherent acoustic phonon that we argue is coherently excited following changes in the electron density of quinhydrone. Using the dynamical information from these ultrafast pump-probe measurements, we find that the fastest process we can resolve does not change whether we pump quinhydrone at either energy. Electron-phonon coupling from both ultrafast coherent vibrational and steady-state resonance Raman spectroscopies allows us to determine that intramolecular electronic excitation of p-benzoquinone also drives the electron transfer process in quinhydrone. These results demonstrate the wide range of electronic excitations of the parent of molecules found in many functional organic materials that can drive coherent lattice phonon excitations useful for applications in electronics, photonics, and information technology.

  19. Small gap semiconducting organic charge-transfer interfaces

    NARCIS (Netherlands)

    Nakano, M.; Alves, H.; Molinari, A.S.; Ono, S.; Minder, N.; Morpurgo, A.F.

    2010-01-01

    We investigated transport properties of organic heterointerfaces formed by single-crystals of two organic donor-acceptor molecules, tetramethyltetraselenafulvalene and 7,7,8,8-tetracyanoquinodimethane (TCNQ). Whereas the individual crystals have unmeasurably high resistance, the interface exhibits a

  20. Spectroscopy of equilibrium and nonequilibrium charge transfer in semiconductor quantum structures

    Science.gov (United States)

    Rössler, C.; Burkhard, S.; Krähenmann, T.; Röösli, M.; Märki, P.; Basset, J.; Ihn, T.; Ensslin, K.; Reichl, C.; Wegscheider, W.

    2014-08-01

    We investigate equilibrium and nonequilibrium charge-transfer processes by performing high-resolution transport spectroscopy. Using electrostatically defined quantum dots for energy-selective emission and detection, we achieved very high spectral resolution and a high degree of tunability of relevant experimental parameters. Most importantly, we observe that the spectral width of elastically transferred electrons can be substantially smaller than the linewidth of a thermally broadened Coulomb peak. This finding indicates that the charge-transfer process is fast compared to the electron-phonon interaction time. By drawing an analogy to double quantum dots, we argue that the spectral width of the elastic resonance is determined by the lifetime broadening hΓ of the emitter and detector states. Good agreement with the model is found also in an experiment in which the charge transfer is in the regime hΓ≫kBT. By performing spectroscopy below the Fermi energy, we furthermore observe elastic and inelastic transfer of holes.

  1. A two-dimensional position sensitive gas chamber with scanned charge transfer readout

    Science.gov (United States)

    Gómez, F.; Iglesias, A.; Lobato, R.; Mosquera, J.; Pardo, J.; Pena, J.; Pazos, A.; Pombar, M.; Rodríguez, A.

    2003-10-01

    We have constructed and tested a two-dimensional position sensitive parallel-plate gas ionization chamber with scanned charge transfer readout. The scan readout method described here is based on the development of a new position-dependent charge transfer technique. It has been implemented by using gate strips perpendicularly oriented to the collector strips. This solution reduces considerably the number of electronic readout channels needed to cover large detector areas. The use of a 25 μm thick kapton etched circuit allows high charge transfer efficiency with a low gating voltage, consequently needing a very simple commutating circuit. The present prototype covers 8×8 cm2 with a pixel size of 1.27×1.27 mm2. Depending on the intended use and beam characteristics a smaller effective pixel is feasible and larger active areas are possible. This detector can be used for X-ray or other continuous beam intensity profile monitoring.

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

    Science.gov (United States)

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

    2016-05-01

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

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

    DEFF Research Database (Denmark)

    Sherafatipour, Golenaz; Madsen, Morten

    charge transfer (CT) excitons, which is Coulombically bound interfacial electron- hole pairs residing at the donor/acceptor heterojunctions. The CT state represents an intermediate state between the exciton dissociation and recombination back to the ground state. Since the recombination of photo...... at the donor/acceptor interface is detected. As a less studied system, we examine here the interfacial charge transfer state recombination in DBP:C70 thin-films. The weak EL from the small molecule solar cell biased in the forward direction gives valuable information about the CT state recombination, from...... which the maximum open-circuit voltage can be estimated, and further can be used in the modeling and optimization of the OPV devices. [1] C. Deibe, T. Strobe, and V. Dyakonov, “Role of the charge transfer state in organic donor-acceptor solar cells,” Adv. Mater., vol. 22, pp. 4097–4111, 2010. [2] K...

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

    Science.gov (United States)

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

    2017-06-05

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

  5. Analysis of incomplete charge transfer effects in a CMOS image sensor

    Institute of Scientific and Technical Information of China (English)

    Han Liqiang; Yao Suying; Xu Jiangtao; Xu Chao; Gao Zhiyuan

    2013-01-01

    A method to judge complete charger transfer is proposed for a four-transistor CMOS image sensor with a large pixel size.Based on the emission current theory,a qualitative photoresponse model is established to the preliminary prediction.Further analysis of noise for incomplete charge transfer predicts the noise variation.The test pixels were fabricated in a specialized 0.18μm CMOS image sensor process and two different processes of buried N layer implantation are compared.The trend prediction corresponds with the test results,especially as it can distinguish an unobvious incomplete charge transfer.The method helps us judge whether the charge transfer time satisfies the requirements of the readout circuit for the given process especially for pixels of a large size.

  6. Charge transfer and excitation in H++CH3 collisions below 10keV

    Science.gov (United States)

    Nagao, Masatoshi; Hida, Ken-Nosuke; Kimura, Mineo; Rai, Sachchida N.; Liebermann, Heinz-Peter; Buenker, Robert J.; Suno, Hiroya; Stancil, Phillip C.

    2008-07-01

    Charge transfer and electronic excitation in collisions of H+ ions with CH3 from a few tens of eV up to 10keV are theoretically investigated. The adiabatic potential energy curves and corresponding wave functions are calculated by using the multireference single- and double-excitation configuration interaction method, and the scattering dynamics is studied based on the semiclassical impact parameter molecular-orbital close-coupling approach. Charge-transfer cross sections are found to be large and rather energy-dependent over the entire energy region studied. Electronic excitation is also energy-dependent with a sharp increase from below 10-17to10-16cm2 . Most of the molecular products produced through charge transfer or excitation are known to be unstable and undergo fragmentation producing various hydrocarbon radical species. Hence, identification of fragmented species and their production mechanism are important for spectroscopic analysis.

  7. Near resonant charge transfer in the reaction F(+) + CO - F + CO(+)

    Science.gov (United States)

    Kusunoki, I.; Ishikawa, T.

    1985-06-01

    Charge transfer reactions in the F(+) + CO system were investigated using a F(+) ion beam in the energy range 10-300 eVlab. The electronically excited product CO(+) A2Pi(i) was observed by the emission from the A-X transitions. At low collisional energy the dominant product is in the vibrational level v' = 5. The reaction cross section sigma(5) is about 1 A-sq at 12 eVc.m. and decreases with increasing collision energy. The large cross section at v' = 5 can be interpreted by near-resonant charge-transfer reactions. The rotational temperature of the product is about 300 K, which is the temperature of the reactant CO gas. For the resonant charge transfer, the translational energy is not effective, but the electronic and vibrational energy couple with each other strongly.

  8. Topological effects of charge transfer in telomere G-quadruplex: Mechanism on telomerase activation and inhibition

    CERN Document Server

    Wang, Xin

    2015-01-01

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

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

    Science.gov (United States)

    Wang, Xin; Liang, Shi-Dong

    2013-02-01

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

  10. Polyoxometalate active charge-transfer material for mediated redox flow battery

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-01-17

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

  11. Photovoltaic effect in organic polymer-iodine complex

    Science.gov (United States)

    Hermann, A. M.; Rembaum, A.

    1967-01-01

    Certain charge transfer complexes formed from organic polymers and iodine generate appreciable voltages at relatively low impedances upon exposure to light. These films show promise in applications requiring chemically and electrically stable films as detectors of optical radiation and as energy converters in photovoltaic cells.

  12. Fullerene-Assisted Photoinduced Charge Transfer of Single-Walled Carbon Nanotubes through a Flavin Helix.

    Science.gov (United States)

    Mollahosseini, Mehdi; Karunaratne, Erandika; Gibson, George N; Gascón, Jose A; Papadimitrakopoulos, Fotios

    2016-05-11

    One of the greatest challenges with single-walled carbon nanotube (SWNT) photovoltaics and nanostructured devices is maintaining the nanotubes in their pristine state (i.e., devoid of aggregation and inhomogeneous doping) so that their unique spectroscopic and transport characteristics are preserved. To this effect, we report on the synthesis and self-assembly of a C60-functionalized flavin (FC60), composed of PCBM and isoalloxazine moieties attached on either ends of a linear, C-12 aliphatic spacer. Small amounts of FC60 (up to 3 molar %) were shown to coassembly with an organic soluble derivative of flavin (FC12) around SWNTs and impart effective dispersion and individualization. A key annealing step was necessary to perfect the isoalloxazine helix and expel the C60 moiety away from the nanotubes. Steady-state and transient absorption spectroscopy illustrate that 1% or higher incorporation of FC60 allows for an effective photoinduced charge transfer quenching of the encased SWNTs through the seamless helical encase. This is enabled via the direct π-π overlap between the graphene sidewalls, isoalloxazine helix, and the C60 cage that facilitates SWNT exciton dissociation and electron transfer to the PCBM moiety. Atomistic molecular simulations indicate that the stability of the complex originates from enhanced van der Waals interactions of the flexible spacer wrapped around the fullerene that brings the C60 in π-π overlap with the isoalloxazine helix. The remarkable spectral purity (in terms of narrow E(S)ii line widths) for the resulting ground-state complex signals a new class of highly organized supramolecular nanotube architecture with profound importance for advanced nanostructured devices.

  13. Charge transfer mediator based systems for electrocatalytic oxygen reduction

    Energy Technology Data Exchange (ETDEWEB)

    Stahl, Shannon S.; Gerken, James B.; Anson, Colin W.

    2017-07-18

    Disclosed are systems for the electrocatalytic reduction of oxygen, having redox mediator/redox catalyst pairs and an electrolyte solution in contact with an electrode. The redox mediator is included in the electrolyte solution, and the redox catalyst may be included in the electrolyte solution, or alternatively, may be in contact with the electrolyte solution. In one form a cobalt redox catalyst is used with a quinone redox mediator. In another form a nitrogen oxide redox catalyst is used with a nitroxyl type redox mediator. The systems can be used in electrochemical cells wherein neither the anode nor the cathode comprise an expensive metal such as platinum.

  14. The description of charge transfer in fast negative ions scattering on water covered Si(100) surfaces

    Science.gov (United States)

    Chen, Lin; Qiu, Shunli; Liu, Pinyang; Xiong, Feifei; Lu, Jianjie; Liu, Yuefeng; Li, Guopeng; Liu, Yiran; Ren, Fei; Xiao, Yunqing; Gao, Lei; Zhao, Qiushuang; Ding, Bin; Li, Yuan; Guo, Yanling; Chen, Ximeng

    2016-11-01

    Doping has significantly affected the characteristics and performance of semiconductor electronic devices. In this work, we study the charge transfer processes for 8.5-22.5 keV C- and F- ions scattering on H2O-terminated p-type Si(100) surfaces with two different doping concentrations. We find that doping has no influence on negative-ion formation for fast collisions in this relatively high energy range. Moreover, we build a model to calculate negative ion fractions including the contribution from positive ions. The calculations support the nonadiabatic feature of charge transfer.

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

    Science.gov (United States)

    Tosh, R. E.; Johnsen, R.

    1993-01-01

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

  16. Molecular Dynamics Simulation on Charge Transfer Relaxation between Myoglobin and Water

    Institute of Scientific and Technical Information of China (English)

    CHENG Wei; ZHANG Feng-Shou; ZHANG Bo-Yang; ZHOU Hong-Yu

    2007-01-01

    Dynamical processes of myoglobin after photon-excited charge transfer between Fe ion and surrounding water anion ale simulated by a molecular dynamics model.The roles of Coulomb interaction effect and water effect in the relaxation process are discussed.It is found that the relaxations before and after charge transfer are similar.Strong Coulomb interactions and less water mobility decrease Coulomb energy fluctuations.An extra transferred charge of Fe ion has impact on water packing with a distance up to 0.86nm.

  17. Charge transfer mechanism for the formation of metallic states at the KTaO3/SrTiO3 interface

    KAUST Repository

    Nazir, Safdar

    2011-03-29

    The electronic and optical properties of the KTaO3/SrTiO3 heterointerface are analyzed by the full-potential linearized augmented plane-wave approach of density functional theory. Optimization of the atomic positions points at subordinate changes in the crystal structure and chemical bonding near the interface, which is due to a minimal lattice mismatch. The creation of metallic interface states thus is not affected by structural relaxation but can be explained by charge transfer between transition metal and oxygen atoms. It is to be expected that a charge transfer is likewise important for related interfaces such as LaAlO3/SrTiO3. The KTaO3/SrTiO3 system is ideal for disentangling the complex behavior of metallic interface states, since almost no structural relaxation takes place.

  18. Molecular adsorption on ZnO(1010) single-crystal surfaces: morphology and charge transfer.

    Science.gov (United States)

    Chen, Jixin; Ruther, Rose E; Tan, Yizheng; Bishop, Lee M; Hamers, Robert J

    2012-07-17

    While ZnO has excellent electrical properties, it has not been widely used for dye-sensitized solar cells, in part because ZnO is chemically less stable than widely used TiO(2). The functional groups typically used for surface passivation and for attaching dye molecules either bind weakly or etch the ZnO surface. We have compared the formation of molecular layers from alkane molecules with terminal carboxylic acid, alcohol, amine, phosphonic acid, or thiol functional groups on single-crystal zinc oxide (1010) surfaces. Atomic force microscopy (AFM) images show that alkyl carboxylic acids etch the surface whereas alkyl amine and alkyl alcohols bind only weakly on the ZnO(1010) surface. Phosphonic acid-terminated molecules were found to bind to the surface in a heterogeneous manner, forming clusters of molecules. Alkanethiols were found to bind to the surface, forming highly uniform monolayers with some etching detected after long immersion times in an alkanethiol solution. Monolayers of hexadecylphosphonic acid and octadecanethiol were further analyzed by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and electrochemical measurements. AFM scratching shows that thiols were bound strongly to the ZnO surface, suggesting the formation of strong Zn-S covalent bonds. Surprisingly, the tridentate phosphonic acids adhered much more weakly than the monodentate thiol. The influence of organic grafting on the charge transfer to ZnO was studied by time-resolved surface photovoltage measurements and electrochemical impedance measurements. Our results show that the grafting of thiols to ZnO leads to robust surfaces and reduces the surface band bending due to midgap surface states.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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

  1. Photophysics of charge transfer in a polyfluorene/violanthrone blend

    Science.gov (United States)

    Cabanillas-Gonzalez, J.; Virgili, T.; Lanzani, G.; Yeates, S.; Ariu, M.; Nelson, J.; Bradley, D. D. C.

    2005-01-01

    We present a study of the photophysical and photovoltaic properties of blends of violanthrone in poly[9, 9-bis (2-ethylhexyl)-fluorene-2, 7-diyl ] (PF2/6) . Photoluminescence quenching and photocurrent measurements show moderate efficiencies for charge generation, characteristic of such polymer/dye blends. Pump-probe measurements on blend films suggest that while ˜47% of the total exciton population dissociates within 4ps of photoexcitation, only ˜32% subsequently results in the formation of dye anions. We attribute the discrepancy to the likely formation of complex species with long lifetimes, such as stabilized interface charge pairs or exciplexes. This conclusion is supported by the appearance of a long lifetime component of 2.4ns in the dynamics of the photoinduced absorption signal associated to polarons in photoinduced absorption bands centered at 560nm .

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1997-01-01

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

  3. Charge transfer polarisation wave in high Tc oxides and superconductive pairing

    Science.gov (United States)

    Chakraverty, B. K.

    1991-01-01

    A general formalism of quantized charge transfer polarization waves was developed. The nature of possible superconductive pairing between oxygen holes is discussed. Unlike optical phonons, these polarization fields will give rise to dielectric bipolarons or bipolaron bubbles. In the weak coupling limit, a new class of superconductivity is to be expected.

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

    NARCIS (Netherlands)

    Gorczak-Vos, N.

    2016-01-01

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

  5. Molecular orbital (SCF-Xα-SW) theory of metal-metal charge transfer processes in minerals

    Science.gov (United States)

    Sherman, David M.

    1987-01-01

    A number of mixed valence iron oxides and silicates (e.g., magnetite, ilvaite) exhibit thermally induced electron delocalization between adjacent Fe2+ and Fe3+ ions and optically induced electronic transitions which are assigned to Fe2+→Fe3+ intervalence charge transfer.

  6. Small-signal charge transfer inefficiency experiments explained by the McWhorter interface state model

    NARCIS (Netherlands)

    Penning De Vries, René G.M.; Wallinga, Hans

    1984-01-01

    The small-signal charge transfer inefficiency (SCTI) of a surface-channel CCD has been studied. The experimentally observed behavior of the SCTI could not be explained by the conventional interface state model. Using the McWhorter model for the interface states, which assumes a distribution of the s

  7. Ground-state charge transfer as a mechanism for surface-enhanced Raman scattering

    Science.gov (United States)

    Lippitsch, Max E.

    1984-03-01

    A model is presented for the contribution of ground-state charge transfer between a metal and adsorbate to surface-enhanced Raman scattering (SERS). It is shown that this contribution can be understood using the vibronic theory for calculating Raman intensities. The enhancement is due to vibronic coupling of the molecular ground state to the metal states, the coupling mechanism being a modulation of the ground-state charge-transfer energy by the molecular vibrations. An analysis of the coupling operator gives the selection rules for this process, which turn out to be dependent on the overall symmetry of the adsorbate-metal system, even if the charge transfer is small enough for the symmetry of the adsorbate to remain the same as that of the free molecule. It is shown that the model can yield predictions on the properties of SERS, e.g., specificity to adsorption geometry, appearance of forbidden bands, dependence on the applied potential, and dependence on the excitation wavelength. The predictions are in good agreement with experimental results. It is also deduced from this model that in many cases atomic-scale roughness is a prerequisite for the observation of SERS. A result on the magnitude of the enhancement can only be given in a crude approximation. Although in most cases an additional electromagnetic enhancement seems to be necessary to give an observable signal, this charge-transfer mechanism should be important in many SERS systems.

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

    Science.gov (United States)

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

    2002-01-01

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

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

    DEFF Research Database (Denmark)

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

    2016-01-01

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

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

    DEFF Research Database (Denmark)

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

    2003-01-01

    We have thoroughly characterized the surfaces of the organic charge-transfer salts TTF-TCNQ and (TMTSF)(2)PF6 which are generally acknowledged as prototypical examples of one-dimensional conductors. In particular x-ray-induced photoemission spectroscopy turns out to be a valuable nondestructive d...

  11. Charge Injection, Charge Trapping and Charge Transfer in Quantum-Dot Solids

    NARCIS (Netherlands)

    Boehme, S.C.

    2015-01-01

    This study reports on fundamental processes in Quantum-Dot Solids, after light absorption. Transient Absorption and Time-resolved Photoluminescence spectrocopy reveal the dynamics of charge transfer and charge trapping processes. Typically, both occur on a picosecond time scale and compete with each

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

    Science.gov (United States)

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

    2016-10-01

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

  13. [Combined hopping-superexchange mechanism of charge transfer in DNA; a model with nearest interactions].

    Science.gov (United States)

    Lakhno, V D; Sultanov, V B

    2007-01-01

    In the framework of the earlier developed combined hopping-superexchange mechanism of charge transfer in DNA, a model with all nearest interactions between nucleobases is proposed. It is shown that the transfer rates for various types of nucleotide sequences calculated within this model are in a good agreement with experimental data.

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

    Science.gov (United States)

    Cai, Yongqing; Feng, Yuan Ping

    2016-12-01

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

  15. The influence of the HGMF on mass-charge transfer in gravisensing cells.

    Science.gov (United States)

    Kondrachuk, A; Belyavskaya, N

    2001-07-01

    The present work is focused on the influence of the high-gradient-magnetic field (HGMF) on spatial distribution of ion fluxes along the roots (a), cytoplasmic streaming (b), and the processes of plant cell growth connected with intracellular mass and charge transfer (c).

  16. Low-energy state-selective charge transfer by multiply charged ions

    NARCIS (Netherlands)

    Lubinski, G; Juhasz, Z; Morgenstern, R; Hoekstra, R

    2001-01-01

    We present a combined rf-guided ion beam and photon emission spectroscopy method, which facilitates state-selective charge-transfer measurements at energies of direct relevance for astrophysics and fusion-plasma diagnostics and modeling. Ion energies have been varied from 1000 eV/amu down to energie

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

    KAUST Repository

    Whited, Matthew T.

    2012-01-01

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

  18. Intramolecular Charge Transfer and Solvation of Photoactive Molecules with Conjugated Push-Pull Structures.

    Science.gov (United States)

    Zhu, Huaning; Wang, Xian; Ma, Renjun; Kuang, Zhuoran; Guo, Qianjin; Xia, Andong

    2016-10-18

    A comparative investigation on the photophysical properties and solvation-related ICT dynamics of three push-pull compounds containing different donors including carbazole, triphenylamine and phenothiazine, was performed. The steady-state spectra and theoretical calculations show the charge transfers from the central donors to the acceptors at each side. The characterization of the extent of charge transfer was determined by various means, including estimation of the dipole moment, the electron density distribution of HOMO and LUMO, CDD and change in Gibb's free energy, which show the charge transfer strength to be in the order PDHP > BDHT > PDHC. This suggests that the electron-donating ability of the donor groups plays a crucial role in the charge transfer in these compounds. The TA data show the excited-state relaxation dynamics follow a sequential model: FC→ICT→ICT'→S0 , and are affected by the solvent polarity. The results presented here demonstrate that the compound with a higher degree of ICT characteristic interacts more strongly with stronger polar solvent molecules, which can accelerate the solvation and spectral evolution to lower energy levels. The A-π-D-π-A architectures with prominent ICT characteristics based on carbazole, triphenylamine and phenothiazine might be potential scaffolds for light-harvesting and photovoltaic devices. These results are of value for understanding structure-property relationships and the rational design of functional materials for photoelectric applications.

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

    Science.gov (United States)

    Beck, Sebastian; Hillebrandt, Sabina; Pucci, Annemarie

    2016-09-01

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

  20. The intramolecular charge transfer state in carbonyl-containing polyenes and carotenoids.

    Science.gov (United States)

    Enriquez, Miriam M; Fuciman, Marcel; LaFountain, Amy M; Wagner, Nicole L; Birge, Robert R; Frank, Harry A

    2010-09-30

    Numerous femtosecond time-resolved optical spectroscopic experiments have reported that the lifetime of the low-lying S(1) state of carbonyl-containing polyenes and carotenoids decreases with increasing solvent polarity. The effect becomes even more pronounced as the number of double bonds in the conjugated π-electron system decreases. The effect has been attributed to an intramolecular charge transfer (ICT) state coupled to S(1), but it is still not clear what the precise molecular nature of this state is, and how it is able to modulate the spectral and dynamic properties of polyenes and carotenoids. In this work, we examine the nature of the ICT state in three substituted polyenes: crocetindial, which contains two terminal, symmetrically substituted carbonyl groups in conjugation with the π-electron system, 8,8'-diapocarotene-8'-ol-8-al, which has one terminal conjugated carbonyl group and one hydroxyl group, and 8,8'-diapocarotene-8,8'-diol, which has two terminal, symmetrically positioned, hydroxyl groups but no carbonyls. Femtosecond time-resolved optical spectroscopic experiments on these molecules reveal that only the asymmetrically substituted 8,8'-diapocarotene-8'-ol-8-al exhibits any substantial effect of solvent on the excited state spectra and dynamics. The data are interpreted using molecular orbital theory which shows that the ICT state develops via mixing of the low-lying S(1) (2(1)A(g)-like) and S(2) (1(1)B(u)-like) excited singlet states to form a resultant state that preferentially evolves in polar solvent and exhibits a very large (∼25 D) dipole moment. Molecular dynamics calculations demonstrate that the features of the ICT state are present in ∼20 fs.

  1. Energy and Charge Transfer in Open Plasmonic Systems

    Science.gov (United States)

    Thakkar, Niket

    Coherent and collective charge oscillations in metal nanoparticles (MNPs), known as localized surface plasmons, offer unprecedented control and enhancement of optical processes on the nanoscale. Since their discovery in the 1950's, plasmons have played an important role in understanding fundamental properties of solid state matter and have been used for a variety of applications, from single molecule spectroscopy to directed radiation therapy for cancer treatment. More recently, experiments have demonstrated quantum interference between optically excited plasmonic materials, opening the door for plasmonic applications in quantum information and making the study of the basic quantum mechanical properties of plasmonic structures an important research topic. This text describes a quantitatively accurate, versatile model of MNP optics that incorporates MNP geometry, local environment, and effects due to the quantum properties of conduction electrons and radiation. We build the theory from first principles, starting with a silver sphere in isolation and working our way up to complex, interacting plasmonic systems with multiple MNPs and other optical resonators. We use mathematical methods from statistical physics and quantum optics in collaboration with experimentalists to reconcile long-standing discrepancies amongst experiments probing plasmons in the quantum size regime, to develop and model a novel single-particle absorption spectroscopy, to predict radiative interference effects in entangled plasmonic aggregates, and to demonstrate the existence of plasmons in photo-doped semiconductor nanocrystals. These examples show more broadly that the theory presented is easily integrated with numerical simulations of electromagnetic scattering and that plasmonics is an interesting test-bed for approximate methods associated with multiscale systems.

  2. Polaron assisted charge transfer in model biological systems

    Science.gov (United States)

    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.

  3. Role of charge transfer interaction and the chemical physics behind effective fulleropyrrolidine/porphyrin non-covalent interaction in solution.

    Science.gov (United States)

    Mondal, Ashis; Santhosh, Kotni; Bauri, Ajoy; Bhattacharya, Sumanta

    2014-01-01

    The present paper reports the photophysical insights on supramolecular interaction of a monoporphyrin derivative, namely, 1, with C60 pyrrolidine tris-acid ethyl ester (PyC60) in toluene and benzonitrile. The ground state interaction between PyC60 and 1 is facilitated through charge transfer interaction. Both UV-Vis and steady state measurements elicit almost similar magnitude of binding constant for the PyC60/1 complex in toluene and benzonitrile, viz., 6825 and 6540 dm(3 )mol(-1), respectively. Life time measurement evokes that rate of charge separation is fast in benzonitrile. Both hybrid-DFT and DFT calculations provide very good support in favor of electronic charge-separation in PyC60/1 system in vacuo.

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

    Science.gov (United States)

    Hestand, Nicholas J.

    The field of organic electronics has received considerable attention over the past several years due to the promise of novel electronic materials that are cheap, flexible and light weight. While some devices based on organic materials have already emerged on the market (e.g. organic light emitting diodes), a deeper understanding of the excited states within the condensed phase is necessary both to improve current commercial products and to develop new materials for applications that are currently in the commercial pipeline (e.g. organic photovoltaics, wearable displays, and field effect transistors). To this end, a model for pi-conjugated molecular aggregates and crystals is developed and analyzed. The model considers two types of electronic excitations, namely Frenkel and charge-transfer excitons, both of which play a prominent role in determining the nature of the excited states within tightly-packed organic systems. The former consist of an electron-hole pair bound to the same molecule while in the later the electron and hole are located on different molecules. The model also considers the important nuclear reorganization that occurs when the system switches between electronic states. This is achieved using a Holstein-style Hamiltonian that includes linear vibronic coupling of the electronic states to the nuclear motion associated with the high frequency vinyl-stretching and ring-breathing modes. Analysis of the model reveals spectroscopic signatures of charge-transfer mediated J- and H-aggregation in systems where the photophysical properties are determined primarily by charge-transfer interactions. Importantly, such signatures are found to be sensitive to the relative phase of the intermolecular electron and hole transfer integrals, and the relative energy of the Frenkel and charge-transfer states. When the charge-transfer integrals are in phase and the energy of the charge-transfer state is higher than the Frenkel state, the system exhibits J

  5. Electronic structure of novel charge transfer compounds: application of Fermi orbital self-interaction corrected density functional theory

    Science.gov (United States)

    Hahn, Torsten; Rückerl, Florian; Liebing, Simon; Pederson, Mark

    We present our experimental and theoretical results on novel Picene/F4TCNQ and Manganese-Phthalocyanine/F4TCNQ donor / acceptor systems. We apply the recently developed Fermi-orbital based approach for self-interaction corrected density functional theory (FO-SIC DFT) to these materials and compare the results to standard DFT calculations and to experimental data obtained by photoemission spectroscopy. We focus our analysis on the description of the magnitude of the ground state charge transfer and on the details of the formed hybrid orbitals. Further, we show that for weakly bound donor / acceptor systems the FO-SIC approach delivers a more realistic description of the electronic structure compared to standard DFT calculations Support by DFG FOR1154 is greatly acknowledged.

  6. Secondary Teachers' Conception of Various Forms of Complex Numbers

    Science.gov (United States)

    Karakok, Gulden; Soto-Johnson, Hortensia; Dyben, Stephenie Anderson

    2015-01-01

    This study explores in-service high school mathematics teachers' conception of various forms of complex numbers and ways in which they transition between different representations of these forms. One 90-min interview was conducted with three high school mathematics teachers after they completed three professional development sessions, each 4 h, on…

  7. Encountering Productive Forms of Complexity in Learning Modern Physics

    Science.gov (United States)

    Levrini, Olivia; Fantini, Paola

    2013-01-01

    This paper aims at supporting the claim that some forms of hyper-simplification, by making physics seem easy, are at risk of dangerously distorting the content as well as the process of learning physics. The paper presents examples of dangerous simplifications in the teaching of quantum physics. Then, examples of productive forms of complexity are…

  8. Electron Doping by Charge Transfer at LaFeO 3 /Sm 2 CuO 4 Epitaxial Interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Bruno, Flavio Y. [Universidad Complutense, Spain; Schmidt, R [Universidad Complutense de Madrid, Spain; Varela, Maria [UCM, Dept Fis Aplicada 3, Madrid, Spain; Garcia-Barriocanal, Javier [Universidad Complutense, Spain; Rivera-Calzada, Alberto [Universidad Complutense, Spain; Cuellar, F. [Universidad Complutense de Madrid, Spain; Leon, Carlos [Universidad Complutense de Madrid, Spain; Thakur, P. [European Synchrotron Radiation Facility (ESRF); Cezar, J. C. [European Synchrotron Radiation Facility (ESRF); Brookes, N. B. [European Synchrotron Radiation Facility (ESRF); Garcia-Hernandez, M [Instituto de Ciencia de Materiales de Madrid (ICMM); Dagotto, Elbio R [ORNL; Pennycook, Stephen J [ORNL; Santamaria, J. [Universidad Complutense, Spain

    2013-01-01

    The breakdown of the lattice translational invariance symmetry that occurs at complex oxide interfaces may profoundly modify their electronic structure, leading to interfacial states with properties drastically different from those of the superlattice individual components. The appearance of a conducting two dimensional (2D) electron gas at the interface between two insulating oxides and induced magnetism in a non-magnetic material are just two among many fascinating examples. [ 1 8 ] One of the key factors underlying novel properties is the modifi cation of the doping and orbital occupancy near those interfaces, which may result from charge transfer processes. [ 3 , 9 11 ] If materials used in heterostructures have different work functions, a non-equilibrium situation will be created at the interface and charge will be transferred until the chemical potential levels off. [ 12 ] The use of such phenomena to modify doping in heterostructures has been proposed theoretically as a new route to avoid the quenched disorder that inevitably accompanies the chemical doping. At the interface between a Mott insulating parent compound of the high critical temperature superconductor (HTSC) family and a suitable material that would act as the charge donor, electron doped phases could be stabilized which would eventually turn metallic and perhaps superconducting. [ 12 , 13 ] Such charge transfer processes have been observed at interfaces involving copper oxides such as La 0.7 Ca 0.3 MnO 3 / YBa 2 Cu 3 O 7 , [ 14 ] La 2 x Sr x CuO 4 /La 2 CuO 4 [ 15 ] and SrTi 1 x Nb x O 3 / Sm 2 CuO 4 . [ 16 ] While a novel 2D superconducting state was found at the La 2-x Sr x CuO 4 /La 2 CuO 4 interface, [ 17 ] the effect of doping by charge transfer could not be examined in the other two cases due to the detrimental effect on the YBa 2 Cu 3 O 7 superconductivity of the spin polarized electrons from La 0.7 Ca 0.3 MnO 3 in one case and due to the conducting nature of the SrTi 1 x Nb x O 3 in the

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

    DEFF Research Database (Denmark)

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

    2013-01-01

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

  10. Dynamical complexity changes during two forms of meditation

    Science.gov (United States)

    Li, Jin; Hu, Jing; Zhang, Yinhong; Zhang, Xiaofeng

    2011-06-01

    Detection of dynamical complexity changes in natural and man-made systems has deep scientific and practical meaning. We use the base-scale entropy method to analyze dynamical complexity changes for heart rate variability (HRV) series during specific traditional forms of Chinese Chi and Kundalini Yoga meditation techniques in healthy young adults. The results show that dynamical complexity decreases in meditation states for two forms of meditation. Meanwhile, we detected changes in probability distribution of m-words during meditation and explained this changes using probability distribution of sine function. The base-scale entropy method may be used on a wider range of physiologic signals.

  11. Charge transfer and polarization for chloride ions bound in ClC transport proteins: natural bond orbital and energy decomposition analyses.

    Science.gov (United States)

    Church, Jonathan; Pezeshki, Soroosh; Davis, Christal; Lin, Hai

    2013-12-19

    ClC transport proteins show a distinct "broken-helix" architecture, in which certain α-helices are oriented with their N-terminal ends pointed toward the binding sites where the chloride ions are held extensively by the backbone amide nitrogen atoms from the helices. To understand the effectiveness of such binding structures, we carried out natural bond orbital analysis and energy decomposition analysis employing truncated active-site model systems for the bound chloride ions along the translocation pore of the EcClC proteins. Our results indicated that the chloride ions are stabilized in such a binding environment by electrostatic, polarization, and charge-transfer interactions with the backbone and a few side chains. Up to ~25% of the formal charges of the chloride ions were found smeared out to the surroundings primarily via charge transfer from the chloride's lone pair n(Cl) orbitals to the protein's antibonding σ*(N-H) or σ*(O-H) orbitals; those σ* orbitals are localized at the polar N-H and O-H bonds in the chloride's first solvation shells formed by the backbone amide groups and the side chains of residues Ser107, Arg147, Glu148, and Tyr445. Polarizations by the chloride ions were dominated by the redistribution of charge densities among the π orbitals and lone pair orbitals of the protein atoms, in particular the atoms of the backbone peptide links and of the side chains of Arg147, Glu148, and Tyr445. The substantial amounts of electron density involved in charge transfer and in polarization were consistent with the large energetic contributions by the two processes revealed by the energy decomposition analysis. The significant polarization and charge-transfer effects may have impacts on the mechanisms and dynamics of the chloride transport by the ClC proteins.

  12. Charge-Transfer Supra-Amphiphiles Built by Water-Soluble Tetrathiafulvalenes and Viologen-Containing Amphiphiles: Supramolecular Nanoassemblies with Modifiable Dimensions.

    Science.gov (United States)

    Lv, Zhong-Peng; Chen, Bin; Wang, Hai-Ying; Wu, Yue; Zuo, Jing-Lin

    2015-08-05

    In this study, multidimensional nanoassemblies with various morphologies such as nanosheets, nanorods, and nanofibers are developed via charge-transfer interaction and supra-amphiphile self-assembling in aqueous phase. The charge-transfer interactions between tetrathiafulvalene derivatives (TTFs) and methyl viologen derivatives (MVs) have been confirmed by the characteristic charger-transfer absorption. (1) H NMR and electrospray ionizsation mass spectrometry (ESI-MS) analyses also indicate supra-amphiphiles are formed by the combination of TTFs and MVs head group through charge-transfer interaction and Coulombic force. X-ray single crystal structural studies, transmission electron microscopy (TEM), and scanning electron microscopy (SEM) reveal that both linkage pattern of TTFs in hydrophilic part and alkane chain structure in hydrophobic part have significant influence on nanoassemblies morphology and microstructure. Moreover, gold nanoparticles (AuNPs) are introduced in the above supramolecular nanoassemblies to construct a supra-amphiphile-driven organic-AuNPs assembly system. AuNPs could be assembled into 1D-3D structures by adding different amount of MVs.

  13. Surfaces with parallel mean curvature vector in complex space forms

    CERN Document Server

    Fetcu, Dorel

    2010-01-01

    We consider a quadratic form defined on the surfaces with parallel mean curvature vector of an any dimensional complex space form and prove that its $(2,0)$-part is holomorphic. When the complex dimension of the ambient space is equal to $2$ we define a second quadratic form with the same property and then determine those surfaces with parallel mean curvature vector on which the $(2,0)$-parts of both of them vanish. We also provide a reduction of codimension theorem and prove a non-existence result for $2$-spheres with parallel mean curvature vector.

  14. Photoinduced intramolecular charge transfer in push-pull polyenes: effects of solvation, electron-donor group, and polyenic chain length.

    Science.gov (United States)

    Akemann, Walther; Laage, Damien; Plaza, Pascal; Martin, Monique M; Blanchard-Desce, Mireille

    2008-01-17

    Subpicosecond absorption spectroscopy is used to characterize the primary photoinduced processes in a class of push-pull polyenes bearing a julolidine end group as the electron donor and a diethylthiobarbituric acid end group as the electron acceptor. The excited-state decay time and relaxation pathway have been studied for four polyenes of increasing chain length (n = 2-5 double bonds) in aprotic solvents of different solvation time, polarity, and viscosity. Intramolecular charge transfer (ICT) leading to a transient state of cyanine-like structure (fully conjugated with no bond length alternation) is observed in all polar solvents at a solvent dependent rate, but the reaction is not observed in cyclohexane, a nonpolar solvent. In polar solvents, the reaction time increases with the average solvation time but remains slightly larger, except in the viscous solvent triacetin. These facts are interpreted as an indication that both solvent reorganization and internal restructuring are involved in the ICT-state formation. The observed photodynamics resemble those we previously found for another class of polyenes bearing a dibutylaniline group as the donor, including a similar charge-transfer rate in spite of the larger electron donor character of the julolidine group. This observation brings further support to the proposal that an intramolecular coordinate is involved in the charge-transfer reaction, possibly a torsional motion of the donor end group. On the other hand, relaxation of the ICT state leads to cis-trans isomerization or crossing to the triplet state, depending on the length of the polyenic chain. In dioxane, tetrahydrofuran, and triacetin, the ICT state of the shorter chains (n = 2, 3) relaxes to the isomer with a viscosity-dependent rate, while that of the longer ones (n = 4, 5) leads to the triplet state with a viscosity-independent rate, as expected. In acetonitrile, the ICT-state lifetime is generally much shorter. A change from photoisomerization to

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

    Science.gov (United States)

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

    2001-01-01

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

  16. Charge-transfer energy in closed-shell ion-atom interactions. [for H and Li ions in He

    Science.gov (United States)

    Alvarez-Rizzatti, M.; Mason, E. A.

    1975-01-01

    The importance of charge-transfer energy in the interactions between closed-shell ions and atoms is investigated. Ab initio calculations on H(plus)-He and Li(plus)-He are used as a guide for the construction of approximate methods for the estimation of the charge-transfer energy for more complicated systems. For many alkali ion-rate gas systems the charge-transfer energy is comparable to the induction energy in the region of the potential minimum, although for doubly charged alkaline-earth ions in rare gases the induction energy always dominates. Surprisingly, an empirical combination of repulsion energy plus asymptotic induction energy plus asymptotic dispersion energy seems to give a fair representation of the total interaction, especially if the repulsion energy is parameterized, despite the omission of any explicit charge-transfer contribution. More refined interaction models should consider the charge-transfer energy contribution.

  17. Luminescent platinum complexes with terdentate ligands forming 6-membered chelate rings: advantageous and deleterious effects in N--N--N and N--C--N-coordinated complexes.

    Science.gov (United States)

    Garner, Katherine L; Parkes, Louise F; Piper, Jason D; Williams, J A Gareth

    2010-01-18

    Platinum(II) complexes of the form [PtL(n)Cl](+) are reported, containing the N--N--N-coordinating ligands 2,6-di(8-quinolyl)pyridine (L(1)), 2,6-di(8-quinolyl)-4-methoxypyridine (L(2)), or 2,6-di(7-aza-indolyl)-pyridine (L(3)). Metathesis of the chloride co-ligand in [PtL(1)Cl](+) can be accomplished under mild conditions, as exemplified by the formation of the complexes [PtL(1)OMe](+) and [PtL(1)(C[triple bond]C-tfp)](+), in which L(1) remains bound as a terdentate ligand {HC[triple bond]C-tfp = 3,5-bis(trifluoromethyl)-phenylacetylene}. An N--C--N-coordinated, cyclometalated analogue of [PtL(1)Cl](+) has also been prepared, namely, PtL(4)Cl where HL(4) is 1,3-di(8-quinolyl)benzene. The common feature among the six new complexes described here is that they contain 6-membered chelate rings, rather than the usual 5-membered rings that form when more common N--N--N ligands, such as 2,2':6',2''-terpyridine (tpy), bind to Pt(II). All the quinolyl-based complexes are phosphorescent in solution at room temperature, with quantum yields up to 4%. This contrasts with the well-established lack of emission from [Pt(tpy)Cl](+) under these conditions. Density functional theory calculations suggest that the improvement may stem, at least in part, from the relief of ring strain associated with the larger chelate ring size, leading to a more optimal bite angle at the metal, close to 180 degrees , and hence to a stronger ligand field. Consideration of the luminescence parameters, including data at 77 K, together with absorption and electrochemical data and the results of TD-DFT calculations, suggests that the lowest-lying singlet states have metal-to-ligand charge-transfer (MLCT) character, but that the triplet state from which emission occurs has more predominant ligand-centered character. The azaindolyl complex [PtL(3)Cl](+) is not emissive at room temperature, apparently owing to a particularly small radiative rate constant. The cyclometalated complex PtL(4)Cl emits at lower

  18. GW-BSE approach on S1 vertical transition energy of large charge transfer compounds: A performance assessment.

    Science.gov (United States)

    Ziaei, Vafa; Bredow, Thomas

    2016-11-07

    In this work, we apply many-body perturbation theory (MBPT) on large critical charge transfer (CT) complexes to assess its performance on the S1 excitation energy. Since the S1 energy of CT compounds is heavily dependent on the Hartree-Fock (HF) exchange fraction in the reference density functional, MBPT opens a new way for reliable prediction of CT S1 energy without explicit knowledge of suitable amount of HF-exchange, in contrary to the time-dependent density functional theory (TD-DFT), where depending on various functionals, large errors can arise. Thus, simply by starting from a (semi-)local reference functional and performing update of Kohn-Sham (KS) energies in the Green's function G while keeping dynamical screened interaction (W(ω)) frozen to the mean-field level, we obtain impressingly highly accurate S1 energy at slightly higher computational cost in comparison to TD-DFT. However, this energy-only updating mechanism in G fails to work if the initial guess contains a fraction or 100% HF-exchange, and hence considerably inaccurate S1 energy is predicted. Furthermore, eigenvalue updating both in G and W(ω) overshoots the S1 energy due to enhanced underscreening of W(ω), independent of the (hybrid-)DFT starting orbitals. A full energy-update on top of HF orbitals even further overestimates the S1 energy. An additional update of KS wave functions within the Quasi-Particle Self-Consistent GW (QSGW) deteriorates results, in stark contrast to the good results obtained from QSGW for periodic systems. For the sake of transferability, we further present data of small critical non-charge transfer systems, confirming the outcomes of the CT-systems.

  19. Charge transfer from 2-aminopurine radical cation and radical anion to nucleobases: A pulse radiolysis study

    Energy Technology Data Exchange (ETDEWEB)

    Manoj, P. [School of Chemical Sciences, Mahatma Gandhi University, Kottayam 686 560, Kerala (India); Mohan, H. [Radiation Chemistry and Chemical Dynamics Division, Bhabha Atomic Research Centre, Mumbai 400 085 (India); Mittal, J.P. [Radiation Chemistry and Chemical Dynamics Division, Bhabha Atomic Research Centre, Mumbai 400 085 (India); Manoj, V.M. [School of Chemical Sciences, Mahatma Gandhi University, Kottayam 686 560, Kerala (India); Aravindakumar, C.T. [School of Chemical Sciences, Mahatma Gandhi University, Kottayam 686 560, Kerala (India)], E-mail: CT-Aravindakumar@rocketmail.com

    2007-01-08

    Pulse radiolysis study has been carried out to investigate the properties of the radical cation of 2-aminopurine (2AP) and the probable charge transfer from the radical cation and radical anion of 2AP to natural nucleobases in aqueous medium. The radical cation of 2AP was produced by the reaction of sulfate radical anion (SO{sub 4}{sup dot-}). The time resolved absorption spectra obtained by the reaction of SO{sub 4}{sup dot-} with 2AP at neutral pH have two distinct maxima at 380 and 470nm and is assigned to the formation of a neutral radical of the form 2AP-N{sup 2}(-H){sup dot} (k{sub 2}=4.7x10{sup 9}dm{sup 3}mol{sup -1}s{sup -1} at pH 7). This neutral radical is formed from the deprotonation reaction of a very short-lived radical cation of 2AP. The transient absorption spectra recorded at pH 10.2 have two distinct maxima at 400 and 480nm and is assigned to the formation of a nitrogen centered radical (2AP-N(9){sup dot}). As the hole transport from 2AP to guanine is a highly probable process, the reaction of SO{sub 4}{sup dot-} is carried out in the presence of guanosine, adenosine and inosine. The spectrum obtained in the presence of guanosine was significantly different from that in the absence and it showed prominent absorption maxima at 380 and 470nm, and a weak broad maximum centered around 625nm which match well with the reported spectrum of a neutral guanine radical (G(-H){sup dot}). The electron transfer reaction from the radical anion of 2AP to thymine (T), cytidine (Cyd) and uridine (Urd) was also investigated at neutral pH. Among the three pyrimidines, only the transient spectrum in the presence of T gave a significant difference from the spectral features of the electron adduct of 2AP, which showed a prominent absorption maximum at 340nm and this spectrum is similar to the electron adduct spectrum of T. The preferential reduction of thymine by 2AP{sup dot-} and the oxidation of guanosine by 2AP{sup dot+} clearly follow the oxidation

  20. Development of a charge-transfer distribution model for stack simulation of solid oxide fuel cells

    Science.gov (United States)

    Onaka, H.; Iwai, H.; Kishimoto, M.; Saito, M.; Yoshida, H.; Brus, G.; Szmyd, J. S.

    2016-09-01

    An overpotential model for planar solid oxide fuel cells (SOFCs) is developed and applied to a stack numerical simulation. Charge-transfer distribution within the electrodes are approximated using an exponential function, based on which the Ohmic loss and activation overpotential are evaluated. The predicted current-voltage characteristics agree well with the experimental results, and also the overpotentials within the cell can reproduce the results obtained from a numerical analysis where the distribution of the charge-transfer current within the electrodes is fully solved. The proposed model is expected to be useful to maintain the accuracy of SOFC simulations when the cell components, consisting of anode, electrolyte and cathode, are simplified into one layer element.

  1. An Accurate and Linear Scaling Method to Calculate Charge-Transfer Excitation Energies and Diabatic Couplings

    CERN Document Server

    Pavanello, Michele; Visscher, Lucas; Neugebauer, Johannes

    2012-01-01

    Quantum--Mechanical methods that are both computationally fast and accurate are not yet available for electronic excitations having charge transfer character. In this work, we present a significant step forward towards this goal for those charge transfer excitations that take place between non-covalently bound molecules. In particular, we present a method that scales linearly with the number of non-covalently bound molecules in the system and is based on a two-pronged approach: The molecular electronic structure of broken-symmetry charge-localized states is obtained with the Frozen Density Embedding formulation of subsystem Density-Functional Theory; subsequently, in a post-SCF calculation, the full-electron Hamiltonian and overlap matrix elements among the charge-localized states are evaluated with an algorithm which takes full advantage of the subsystem DFT density partitioning technique. The method is benchmarked against Coupled-Cluster calculations and achieves chemical accuracy for the systems considered...

  2. Charge-transfer-directed radical substitution enables para-selective C-H functionalization

    Science.gov (United States)

    Boursalian, Gregory B.; Ham, Won Seok; Mazzotti, Anthony R.; Ritter, Tobias

    2016-08-01

    Efficient C-H functionalization requires selectivity for specific C-H bonds. Progress has been made for directed aromatic substitution reactions to achieve ortho and meta selectivity, but a general strategy for para-selective C-H functionalization has remained elusive. Herein we introduce a previously unappreciated concept that enables nearly complete para selectivity. We propose that radicals with high electron affinity elicit arene-to-radical charge transfer in the transition state of radical addition, which is the factor primarily responsible for high positional selectivity. We demonstrate with a simple theoretical tool that the selectivity is predictable and show the utility of the concept through a direct synthesis of aryl piperazines. Our results contradict the notion, widely held by organic chemists, that radical aromatic substitution reactions are inherently unselective. The concept of radical substitution directed by charge transfer could serve as the basis for the development of new, highly selective C-H functionalization reactions.

  3. A comparison of various surface charge transfer hole doping of graphene grown by chemical vapour deposition

    Science.gov (United States)

    Chandramohan, S.; Seo, Tae Hoon; Janardhanam, V.; Hong, Chang-Hee; Suh, Eun-Kyung

    2017-10-01

    Charge transfer doping is a renowned route to modify the electrical and electronic properties of graphene. Understanding the stability of potentially important charge-transfer materials for graphene doping is a crucial first step. Here we present a systematic comparison on the doping efficiency and stability of single layer graphene using molybdenum trioxide (MoO3), gold chloride (AuCl3), and bis(trifluoromethanesulfonyl)amide (TFSA). Chemical dopants proved to be very effective, but MoO3 offers better thermal stability and device fabrication compatibility. Single layer graphene films with sheet resistance values between 100 and 200 ohm/square were consistently produced by implementing a two-step growth followed by doping without compromising the optical transmittance.

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

    Science.gov (United States)

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

    2013-10-14

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

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

    DEFF Research Database (Denmark)

    Sherafatipour, Golenaz; Benduhn, Johannes; Spoltore, Donato

    -acceptor interface via delocalized charge-transfer (CT) states, which represents an intermediate state between the exciton dissociation and recombination back to the ground state. In this work we perform the electroluminescence (EL) created by bimolecular free career recombination and sensitive external quantum....... Electroluminescence from charge transfer states in polymer solar cells. J. Am. Chem. Soc. 131, 11819–11824 (2009)....... efficiency measurements (sEQE) in DBP:C70 based SCs as a less studied system in order to study the energy and effect of CT states on degradation of the devices2. The results from these measurements reveal valuable information about the loss mechanism during the aging experiment as well as the energy...

  6. Combining intra- and intermolecular charge-transfer: a new strategy towards molecular ferromagnets and multiferroics.

    Science.gov (United States)

    Di Maiolo, Francesco; Sissa, Cristina; Painelli, Anna

    2016-01-21

    Organic ferroelectric materials are currently a hot research topic, with mixed stack charge transfer crystals playing a prominent role with their large, electronic-in-origin polarization and the possibility to tune the transition temperature down to the quantum limit and/or to drive the ferroelectric transition via an optical stimulus. By contrast, and in spite of an impressive research effort, organic ferromagnets are rare and characterized by very low transition temperatures. Coexisting magnetic and electric orders in multiferroics offer the possibility to control magnetic (electric) properties by an applied electric (magnetic) field with impressive technological potential. Only few examples of multiferroics are known today, based on inorganics materials. Here we demonstrate that, by decorating mixed stack charge transfer crystals with organic radicals, a new family of robust molecular ferromagnets can be designed, stable up to ambient temperature, and with a clear tendency towards multiferroic behaviour.

  7. Multicolour Emission States from Charge Transfer between Carbon Dots and Surface Molecules

    Directory of Open Access Journals (Sweden)

    Shengliang Hu

    2017-02-01

    Full Text Available The emissive states of carbon dots have been tuned by controlling the charge transfer process. The carbon dots couple with molecules, which are made of a benzene ring and different heteroatom substituents, through amino-carboxylic bonds that are generally identified as charge transfer promoters at the interface. New ways of radiative recombination are created due to the transfer of photo-excited electrons from carbon dots to the lowest unoccupied molecular orbital (LUMO of the grafted molecules. By variation of the molecular orbital energy levels via heteroatom substituents in the benzene ring, the different optical properties and emission colors of the carbon dots were presented. This work opens up new opportunities for the application of carbon dots since different heteroatom substituents could lead to many possibilities for conjugation with drugs and biomolecules.

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

    Science.gov (United States)

    Kwong, Victor H. S.

    1997-01-01

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

  9. Photodissociation and charge transfer dynamics of negative ions studied with femtosecond photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Zanni, Martin Thomas [Univ. of California, Berkeley, CA (United States)

    1999-12-01

    This dissertation presents studies aimed at understanding the potential energy surfaces and dynamics of isolated negative ions, and the effects of solvent on each. Although negative ions play important roles in atmospheric and solution phase chemistry, to a large extent the ground and excited state potential energy surfaces of gas phase negative ions are poorly characterized, and solvent effects even less well understood. In an effort to fill this gap, the author's coworkers and the author have developed a new technique, anion femtosecond photoelectron spectroscopy, and applied it to gas phase photodissociation and charge transfer processes. Studies are presented that (1) characterize the ground and excited states of isolated and clustered anions, (2) monitor the photodissociation dynamics of isolated and clustered anions, and (3) explore the charge-transfer-to-solvent states of atomic iodide clustered with polar and non-polar solvents.

  10. Dual Fluorescence in GFP Chromophore Analogues: Chemical Modulation of Charge Transfer and Proton Transfer Bands.

    Science.gov (United States)

    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.

  11. Photodissociation and charge transfer dynamics of negative ions studied with femtosecond photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Zanni, Martin T.

    1999-12-17

    This dissertation presents studies aimed at understanding the potential energy surfaces and dynamics of isolated negative ions, and the effects of solvent on each. Although negative ions play important roles in atmospheric and solution phase chemistry, to a large extent the ground and excited state potential energy surfaces of gas phase negative ions are poorly characterized, and solvent effects even less well understood. In an effort to fill this gap, the author's coworkers and the author have developed a new technique, anion femtosecond photoelectron spectroscopy, and applied it to gas phase photodissociation and charge transfer processes. Studies are presented that (1) characterize the ground and excited states of isolated and clustered anions, (2) monitor the photodissociation dynamics of isolated and clustered anions, and (3) explore the charge-transfer-to-solvent states of atomic iodide clustered with polar and non-polar solvents.

  12. Crater Formation on Electrodes during Charge Transfer with Aqueous Droplets or Solid Particles

    Science.gov (United States)

    Elton, E. S.; Rosenberg, E. R.; Ristenpart, W. D.

    2017-09-01

    We report that metallic electrodes are physically pitted during charge transfer events with water droplets or other conductive objects moving in strong electric fields (>1 kV /cm ). Post situ microscopic inspection of the electrode shows that an individual charge transfer event yields a crater approximately 1-3 μ m wide, often with features similar to a splash corona. We interpret the crater formation in terms of localized melting of the electrode via resistive heating concurrent with dielectric breakdown through the surrounding insulating fluid. A scaling analysis indicates that the crater diameter scales as the inverse cube root of the melting point temperature Tm of the metal, in accord with measurements on several metals (660 °C ≤Tm≤3414 °C ). The process of crater formation provides a possible explanation for the longstanding difficulty in quantitatively corroborating Maxwell's prediction for the amount of charge acquired by spheres contacting a planar electrode.

  13. Isotope effect in charge-transfer collisions of H with He{sup +}

    Energy Technology Data Exchange (ETDEWEB)

    Loreau, J.; Dalgarno, A. [Institute for Theoretical Atomic, Molecular and Optical Physics, Harvard-Smithsonian Center for Astrophysics, Cambridge, Massachusetts 02138 (United States); Ryabchenko, S. [Northern (Arctic) Federal University, 17 Severnaya Dvina Emb., 163002 Arkhangelsk (Russian Federation); Laboratoire de Chimie Quantique et Photophysique, Universite Libre de Bruxelles (ULB), CP160/09, 1050 Bruxelles (Belgium); Vaeck, N. [Laboratoire de Chimie Quantique et Photophysique, Universite Libre de Bruxelles (ULB), CP160/09, 1050 Bruxelles (Belgium)

    2011-11-15

    We present a theoretical study of the isotope effect arising from the replacement of H by T in the charge-transfer collision H(n=2) + He{sup +}(1s) at low energy. Using a quasimolecular approach and a time-dependent wave-packet method, we compute the cross sections for the reaction including the effects of the nonadiabatic radial and rotational couplings. For H(2s) + He{sup +}(1s) collisions, we find a strong isotope effect at energies below 1 eV/amu for both singlet and triplet states. We find a much smaller isotopic dependence of the cross section for H(2p) + He{sup +}(1s) collisions in triplet states, and no isotope effect in singlet states. We explain the isotope effect on the basis of the potential energy curves and the nonadiabatic couplings, and we evaluate the importance of the isotope effect on the charge-transfer rate coefficients.

  14. Bio-batteries and bio-fuel cells: leveraging on electronic charge transfer proteins.

    Science.gov (United States)

    Kannan, A M; Renugopalakrishnan, V; Filipek, S; Li, P; Audette, G F; Munukutla, L

    2009-03-01

    Bio-fuel cells are alternative energy devises based on bio-electrocatalysis of natural substrates by enzymes or microorganisms. Here we review bio-fuel cells and bio-batteries based on the recent literature. In general, the bio-fuel cells are classified based on the type of electron transfer; mediated electron transfer and direct electron transfer or electronic charge transfer (ECT). The ECT of the bio-fuel cells is critically reviewed and a variety of possible applications are considered. The technical challenges of the bio-fuel cells, like bioelectrocatalysis, immobilization of bioelectrocatalysts, protein denaturation etc. are highlighted and future research directions are discussed leveraging on the use of electron charge transfer proteins. In addition, the packaging aspects of the bio-fuel cells are also analyzed and the found that relatively little work has been done in the engineering development of bio-fuel cells.

  15. Non-Linearity in Wide Dynamic Range CMOS Image Sensors Utilizing a Partial Charge Transfer Technique

    Directory of Open Access Journals (Sweden)

    Izhal Abdul Halin

    2009-11-01

    Full Text Available The partial charge transfer technique can expand the dynamic range of a CMOS image sensor by synthesizing two types of signal, namely the long and short accumulation time signals. However the short accumulation time signal obtained from partial transfer operation suffers of non-linearity with respect to the incident light. In this paper, an analysis of the non-linearity in partial charge transfer technique has been carried, and the relationship between dynamic range and the non-linearity is studied. The results show that the non-linearity is caused by two factors, namely the current diffusion, which has an exponential relation with the potential barrier, and the initial condition of photodiodes in which it shows that the error in the high illumination region increases as the ratio of the long to the short accumulation time raises. Moreover, the increment of the saturation level of photodiodes also increases the error in the high illumination region.

  16. Non-Linearity in Wide Dynamic Range CMOS Image Sensors Utilizing a Partial Charge Transfer Technique

    Science.gov (United States)

    Shafie, Suhaidi; Kawahito, Shoji; Halin, Izhal Abdul; Hasan, Wan Zuha Wan

    2009-01-01

    The partial charge transfer technique can expand the dynamic range of a CMOS image sensor by synthesizing two types of signal, namely the long and short accumulation time signals. However the short accumulation time signal obtained from partial transfer operation suffers of non-linearity with respect to the incident light. In this paper, an analysis of the non-linearity in partial charge transfer technique has been carried, and the relationship between dynamic range and the non-linearity is studied. The results show that the non-linearity is caused by two factors, namely the current diffusion, which has an exponential relation with the potential barrier, and the initial condition of photodiodes in which it shows that the error in the high illumination region increases as the ratio of the long to the short accumulation time raises. Moreover, the increment of the saturation level of photodiodes also increases the error in the high illumination region. PMID:22303133

  17. Energy and Charge Transfer from Guest to Host in Doped Organic Electroluminescent Devices

    Institute of Scientific and Technical Information of China (English)

    李宏建; 彭景翠; 许雪梅; 瞿述; 罗小华; 赵楚军

    2002-01-01

    The luminescence properties of doped organic electroluminescent devices are explained by means off Hamiltonian model. The results show that there is a corresponding relation between the amount of transferred charge and the change of the energy originating from charge transfer, and the relation can be influenced by dopant concentration.As the amount of transferred charge increases, the total energy decreases and the luminescence intensity increases.Therefore, we deduce that the energy transfer from guest to host may be derived from the charge transfer. For a given organic electroluminescent device, the maximum value of the conductivity can be observed in a specific dopant concentration. The calculated results show that the greater the transferred charges, the higher the conductivities in doped organic electroluminescent devices. The results agree basically with experimental results.

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

    Science.gov (United States)

    Sun, Baichuan; Barnard, Amanda S.

    2016-07-01

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

  19. Charge-transfer gap closure in transition-metal halides under pressure

    Energy Technology Data Exchange (ETDEWEB)

    Chen, A.L.; Yu, P.Y.

    1995-01-01

    Insulator-to-metal transition induced by pressure has been studied in three transition metal iodides: NiI{sub 2}, CoI{sub 2} and FeI{sub 2} using optical absorption and resistivity measurements at room temperature. Comparisons between the results obtained by these two techniques suggested that the closure of the charge-transfer gap is the principal mechanism responsible for the insulator-to-metal transition in these materials.

  20. First-principles study of the interaction and charge transfer between graphene and metals

    OpenAIRE

    Khomyakov, P.A.; Giovannetti, G.; Rusu, P. C.; Brocks, G.; Brink, J.G.J. van den; Kelly, P. J.

    2009-01-01

    Measuring the transport of electrons through a graphene sheet necessarily involves contacting it with metal electrodes. We study the adsorption of graphene on metal substrates using first-principles calculations at the level of density functional theory. The bonding of graphene to Al, Ag, Cu, Au and Pt(111) surfaces is so weak that its unique "ultrarelativistic" electronic structure is preserved. The interaction does, however, lead to a charge transfer that shifts the Fermi level by up to 0.5...

  1. Imidazole as a parent π-conjugated backbone in charge-transfer chromophores

    Directory of Open Access Journals (Sweden)

    Jiří Kulhánek

    2012-01-01

    Full Text Available Research activities in the field of imidazole-derived push–pull systems featuring intramolecular charge transfer (ICT are reviewed. Design, synthetic pathways, linear and nonlinear optical properties, electrochemistry, structure–property relationships, and the prospective application of such D-π-A organic materials are described. This review focuses on Y-shaped imidazoles, bi- and diimidazoles, benzimidazoles, bis(benzimidazoles, imidazole-4,5-dicarbonitriles, and imidazole-derived chromophores chemically bound to a polymer chain.

  2. An experimental and computational study on intramolecular charge transfer: a tetrathiafulvalene-fused dipyridophenazine molecule.

    Science.gov (United States)

    Jia, Chunyang; Liu, Shi-Xia; Tanner, Christian; Leiggener, Claudia; Neels, Antonia; Sanguinet, Lionel; Levillain, Eric; Leutwyler, Samuel; Hauser, Andreas; Decurtins, Silvio

    2007-01-01

    To study the electronic interactions in donor-acceptor (D-A) ensembles, D and A fragments are coupled in a single molecule. Specifically, a tetrathiafulvalene (TTF)-fused dipyrido[3,2-a:2',3'-c]phenazine (dppz) compound having inherent redox centers has been synthesized and structurally characterized. Its electronic absorption, fluorescence emission, photoinduced intramolecular charge transfer, and electrochemical behavior have been investigated. The observed electronic properties are explained on the basis of density functional theory.

  3. Coarse-Grained Theory of Biological Charge Transfer with Spatially and Temporally Correlated Noise.

    Science.gov (United States)

    Liu, Chaoren; Beratan, David N; Zhang, Peng

    2016-04-21

    System-environment interactions are essential in determining charge-transfer (CT) rates and mechanisms. We developed a computationally accessible method, suitable to simulate CT in flexible molecules (i.e., DNA) with hundreds of sites, where the system-environment interactions are explicitly treated with numerical noise modeling of time-dependent site energies and couplings. The properties of the noise are tunable, providing us a flexible tool to investigate the detailed effects of correlated thermal fluctuations on CT mechanisms. The noise is parametrizable by molecular simulation and quantum calculation results of specific molecular systems, giving us better molecular resolution in simulating the system-environment interactions than sampling fluctuations from generic spectral density functions. The spatially correlated thermal fluctuations among different sites are naturally built-in in our method but are not readily incorporated using approximate spectral densities. Our method has quantitative accuracy in systems with small redox potential differences (charge-transfer rates; however, in a system of units with different site energies, spatial correlations slow the fluctuations to bring units into degeneracy, in turn, slowing the charge-transfer rates. The spatial and temporal correlations of condensed phase medium fluctuations provide another source to control and tune the kinetics and dynamics of charge-transfer systems.

  4. Strongly Dichroic Organic Films via Controlled Assembly of Modular Aromatic Charge-Transfer Liquid Crystals.

    Science.gov (United States)

    Bé, Ariana Gray; Tran, Cheryl; Sechrist, Riley; Reczek, Joseph J

    2015-10-02

    The formation of highly anisotropic organic thin films based on the designed self-assembly of mixed-stack liquid crystals is reported. A series of alkoxyanthracene donors is combined in a modular fashion with a naphthalenediimide acceptor to generate new charge-transfer columnar liquid crystals. Materials characterization and molecular modeling provides insight into structure-function relationships in these organic materials that lead to the striking bulk dichroic properties of certain molecular assemblies.

  5. Modulating Charge Transfer Through Cyclic D,L α-Peptide Self-Assembly

    OpenAIRE

    Horne, W. Seth; Ashkenasy, Nurit; Ghadiri, M. Reza

    2005-01-01

    We describe a concise solid support-based synthetic method for the preparation of cyclic D,L α-peptides bearing 1,4,5,8-naphthalenetetracarboxylic diimide (NDI) side chains. Studies of the structural and photoluminescence properties of these molecules in solution show that the hydrogen bond directed self-assembly of the cyclic D,L α-peptide backbone promotes intermolecular NDI excimer formation. The efficiency of NDI charge transfer in the resulting supramolecular assemblies is shown to depen...

  6. Swelling/syneresis phenomena in gel-forming interpolymer complexes.

    Science.gov (United States)

    Bell, C L; Peppas, N A

    1996-01-01

    Grafted poly(methacrylic acid-g-ethylene glycol) (P(MAA-g-EG)) copolymers were synthesized and their pH sensitivity investigated as a function of copolymer composition and PEG graft molecular weight. Interpolymer complexation occurred by hydrogen bonding between carboxylic groups on poly(methacrylic acid) (PMAA) and ether groups on poly(ethylene glycol) (PEG). This complexation was sensitive to the surrounding environment as complexes formed at pH levels low enough to insure substantial protonation of PMAA acid groups. At high pH, the acid groups became neutralized and did not form complexes. P(MAA-g-EG) membranes showed pH-sensitivity due to complex formation and dissociation. Uncomplexed equilibrium swelling ratios were much higher than those of the complexed states and varied according to copolymer composition and PEG graft length. Mesh sizes in the two states were determined. Swelling under oscillatory pH conditions and constant ionic strength revealed the dynamic sensitivity of P(MAA-g-EG) membranes. Under changing pH conditions, network syneresis (complexation) occurred more rapidly than network expansion (decomplexation) because of the rates of diffusion of specific ions causing the responses. No distinct water fronts were observed. Instead, water transport was continuous through the gel. These gels show great promise for a number of biomedical applications where fast biomaterial response is necessary.

  7. A two-dimensional position sensitive gas chamber with scanned charge transfer readout

    Energy Technology Data Exchange (ETDEWEB)

    Gomez, F. E-mail: faustgr@usc.es; Iglesias, A.; Lobato, R.; Mosquera, J.; Pardo, J.; Pena, J.; Pazos, A.; Pombar, M.; Rodriguez, A

    2003-10-21

    We have constructed and tested a two-dimensional position sensitive parallel-plate gas ionization chamber with scanned charge transfer readout. The scan readout method described here is based on the development of a new position-dependent charge transfer technique. It has been implemented by using gate strips perpendicularly oriented to the collector strips. This solution reduces considerably the number of electronic readout channels needed to cover large detector areas. The use of a 25 {mu}m thick kapton etched circuit allows high charge transfer efficiency with a low gating voltage, consequently needing a very simple commutating circuit. The present prototype covers 8x8 cm{sup 2} with a pixel size of 1.27x1.27 mm{sup 2}. Depending on the intended use and beam characteristics a smaller effective pixel is feasible and larger active areas are possible. This detector can be used for X-ray or other continuous beam intensity profile monitoring.

  8. Rate limiting activity of charge transfer during lithiation from ionic liquids

    Science.gov (United States)

    Rodrigues, Marco-Tulio F.; Lin, Xinrong; Gullapalli, Hemtej; Grinstaff, Mark W.; Ajayan, Pulickel M.

    2016-10-01

    Given the increased use of room temperature ionic liquid electrolytes in Li-ion batteries, due to their non-flammability and negligible volatility, this study evaluates the lithiation kinetics to understand and improve the rate performance of Li-ion batteries. Lithium titanate spinel is used as a model electrode and the electrolyte is composed of LiTFSI and TFSI-coordinated alkoxy-modified phosphonium ionic liquid. Based on the analysis of activation energies for each process, we report that the charge-transfer reaction at the electrode/electrolyte interface is the rate-limiting step for cell operation. This finding is further supported by the observation that a 50-fold decrease in charge-transfer resistance at higher temperatures leads to a significant performance improvement over that of a traditional organic electrolyte at room temperature. Charge-transfer resistance and electrolyte wetting on the electrode surface are critical processes for optimal battery performance, and such processes need to be included when designing new ionic liquids in order to exceed the power density obtained with the use of current carbonate-based electrolytes.

  9. Communication: Modeling of concentration dependent water diffusivity in ionic solutions: Role of intermolecular charge transfer.

    Science.gov (United States)

    Yao, Yi; Berkowitz, Max L; Kanai, Yosuke

    2015-12-28

    The translational diffusivity of water in solutions of alkali halide salts depends on the identity of ions, exhibiting dramatically different behavior even in solutions of similar salts of NaCl and KCl. The water diffusion coefficient decreases as the salt concentration increases in NaCl. Yet, in KCl solution, it slightly increases and remains above bulk value as salt concentration increases. Previous classical molecular dynamics simulations have failed to describe this important behavior even when polarizable models were used. Here, we show that inclusion of dynamical charge transfer among water molecules produces results in a quantitative agreement with experiments. Our results indicate that the concentration-dependent diffusivity reflects the importance of many-body effects among the water molecules in aqueous ionic solutions. Comparison with quantum mechanical calculations shows that a heterogeneous and extended distribution of charges on water molecules around the ions due to ion-water and also water-water charge transfer plays a very important role in controlling water diffusivity. Explicit inclusion of the charge transfer allows us to model accurately the difference in the concentration-dependent water diffusivity between Na(+) and K(+) ions in simulations, and it is likely to impact modeling of a wide range of systems for medical and technological applications.

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

    Science.gov (United States)

    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.

  11. Ultrafast intramolecular charge transfer of formyl perylene observed using femtosecond transient absorption spectroscopy.

    Science.gov (United States)

    Mohammed, Omar F

    2010-11-04

    The excited-state photophysics of formylperylene (FPe) have been investigated in a series of nonpolar, polar aprotic, and polar protic solvents. A variety of experimental and theoretical methods were employed including femtosecond transient absorption (fs-TA) spectroscopy with 130 fs temporal resolution. We report that the ultrafast intramolecular charge transfer from the perylene unit to the formyl (CHO) group can be facilitated drastically by hydrogen-bonding interactions between the carbonyl group oxygen of FPe and hydrogen-donating solvents in the electronically excited state. The excited-state absorption of FPe in methanol (MeOH) is close to the reported perylene radical cation produced by bimolecular quenching by an electron acceptor. This is a strong indication for a substantial charge transfer in the S(1) state in protic solvents. The larger increase of the dipole moment change in the protic solvents than that in aprotic ones strongly supports this observation. Relaxation mechanisms including vibrational cooling and solvation coupled to the charge-transfer state are also discussed.

  12. Ab initio calculation of H + He$^+$ charge transfer cross sections for plasma physics

    CERN Document Server

    Loreau, J; Lauvergnat, D; Desouter-Lecomte, M; Vaeck, N

    2010-01-01

    The charge transfer in low energy (0.25 to 150 eV/amu) H($nl$) + He$^+(1s)$ collisions is investigated using a quasi-molecular approach for the $n=2,3$ as well as the first two $n=4$ singlet states. The diabatic potential energy curves of the HeH$^+$ molecular ion are obtained from the adiabatic potential energy curves and the non-adiabatic radial coupling matrix elements using a two-by-two diabatization method, and a time-dependent wave-packet approach is used to calculate the state-to-state cross sections. We find a strong dependence of the charge transfer cross section in the principal and orbital quantum numbers $n$ and $l$ of the initial or final state. We estimate the effect of the non-adiabatic rotational couplings, which is found to be important even at energies below 1 eV/amu. However, the effect is small on the total cross sections at energies below 10 eV/amu. We observe that to calculate charge transfer cross sections in a $n$ manifold, it is only necessary to include states with $n^{\\prime}\\leq n$...

  13. N+ charge transfer and N+2 dissociation in N2 at swarm energies.

    Science.gov (United States)

    Basurto, E; de Urquijo, J; Cisneros, C; Alvarez, I

    2001-01-01

    This paper reports a drift-tube-mass-spectrometer measurement of the relative abundances of N+ and N+2 in pure nitrogen, over a ratio of electric field to gas density, E/N, from 800 to 7200 Td [1 townsend (Td)=10(-17) V cm(2)]. A proposed charge transfer dissociation scheme between the above two ions and N2 allowed us to obtain spatial rate coefficients for charge transfer and dissociation over the E/N range 800-2800 Td. Using previously measured cross sections for the above processes, and assuming a Maxwellian distribution of ion velocities, we calculated the reaction coefficients, which were found to be in good agreement with our measured values. In particular, the present results support the trend toward fairly high charge transfer cross section values for N+ energies above 10 eV. In the overlap range between 2.4 and 7.2 kTd, our concentration ratio [N(+)/N(+)(2)] is about five times smaller than that measured previously from a diffuse Townsend discharge in which electron impact is involved in addition to N+2 collisional dissociation with N2, but has the same trend. Thus it seems that, besides N+2 dissociation by electron impact, collisional dissociation becomes important at elevated values of E/N. In connection with previous discharge work in nitrogen, the present study may help explain the enhanced cathode yields observed.

  14. Simplified charge transfer inefficiency correction in CCDs by trap-pumping

    Science.gov (United States)

    Gow, Jason P. D.; Murray, Neil J.

    2016-08-01

    A major concern when using Charge-Coupled Devices in hostile radiation environments is radiation induced Charge Transfer Inefficiency. The displacement damage from non-ionising radiation incident on the detector creates defects within the silicon lattice, these defects can capture and hold charge for a period of time dependent on the operating temperature and the type of defect, or "trap species". The location and type of defect can be determined to a high degree of precision using the trap-pumping technique, whereby background charges are input and then shuffled forwards and backwards between pixels many times and repeated using different transfer timings to promote resonant charge-pumping at particular defect sites. Where the charge transfer timings used in the trap-pumping process are equivalent to the nominal CCD readout modes, a simple "trap-map" of the defects that will most likely contribute to charge transfer inefficiency in the CCD array can be quickly generated. This paper describes a concept for how such a "trap-map" can be used to correct images subject to non-ionising radiation damage and provides initial results from an analytical algorithm and our recommendations for future developments.

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

    Science.gov (United States)

    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.

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

    Directory of Open Access Journals (Sweden)

    Andrius VASILIAUSKAS

    2011-03-01

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

  17. Differentiating morphology, form, and meaning: neural correlates of morphological complexity.

    Science.gov (United States)

    Bozic, Mirjana; Marslen-Wilson, William D; Stamatakis, Emmanuel A; Davis, Matthew H; Tyler, Lorraine K

    2007-09-01

    The role of morphological structure in word recognition raises issues about the nature and structure of the language system. One major issue is whether morphological factors provide an independent principle for lexical organization and processing, or whether morphological effects can be reduced to the joint contribution of form and meaning. The independence of form, meaning, and morphological structure can be directly investigated using derivationally complex words, because derived words can share form but need not share meaning (e.g., archer-arch). We used an event-related functional magnetic resonance imaging paradigm to investigate priming between pairs of words that potentially shared a stem, where this link was either semantically transparent (e.g., bravely-brave) or opaque (e.g., archer-arch). These morphologically related pairs were contrasted with identity priming (e.g., mist-mist) and priming for pairs of words that shared only form (e.g., scandal-scan) or meaning (e.g., accuse-blame). Morphologically related words produced significantly reduced activation in left frontal regions, whether the pairs were semantically transparent or opaque. The effect was not found for any of the control conditions (identity, form, or meaning). Morphological effects were observed separately from processing form and meaning and we propose that they reflect segmentation of complex derived words, a process triggered by surface morphological structure of complex words.

  18. Utility of 7,7,8,8-tetracyanoquinodimethane charge transfer reagent for the spectrophotometric determination of trazodone, amineptine and amitriptyline hydrochlorides

    Science.gov (United States)

    Mohamed, Gehad G.; El-Dien, Faten A. F. Nour; Mohamed, Nehad A.

    2007-12-01

    A simple and rapid spectrophotometric method has been developed for the determination of tricyclic anti-depressant drugs such as trazodone (TZH), amineptine (APH) and amitriptyline (ATPH) hydrochlorides in pure form and in different pharmaceutical preparations. The charge transfer (CT) reaction between TZH, APH and ATPH as electron donors and TCNQ as electron acceptor was utilized for their spectrophotometric determination. The optimum experimental conditions, like time, temperature, stoichiometry, solvents, for the CT complex formation are established. The method permits the determination of TZH, APH and ATPH over a concentration range of 10-400, 10-440 and 10-300 μg ml -1, respectively. The sensitivity ( S) is found to be 0.09, 0.087 and 0.069 g cm -2 for TZH, APH and ATPH, respectively. The SD values are found to be 0.146-0.293, 0.154-0.285 and 0.091-0.212 and RSD values are 0.142-1.92, 0.297-1.92 and 0.212-0.915 for TZH, APH and ATPH, respectively. The low values of the relative standard deviation indicate the high accuracy and precision of the method. The mean recovery values obtained together with a high correlation coefficient values, amount in the range 98-101.5, 98.7-102.9 and 93-101.9 for TZH, APH and ATPH, respectively. The method is applicable for the assay of the investigated drugs in different dosage forms and the results are in good agreement with those obtained by the official method.

  19. Charge-transfer (CT) orbitals for the one-electron description of CT excitations in a wide range of donor-acceptor separations

    Science.gov (United States)

    Gritsenko, O. V.

    2017-01-01

    A transformation of the virtual Kohn-Sham orbitals is proposed to a set of charge-transfer orbitals (CTOs) adapted to description of CT excitations. The CTO scheme offers a simple estimate of the CT excitation energy with an orbital energy difference. This estimate reproduces well the reference values of the configuration interaction (CI) method in a wide range of donor-acceptor separations in the paradigmatic He -Be complex. CTO-based orbital energy and shape indices are proposed to assess the suitability of the CT description with virtual orbitals of a given basis set. Both indices yield correct trends for the Kohn-Sham and Hartree-Fock orbitals.

  20. Strategic directions of personnel potential forming of a building complex

    Directory of Open Access Journals (Sweden)

    Simonova Marina

    2016-01-01

    Full Text Available The analysis of directions of strategic approach forming of labor potential management of a building complex is carried out in this paper. On the basis of this analysis the system of actions for strategy forming divided into consecutive stages is offered. The development of the personnel forecast is a strategic planning basis. One of personnel forecast variants is the correlation of needs estimates in personnel of a building complex with available allowances. On the basis of the personnel forecast strategic analysis it is possible to compose working programs for the stated goals of implementation. Operational assessment of personnel requirements of a building complex is proved to be combined with strategic objectives. Some assessment approaches to qualitative and quantitative need for specialists of a building complex are offered. The fact that high-quality labor power supply system of a building complex with should be based on industry development forecast and increase in construction products competitiveness is revealed in the article. Strategic management priority will allow to react immediately to the current situation changes, to introduce amendments both into tactical, and operational management.

  1. Structure of Block Copolymer Hydrogel Formed by Complex Coacervate Process

    Science.gov (United States)

    Choi, Soohyung; Ortony, Julia; Krogstad, Daniel; Spruell, Jason; Lynd, Nathaniel; Han, Songi; Kramer, Edward

    2012-02-01

    Complex coacervation occurs when oppositely charged polyelectrolytes associate in solution, forming dense micron-sized droplets. Hydrogels with coacervate block domains were formed by mixing two ABA and A'BA' triblock copolymer solutions in water where the A and A' blocks are oppositely charged. Small-angle neutron scattering (SANS) was used to investigate the structure of hydrogels formed by ABA triblock copolymers (A block: poly(allyl glycidyl ether) functionalized with guanidinium (A) or sulfonate (A'), B block: poly(ethylene oxide)). By using an appropriate fitting model, structural information such as coacervate core block radius and water volume fraction w can be extracted from SANS data. The results reveal that w in the coacervate core block was significantly higher than in conventional triblock copolymer hydrogels where microphase separation is driven by the hydrophobicity of the core-forming blocks.

  2. Determination of individual proton affinities of ofloxacin from its UV-Vis absorption, fluorescence and charge-transfer spectra: effect of inclusion in beta-cyclodextrin on the proton affinities.

    Science.gov (United States)

    Ghosh, Bankim Chandra; Deb, Nipamanjari; Mukherjee, Asok K

    2010-08-01

    Individual proton affinities of the four dissociable functional groups of (+/-)-9-fluoro-2,3-dihydro-3-methyl-10-(4-methyl-1-piperazinyl)-7-oxo-7H-pyrido[1,2,3-de]-1,4-benzoxazine-6-carboxylic acid (commonly called "ofloxacin" and to be denoted henceforth as OflH), have been determined from the pH-dependent variation of the UV-vis absorption and fluorescence spectra of the compound itself and of its charge transfer complexes (CT) with p-bromanil and p-chloranil (in aqueous medium containing 0.1% ethanol, v/v). To utilize the CT spectra for determination of the proton affinity of the anilinic N, the CT absorption band of the ofloxacin-p-bromanil complex has been studied by changing the pH of the medium. Further, the effect of inclusion on the proton affinities of the four dissociable groups of OflH has been studied in presence of beta-cyclodextrin (beta-CD). Two pK(a) values corresponding to anilinic and tertiary N atoms change, whereas those corresponding to phenolic -OH and aromatic -COOH groups remain unchanged by the addition of beta-CD, a fact that indicates partial inclusion of the ofloxacin molecule in beta-CD. Formation constant and related thermodynamic parameters for the OflH(2)(+).beta-CD inclusion complex in aqueous solution have been determined from absorption intensities. A general relation between pK(a) values of guests having proton-releasing functional groups and formation constants of the inclusion complexes of the protonated and deprotonated forms with a host molecule has been utilized for determination of the formation constant of the OflH(3)(+2).beta-CD complex from the pK(a) values of OflH(3)(+2) in the presence and absence of beta-CD, along with the formation constant of the OflH(2)(+).beta-CD complex. Results of the present study reveal that the N-methylpiperazinyl moiety of ofloxacin is included in beta-CD, and the remaining part of the guest molecule remains outside. Also, in molecular interaction with quinone-type electron acceptors

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

    Science.gov (United States)

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

    2016-12-01

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

  4. Donor-to-Donor vs Donor-to-Acceptor Interfacial Charge Transfer States in the Phthalocyanine-Fullerene Organic Photovoltaic System.

    Science.gov (United States)

    Lee, Myeong H; Dunietz, Barry D; Geva, Eitan

    2014-11-06

    Charge transfer (CT) states formed at the donor/acceptor heterointerface are key for photocurrent generation in organic photovoltaics (OPV). Our calculations show that interfacial donor-to-donor CT states in the phthalocyanine-fullerene OPV system may be more stable than donor-to-acceptor CT states and that they may rapidly recombine, thereby constituting a potentially critical and thus far overlooked loss mechanism. Our results provide new insight into processes that may compete with charge separation, and suggest that the efficiency for charge separation may be improved by destabilizing donor-to-donor CT states or decoupling them from other states.

  5. Studies on the interfacial charge transfer processes of nanocrystalline CdSe thin film electrodes by intensity modulated photocurrent spectroscopy

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Interfacial charge transfer kinetics of the nanocrystalline CdSe thin film electrodes have been studied in sodium polysulfide solutions by intensity modulated photocurrent spectroscopy (IMPS). The interfacial direct and indirect charge transfer and recombination processes were analyzed in terms of the parameters: normalized steady state photocurrents and surface state lifetimes obtained by measuring the IMPS responses under different applied potentials and different solution concentrations. IMPS responses of polycrystalline CdSe thin film electrodes were also presented for comparison.

  6. Charge-transfer-to-solvent reactions from I(-) to water, methanol, and ethanol studied by time-resolved photoelectron spectroscopy of liquids.

    Science.gov (United States)

    Okuyama, Haruki; Suzuki, Yoshi-Ichi; Karashima, Shutaro; Suzuki, Toshinori

    2016-08-21

    The charge-transfer-to-solvent (CTTS) reactions from iodide (I(-)) to H2O, D2O, methanol, and ethanol were studied by time-resolved photoelectron spectroscopy of liquid microjets using a magnetic bottle time-of-flight spectrometer with variable pass energy. Photoexcited iodide dissociates into a weak complex (a contact pair) of a solvated electron and an iodine atom in similar reaction times, 0.3 ps in H2O and D2O and 0.5 ps in methanol and ethanol, which are much shorter than their dielectric relaxation times. The results indicate that solvated electrons are formed with minimal solvent reorganization in the long-range solvent polarization field created for I(-). The photoelectron spectra for CTTS in H2O and D2O-measured with higher accuracy than in our previous study [Y. I. Suzuki et al., Chem. Sci. 2, 1094 (2011)]-indicate that internal conversion yields from the photoexcited I(-*) (CTTS) state are less than 10%, while alcohols provide 2-3 times greater yields of internal conversion from I(-*). The overall geminate recombination yields are found to be in the order of H2O > D2O > methanol > ethanol, which is opposite to the order of the mutual diffusion rates of an iodine atom and a solvated electron. This result is consistent with the transition state theory for an adiabatic outer-sphere electron transfer process, which predicts that the recombination reaction rate has a pre-exponential factor inversely proportional to a longitudinal solvent relaxation time.

  7. Charge-transfer-to-solvent reactions from I- to water, methanol, and ethanol studied by time-resolved photoelectron spectroscopy of liquids

    Science.gov (United States)

    Okuyama, Haruki; Suzuki, Yoshi-Ichi; Karashima, Shutaro; Suzuki, Toshinori

    2016-08-01

    The charge-transfer-to-solvent (CTTS) reactions from iodide (I-) to H2O, D2O, methanol, and ethanol were studied by time-resolved photoelectron spectroscopy of liquid microjets using a magnetic bottle time-of-flight spectrometer with variable pass energy. Photoexcited iodide dissociates into a weak complex (a contact pair) of a solvated electron and an iodine atom in similar reaction times, 0.3 ps in H2O and D2O and 0.5 ps in methanol and ethanol, which are much shorter than their dielectric relaxation times. The results indicate that solvated electrons are formed with minimal solvent reorganization in the long-range solvent polarization field created for I-. The photoelectron spectra for CTTS in H2O and D2O—measured with higher accuracy than in our previous study [Y. I. Suzuki et al., Chem. Sci. 2, 1094 (2011)]—indicate that internal conversion yields from the photoexcited I-* (CTTS) state are less than 10%, while alcohols provide 2-3 times greater yields of internal conversion from I-*. The overall geminate recombination yields are found to be in the order of H2O > D2O > methanol > ethanol, which is opposite to the order of the mutual diffusion rates of an iodine atom and a solvated electron. This result is consistent with the transition state theory for an adiabatic outer-sphere electron transfer process, which predicts that the recombination reaction rate has a pre-exponential factor inversely proportional to a longitudinal solvent relaxation time.

  8. Probing charge transfer and hot carrier dynamics in organic solar cells with terahertz spectroscopy

    Science.gov (United States)

    Cunningham, Paul D.; Lane, Paul A.; Melinger, Joseph S.; Esenturk, Okan; Heilweil, Edwin J.

    2016-04-01

    Time-resolved terahertz spectroscopy (TRTS) was used to explore charge generation, transfer, and the role of hot carriers in organic solar cell materials. Two model molecular photovoltaic systems were investigated: with zinc phthalocyanine (ZnPc) or alpha-sexathiophene (α-6T) as the electron donors and buckminsterfullerene (C60) as the electron acceptor. TRTS provides charge carrier conductivity dynamics comprised of changes in both population and mobility. By using time-resolved optical spectroscopy in conjunction with TRTS, these two contributions can be disentangled. The sub-picosecond photo-induced conductivity decay dynamics of C60 were revealed to be caused by auto-ionization: the intrinsic process by which charge is generated in molecular solids. In donor-acceptor blends, the long-lived photo-induced conductivity is used for weight fraction optimization of the constituents. In nanoscale multilayer films, the photo-induced conductivity identifies optimal layer thicknesses. In films of ZnPc/C60, electron transfer from ZnPc yields hot charges that localize and become less mobile as they thermalize. Excitation of high-lying Franck Condon states in C60 followed by hole-transfer to ZnPc similarly produces hot charge carriers that self-localize; charge transfer clearly precedes carrier cooling. This picture is contrasted to charge transfer in α-6T/C60, where hole transfer takes place from a thermalized state and produces equilibrium carriers that do not show characteristic signs of cooling and self-localization. These results illustrate the value of terahertz spectroscopic methods for probing charge transfer reactions.

  9. Ultrafast charge-transfer in organic photovoltaic interfaces: geometrical and functionalization effects.

    Science.gov (United States)

    Santos, Elton J G; Wang, W L

    2016-09-21

    Understanding the microscopic mechanisms of electronic excitation in organic photovoltaic cells is a challenging problem in the design of efficient devices capable of performing sunlight harvesting. Here we develop and apply an ab initio approach based on time-dependent density functional theory and Ehrenfest dynamics to investigate photoinduced charge transfer in small organic molecules. Our calculations include mixed quantum-classical dynamics with ions moving classically and electrons quantum mechanically, where no experimental external parameter other than the material geometry is required. We show that the behavior of photocarriers in zinc phthalocyanine (ZnPc) and C60 systems, an effective prototype system for organic solar cells, is sensitive to the atomic orientation of the donor and the acceptor units as well as the functionalization of covalent molecules at the interface. In particular, configurations with the ZnPc molecules facing on C60 facilitate charge transfer between substrate and molecules that occurs within 200 fs. In contrast, configurations where ZnPc is tilted above C60 present extremely low carrier injection efficiency even at longer times as an effect of the larger interfacial potential level offset and higher energetic barrier between the donor and acceptor molecules. An enhancement of charge injection into C60 at shorter times is observed as binding groups connect ZnPc and C60 in a dyad system. Our results demonstrate a promising way of designing and controlling photoinduced charge transfer on the atomic level in organic devices that would lead to efficient carrier separation and maximize device performance.

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

    Science.gov (United States)

    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.

  11. Examination of charge transfer in Au/YSZ for high-temperature optical gas sensing

    Energy Technology Data Exchange (ETDEWEB)

    Baltrus, John P. [U.S. DOE; Ohodnicki, Paul R. [U.S. DOE

    2014-01-01

    Au-nanoparticle incorporated oxide thin film materials demonstrate significant promise as functionalsensor materials for high temperature optical gas sensing in severe environments relevant for fossil andnuclear based power generation. The Au/yttria-stabilized zirconia (YSZ) system has been extensivelystudied in the literature and serves as a model system for fundamental investigations that seek to betterunderstand the mechanistic origin of the plasmonic gas sensing response. In this work, X-ray photoelec-tron spectroscopy techniques are applied to Au/YSZ films in an attempt to provide further experimentalevidence for a proposed sensing mechanism involving a change in free carrier density of Au nanoparticles due to charge transfer.

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

    Science.gov (United States)

    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.

  13. Efficient Charge Transfer Mechanism in Polyfluorene/ZnO Nanocomposite Thin Films

    OpenAIRE

    Bandar Ali Al-Asbahi; Mohammad Hafizuddin Haji Jumali; Rashad Al-Gaashani

    2014-01-01

    The optical properties and charge transfer mechanism of poly (9,9′-di-n-octylfluorenyl-2.7-diyl) (PFO)/ZnO thin films have been investigated. The ZnO nanorods (NRs) were prepared via a microwave technique. The solution blending method was used to prepare the PFO/ZnO nanocomposites. X-ray diffraction (XRD) and field emission scanning electron microscope (FE-SEM) were used to determine the structural properties, while UV-Vis and photoluminescence (PL) were employed to investigate the optical p...

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

    Science.gov (United States)

    Mančev, I.

    2009-02-01

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

  15. Excited state intramolecular charge transfer reaction in 4-(1-azetidinyl)benzonitrile: Solvent isotope effects

    Indian Academy of Sciences (India)

    Tuhin Pradhan; Piue Ghoshal; Ranjit Biswas

    2009-01-01

    Excited state intramolecular charge transfer reaction of 4-(1-azetidinyl) benzonitrile (P4C) in deuterated and normal methanol, ethanol and acetonitrile has been studied in order to investigate the solvent isotope effects on reaction rates and yields. These quantities (reaction rates and yields) along with several other properties such as quantum yield and radiative rates have been found to be insensitive to the solvent isotope substitution in all these solvents. The origin of the solvent isotope insensitivity of the reaction is discussed and correlated with the observed slowing down of the solvation dynamics upon isotope substitution.

  16. Infrared light irradiation diminishes effective charge transfer in slow sodium channel gating system

    Science.gov (United States)

    Plakhova, Vera B.; Bagraev, Nikolai T.; Klyachkin, Leonid E.; Malyarenko, Anna M.; Romanov, Vladimir V.; Krylov, Boris V.

    2001-02-01

    Effects of infrared light irradiation (IR) on cultured dorsal root ganglia cells were studied by the whole-cell patch-clamp technique. The IR field is demonstrated to diminish the effective charge transfer in the activation system from 6.2 +-0.6 to 4.5 +-0.4 in units of electron charge per e-fold change in membrane potential. The effects was blocked with ouabain. Our data is the first indication that sodium pump might be the molecular sensor of infrared irradiation in animal kingdom.

  17. Photoinduced intramolecular charge transfer process of betaine pyridinium: A theoretical spectroscopic study

    Science.gov (United States)

    Perrier, Aurélie; Aloïse, Stéphane; Pawlowska, Zuzanna; Sliwa, Michel; Maurel, François; Abe, Jiro

    2011-10-01

    Using Time-Dependent Density Functional Theory and taking into account bulk solvent effects, we investigate the absorption and emission spectra of a betaine pyridinium molecule, the 2-(1-pyridinio) benzimidazolate (SBPa). This molecule exhibits strong photoinduced intramolecular charge transfer (ICT). We have identified two different electronic states involved, respectively, in the strong bathochromic ICT absorption band (S 2) and in the moderate emission band (S 1). The ICT process is analyzed in terms of charge distribution and dipole moment evolutions upon photoexcitation. These results are compared with steady-state spectroscopic measurements.

  18. Thermodynamic, kinetic and electronic structure aspects of a charge-transfer active bichromophoric organofullerene

    Indian Academy of Sciences (India)

    K Senthil Kumar; Archita Patnaik

    2013-03-01

    Our recent work on charge transfer in the electronically push-pull dimethylaminoazobenzene-fullerene C60 donor-bridge-acceptor dyad through orbital picture revealed charge displacement from the n(N=N) (non-bonding) and (N=N) type orbitals centred on the donor part to the purely fullerene centred LUMOs and (LUMO+n) orbitals, delocalized over the entire molecule. Consequently, this investigation centres around the kinetic and thermodynamic parameters involved in the solvent polarity dependent intramolecular photo-induced electron transfer processes in the dyad, indispensable for artificial photosynthetic systems. A quasi-reversible electron transfer pathway was elucidated with electrode-specific heterogeneous electron transfer rate constants.

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

    Science.gov (United States)

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

    2014-03-01

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

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

    DEFF Research Database (Denmark)

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

    2010-01-01

    Ultrahigh vacuum (UHV)-deposited films of the mixed phase of tetramethoxypyrene and tetracyanoquinodimethane (TMP -TCNQ ) on gold have been studied using ultraviolet photoelectron spectroscopy (UPS), x-ray diffraction (XRD), infrared (IR) spectroscopy, and scanning tunneling spectroscopy (STS......). The formation of an intermolecular charge-transfer (CT) compound is evident from the appearance of new reflexes in XRD (d =0.894nm and d =0.677nm). A softening of the CN stretching vibration (redshift by 7 cm⊃-1) of TCNQ is visible in the IR spectra, being indicative of a CT on the order of 0.3e from TMP...

  1. Luminescence from low-energy He/sup +//Xe charge-transfer reactions

    Energy Technology Data Exchange (ETDEWEB)

    Jones, E.G.; Hughes, B.M.; Fee, D.C.; Tiernan, T.O.

    1977-04-01

    Optical emissions produced by collision of 100-eV He/sup +/ ions with Xe atoms have been studied over the spectral range from 40 to 900 nm. All of the major lines in the emission spectrum can be assigned to transitions in Xe II resulting from charge-transfer reactions. Emission cross sections for the major lines in the vacuum-ultraviolet and visible spectral regions are reported and the importance of cascading is assessed. The kinetic energy dependence is discussed for several of these lines.

  2. Indolizino[5,6-b]quinoxaline Derivatives: Intramolecular Charge Transfer Characters and NIR Fluorescence.

    Science.gov (United States)

    Kojima, Mitsuru; Hayashi, Hironobu; Aotake, Tatsuya; Ikeda, Shinya; Suzuki, Mitsuharu; Aratani, Naoki; Kuzuhara, Daiki; Yamada, Hiroko

    2015-11-01

    Indolizino[5,6-b]quinoxaline derivatives (1 a and 1 b) with a push-pull structure were prepared to show intramolecular charge-transfer properties. Compounds 1 a and 1 b are strongly fluorescent in aprotic solvents while symmetrical derivatives (2 a and 2 b) were non-fluorescent. The π-expanded α-α linked dimer (10) of indolizino[5,6-b]quinoxaline 1 b was serendipitously obtained to show NIR absorption over 800 nm and the fluorescence edge reached to 1400 nm.

  3. Topological charge transfer in frequency doubling of fractional orbital angular momentum state

    Science.gov (United States)

    Ni, R.; Niu, Y. F.; Du, L.; Hu, X. P.; Zhang, Y.; Zhu, S. N.

    2016-10-01

    Nonlinear frequency conversion is promising for manipulating photons with orbital angular momentum (OAM). In this letter, we investigate the second harmonic generation (SHG) of light beams carrying fractional OAM. By measuring the OAM components of the generated second harmonic (SH) waves, we find that the integer components of the fundamental beam will interact with each other during the nonlinear optical process; thus, we figure out the law for topological charge transfer in frequency doubling of the fractional OAM state. Theoretical predictions by solving the nonlinear coupled wave equations are consistent with the experimental results.

  4. Scale-model charge-transfer technique for measuring enhancement factors

    Science.gov (United States)

    Kositsky, J.; Nanevicz, J. E.

    1991-01-01

    Determination of aircraft electric field enhancement factors is crucial when using airborne field mill (ABFM) systems to accurately measure electric fields aloft. SRI used the scale model charge transfer technique to determine enhancement factors of several canonical shapes and a scale model Learjet 36A. The measured values for the canonical shapes agreed with known analytic solutions within about 6 percent. The laboratory determined enhancement factors for the aircraft were compared with those derived from in-flight data gathered by a Learjet 36A outfitted with eight field mills. The values agreed to within experimental error (approx. 15 percent).

  5. Nanometer scale carbon structures for charge-transfer systems and photovoltaic applications.

    Science.gov (United States)

    Guldi, Dirk M

    2007-03-28

    This article surveys and highlights the integration of nanometer scale carbon structures--in combination with chromophores that exhibit (i) significant absorption cross section throughout the visible part of the solar spectrum and (ii) good electron donating power--into novel electron donor-acceptor conjugates (i.e., covalent) and hybrids (i.e., non-covalent). The focus of this article is predominantly on performance features--charge-transfer and photovoltaic--of the most promising solar energy conversion systems. Besides documenting fundamental advantages as they emerge around nanometer scale carbon structures, critical evaluations of the most recent developments in the fields are provided.

  6. Imidazole-annulated tetrathiafulvalenes exhibiting pH-tuneable intramolecular charge transfer and redox properties.

    Science.gov (United States)

    Wu, Jincai; Dupont, Nathalie; Liu, Shi-Xia; Neels, Antonia; Hauser, Andreas; Decurtins, Silvio

    2009-03-02

    In order to study the electronic interactions in donor-acceptor ensembles as a function of pH, an efficient synthetic route to three imidazole-annulated tetrathiafulvalene (TTF) derivatives 1-3 is reported. Their electronic absorption spectra, in view of photoinduced intramolecular charge transfer, and their electrochemical behavior were investigated, and pK(a) values for the two protonation processes on the acceptor unit were determined in organic solvents by photometric titration. The influence of the TTF moiety on these values is discussed.

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

    Science.gov (United States)

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

    2017-07-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1983-11-01

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

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

    KAUST Repository

    Amin, B.

    2013-04-23

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

  10. Multi-state charge transfer dynamics and trapping of hyperthermal and low energy alkali ions

    Science.gov (United States)

    Dahl, Eric Brian

    Experimental and theoretical studies were performed of the scattering of hyperthermal and keV energy Lisp+ and Nasp+ ions from Cu(001) surfaces. Chapter one presents measurements of relative total Li(2p) and Na(3p) yields, for 400 eV Lisp+ and 1320 eV Nasp+ scattering from clean and alkali-covered Cu(001). These excited-state yields were measured because they provide a sensitive test of multi-state models of resonant charge transfer, that is, models that are capable of treating more than two atomic states. Chapter two presents a detailed conceptual analysis of two multi-state models: a rate-equation model and the Marston model. The rate-equation model fails to reproduce the measured Li(2p) and Na(3p) yields, whereas the Marston model reproduces the primary trends in the yields. The different behaviors of these models are explained by physical reasoning. The rate-equation model is a fundamentally flawed description of resonant charge transfer, because it includes neither hybridization nor non-adiabatic excitations. Both aspects of resonant charge transfer are required to explain the Li(2p) and Na(3p) yields. These aspects are included in the Marston model, which describes the atom-metal system quantum-mechanically. The quantum mechanics of the atom-metal system can be understood from a physical viewpoint by the use of a few basic principles-principles which are broadly applicable to resonant charge transfer. A key principle is the tendency of the atom-metal system to electronically equilibrate throughout the scattering trajectory of an atom. Additional principles follow from an examination of the many-electron basis states of the atom-metal system. Chapter three presents measurements of the probability that 5 to 600 eV Nasp+ ions incident on Cu(001) become trapped on top of the surface. At a near-normal incident geometry the on-top trapping probability decreased monotonically as the incident energy was decreased. At 45sp° incidence along the azimuth, a surprising

  11. High pressure induced charge transfer in 3d-4f bimetallic photomagnetic materials.

    Science.gov (United States)

    Wu, Lai-Chin; Nielsen, Morten Bormann; Bremholm, Martin; Madsen, Solveig Røgild; Overgaard, Jacob; Newville, Matt; Chen, Yu-Sheng; Iversen, Bo Brummerstedt

    2015-05-25

    Pressure-induced crystal color change of photo-magnetic materials [Ln(DMF)4(H2O)3(μ-CN)M(CN)5]·H2O, Ln = Y, M = Fe (1), Ln = Y, M = Co (2), Ln = Nd, M = Fe (3) (DMF = N,N-dimethyl formamide) are investigated using variable pressure X-ray Absorption Near-Edge Structure (XANES) spectroscopy and X-ray diffraction. For 1 the effect is caused by ligand-to-metal charge transfer (LMCT) on the iron site.

  12. A Validated High-Throughput Fluorometric Method for Determination of Omeprazole in Quality Control Laboratory via Charge Transfer Sensitized Fluorescence.

    Science.gov (United States)

    Mahmoud, Ashraf M; Ahmed, Sameh A

    2016-03-01

    A high-throughput 96-microwell plate fluorometric method was developed and validated to determine omeprazole (OMZ) in its dosage forms. The method was based on the charge-transfer (CT) sensitized fluorescence reaction of OMZ with 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone (DDQ). This fluorescence reaction provided a new approach for simple, sensitive and selective determinations of OMZ in pharmaceutical preparations. In the present method, the fluorescence reaction was carried out in 96-microwell plates as reaction vessels in order to increase the automation of the methodology and the efficiency of its use in quality control laboratories. All factors affecting the fluorescence reaction were carefully studied and the conditions were optimized. The stoichiometry of the fluorescence reaction between OMZ and DDQ was determined and the reaction mechanism was suggested. Under the optimum conditions, the linear range was 100-6000 ng/ml with the lowest LOD of 33 ng/ml. Analytical performance of the proposed assay, in terms of accuracy and precision, was statistically validated and the results were satisfactory; RSD was <2.6 % and the accuracy was 98.6-101.6 %. The method was successfully applied to the analysis of OMZ in its dosage forms; the recovery values were 98.26-99.60 ± 0.95-2.22 %. The developed methodology may provide a safer, automated and economic tool for the analysis of OMZ in quality control laboratories.

  13. Evanescent-field spectroscopy using structured optical fibers: detection of charge-transfer at the porphyrin-silica interface.

    Science.gov (United States)

    Martelli, Cicero; Canning, John; Reimers, Jeffrey R; Sintic, Maxine; Stocks, Danial; Khoury, Tony; Crossley, Maxwell J

    2009-03-04

    The fabrication of porphyrin thin films derived from dichloro[5,10,15,20-tetra(heptyl)porphyrinato]tin(IV) [Cl-Sn(THP)-Cl] in the holes of photonic crystal fibers over 90 cm in length is described. Evanescent field spectroscopy (EFS) is used to investigate the interfacial properties of the films, with the high surface optical intensity and the long path length combining to produce significant absorption. By comparison with results obtained for similar films formed from Cl-Sn(THP)-Cl inside fused-silica cuvettes and on glass slides, the film is shown to be chemisorbed as a surface Si-O-Sn(THP)-X (X = Cl or OH) species. In addition to the usual porphyrin Q and Soret bands, new absorptions in the in-fiber films are observed by EFS at 445 nm and between 660-930 nm. The 660-930 nm band is interpreted as a porphyrin to silicon charge-transfer transition and postulated to arise following chemisorption at mechanical-strain induced defect sites on the silica surface. Such defect sites are caused by the optical fiber production process and are less prevalent on other glass surfaces. EFS within optical fibers therefore offers new ways for understanding interface phenomena such as surface adsorbates on glass. Such understanding will benefit all devices that exploit interface phenomena, both in optical fibers and other integrated waveguide forms. They may be directly exploited to create ultrasensitive molecular detectors and could yield novel photonic devices.

  14. Probing Electronic, Structural, and Charge Transfer Properties of Organic Semiconductor/Inorganic Oxide Interfaces Using Field-Effect Transistors

    Science.gov (United States)

    Spalenka, Josef Wade

    Interfaces between organic semiconductors and inorganic oxides provide the functionality for devices including field-effect transistors (FETs) and organic photovoltaics. Organic FETs are sensitive to the physical structure and electronic properties of the few molecular layers of material at the interface between the semiconducting channel and the gate dielectric, and provide quantitative information such as the field-effect mobility of charge carriers and the concentration of trapped charge. In this thesis, FET interfaces between organic small-molecule semiconductors and SiO2, and donor/acceptor interfaces between organic small-molecules and the wide bandgap semiconductor ZnO are studied using electrical measurements of field-effect transistor devices. Monolayer-scale films of dihexyl sexithiophene are shown to have higher hole mobility than other monolayer organic semiconductors, and the origin of the high mobility is discussed. Studies of the crystal structure of the monolayer using X-ray structural probes and atomic force microscopy reveal the crystal structure is different in the monolayer regime compared to thicker films and bulk crystals. Progress and remaining challenges are discussed for in situ X-ray diffraction studies of the dynamic changes in the local crystal structure in organic monolayers due to charge carriers generated during the application of electric fields from the gate electrode in working FETs. Studies were conducted of light sensitive organic/inorganic interfaces that are modified with organic molecules grafted to the surface of ZnO nanoparticles and thin films. These interfaces are models for donor/acceptor interfaces in photovoltaics. The process of exciton dissociation at the donor/acceptor interface was sensitive to the insulating or semiconducting molecules grafted to the ZnO, and the photoinduced charge transfer process is measured by the threshold voltage shift of FETs during illumination. Charge transfer between light sensitive donor

  15. Photoinduced Charge Transfer at Metal Oxide/Oxide Interfaces Prepared with Plasma Enhanced Atomic Layer Deposition

    Science.gov (United States)

    Kaur, Manpuneet

    LiNbO3 and ZnO have shown great potential for photochemical surface reactions and specific photocatalytic processes. However, the efficiency of LiNbO3 is limited due to recombination or back reactions and ZnO exhibits a chemical instability in a liquid cell. In this dissertation, both materials were coated with precise thickness of metal oxide layers to passivate the surfaces and to enhance their photocatalytic efficiency. LiNbO 3 was coated with plasma enhanced atomic layer deposited (PEALD) ZnO and Al2O3, and molecular beam deposited TiO2 and VO2. On the other hand, PEALD ZnO and single crystal ZnO were passivated with PEALD SiO2 and Al2O3. Metal oxide/LiNbO3 heterostructures were immersed in aqueous AgNO3 solutions and illuminated with ultraviolet (UV) light to form Ag nanoparticle patterns. Alternatively, Al2O3 and SiO2/ZnO heterostructures were immersed in K3PO 4 buffer solutions and studied for photoelectrochemical reactions. A fundamental aspect of the heterostructures is the band alignment and band bending, which was deduced from in situ photoemission measurements. This research has provided insight to three aspects of the heterostructures. First, the band alignment at the interface of metal oxides/LiNbO 3, and Al2O3 or SiO2/ZnO were used to explain the possible charge transfer processes and the direction of carrier flow in the heterostructures. Second, the effect of metal oxide coatings on the LiNbO3 with different internal carrier concentrations was related to the surface photochemical reactions. Third is the surface passivation and degradation mechanism of Al2O 3 and SiO2 on ZnO was established. The heterostructures were characterized after stability tests using atomic force microscopy (AFM), scanning electron microscopy (SEM), and cross-section transmission electron microscopy (TEM). The results indicate that limited thicknesses of ZnO or TiO2 on polarity patterned LiNbO3 (PPLN) enhances the Ag+ photoinduced reduction process. ZnO seems more efficient

  16. A simple framework for integrated design of complex architectural forms

    CERN Document Server

    Svoboda, Ladislav; Zeman, Jan; Kurilla, Lukáš

    2012-01-01

    This paper presents preliminary results of a newly developed methodology and a software tool for parametric design of complex architectural objects, so called digital or algorithmic forms. In order to provide a maximally flexible solution, the proposed design philosophy yields two open source utilities Donkey and MIDAS written in Grashopper algorithm editor and C++, respectively, that are to be linked with a scripting-based architectural modellers Rhinoceros(C), AutoCAD(C) and the open source Finite Element solver OOFEM. The emphasis is on the mechanical response of designed objects in order to provide architects with a consistent learning framework and wise insight into structural behaviour of their artworks. As demonstrated on several case studies, the combination of the utilities may handle objects of considerable structural complexity and boosts the algorithmic architectural design in terms of accelerating the process of finding procedural design parameters from orders of weeks to days or hours.

  17. SLANT IMMERSIONS OF COMPLEX SPACE FORMS AND CHEN'S INEQUALITY

    Institute of Scientific and Technical Information of China (English)

    Li Guanghan; Wu Chuanxi

    2005-01-01

    A submanifold in a complex space form is called slant if it has constant Wirtinger angles. B. Y. Chen and Y. Tazawa proved that there do not exist minimal proper slant surfaces in CP2 and CH2. So it seems that the slant immersion has some interesting properties. The authors have great interest to consider slant immersions satisfying some additional conditions, such as unfull first normal bundles or Chen's equality holding. They prove that there do not exist n-dimensional Kaehlerian slant immersions in CPn and CHn with unfull first normal bundles. Next, it is seen that every Kaehlerian slant submanifold satisfying an equality of Chen is minimal which is similar to that of Lagrangian immersions. But in contrast, it is shown that a large class of slant immersions do not exist thoroughly. Finally, they give an application of Chen's inequality to general slant immersions in a complex projective space, which generalizes a result of Chen.

  18. Trifluoromethylmetallate anions as components of molecular charge transfer salts and superconductors.

    Energy Technology Data Exchange (ETDEWEB)

    Schlueter, J. A.

    1998-10-14

    Whereas polymeric and common inorganic anions frequently deprive the synthetic chemist of a chance to modify a charge transfer salt's structure through anion alterations, discrete organometallic anions provide a vast opportunity to probe the structure/property correlations of a material through rational synthetic methods. We have recently undertaken a research effort aimed at the crystallization of conducting charge transfer salts which possess modifiable, organometallic anions as the charge compensating entities. This research has been richly rewarded with the discovery of a new family of bis(ethylenedithio) tetrathiafulvalene (BEDT-TTF or ET) based molecular superconductors. Herein is presented a summary of over twenty {kappa}(ET){sub 2}M(CF{sub 3}){sub 4}(1,1,2-trihaloethane) (M = Cu, Ag, Au) superconducting salts. Three new related salts are also reported: (ET){sub 2} [trans-Ag(CF{sub 3}),(CN){sub 2}], {kappa}{sub L}(BEDT-TSF){sub 2}Ag(CF{sub 3}){sub 4}(TCE), and {kappa}{sub L}(ET){sub 2}Ag(CF{sub 3}){sub 3}Cl(TCE).

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

    Science.gov (United States)

    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.

  20. Photoinduced Intramolecular Charge Transfer in Donor-acceptor Dyad and Donor-bridge-acceptor Triad

    Institute of Scientific and Technical Information of China (English)

    Yong Ding; Yuan-zuo Li; Feng-cai Ma

    2008-01-01

    The ground and excited state properties of the [60]fullerene,diphenylbenzothiadiazole-triphenylamine (PBTDP-TPA) dyad and fullerene-diphenylbenzothiadiazole-triphenylamine (fullerene-PBTDP-TPA) triad were investigated theoretically using density functional theory with B3LYP functional and 3-21G basis set and time-dependent density functional theory with B3LYP functional and STO-3G basis set as well as 2D and 3D real space analysis methods.The 2D site representation reveals the electron-hole coherence on exci- tation.The 3D transition density shows the orientation and strength of the transition dipole moment,and the 3D charge difference density gives the orientation and result of the intramolecular charge transfer.Also, photoinduced intermolecular charge transfer (ICT) in PBTDP-TPA-fullerene triad are identified with 2D and 3D representations,which reveals the mechanisms of ICT in donor-bridge-acceptor triad on excitation. Besides that we also found that the direct superexchange ICT from donor to acceptor (tunneling through the bridge) strongly promotes the ICT in the donor-bridge-acceptor triad.

  1. Charge transfer at carbon nanotube-graphene van der Waals heterojunctions

    Science.gov (United States)

    Liu, Yuanda; Wang, Fengqiu; Liu, Yujie; Wang, Xizhang; Xu, Yongbing; Zhang, Rong

    2016-06-01

    Carbon nanotubes and graphene are two most widely investigated low-dimensional materials for photonic and optoelectronic devices. Combining these two materials into all-carbon hybrid nanostructures has shown enhanced properties in a range of devices, such as photodetectors and flexible electrodes. Interfacial charge transfer is the most fundamental physical process that directly impacts device design and performance, but remains a subject less well studied. Here, we complemented Raman spectroscopy with photocurrent probing, a robust way of illustrating the interfacial built-in fields, and unambiguously revealed both static and dynamic (photo-induced) charge transfer processes at the nanotube-graphene interfaces. Significantly, the effects of nanotube species, i.e. metallic as opposed to semiconducting, are for the first time compared. Of all the devices examined, the graphene sheet was found to be p-type doped with (6, 5) chirality-enriched semiconducting SWNTs (s-SWNTs), while n-type doped with highly pure (>99%) metallic SWNTs (m-SWNTs). Our results provide important design guidelines for all-carbon hybrid based devices.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2009-01-01

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

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

    Science.gov (United States)

    Bai, Peng; Bazant, Martin Z.

    2014-04-01

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

  4. Ferromagnetism induced by the charge transfer in Al-doped ZnO nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Yanyu; Zhou, Wei; Wu, Ping, E-mail: pingwu@tju.edu.cn

    2014-12-05

    Highlights: • A systematical investigation has been carried out on Zn{sub 1−x}Al{sub x}O system. • Our results confirm that Zn{sub 1−x}Al{sub x}O nanoparticles are magnetic. • The magnetism originates from charge transfer between different cations. • The accordant conclusion is drawn both theoretically and experimentally. • The ferromagnetism would render it to realize more comprehensive applications. - Abstract: The mechanism of ferromagnetism in Al-doped ZnO was investigated both theoretically and experimentally. The density functional theory calculations were carried out to explore the electronic structure origin of ferromagnetism. The Al dopants both doping in a bulk ZnO and absorbing on the ZnO surface are taken into account. Based on the Bader charge analysis for the clear and adsorbed ZnO surface, it is found that the ionic state of Zn decreases after Al doping. The corresponding room temperature ferromagnetism was also confirmed by experiments. Moreover, the experimental analysis rules out that the ferromagnetism results from zinc vacancy or oxygen vacancy. Thus, the physical origin of the induced magnetism was indicated originating from the charge transfer between Zn atoms and adsorbed Al atoms.

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

    Science.gov (United States)

    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.

  6. Relation between Nonlinear Optical Properties of Push-Pull Molecules and Metric of Charge Transfer Excitations.

    Science.gov (United States)

    List, Nanna Holmgaard; Zaleśny, Robert; Murugan, N Arul; Kongsted, Jacob; Bartkowiak, Wojciech; Ågren, Hans

    2015-09-08

    We establish the relationships between the metric of charge transfer excitation (Δr) for the bright ππ* state and the two-photon absorption probability as well as the first hyperpolarizability for two families of push-pull π-conjugated systems. As previously demonstrated by Guido et al. (J. Chem. Theory Comput. 2013, 9, 3118-3126), Δr is a measure for the average hole-electron distance upon excitation and can be used to discriminate between short- and long-range electronic excitations. We indicate two new benefits from using this metric for the analyses of nonlinear optical properties of push-pull systems. First, the two-photon absorption probability and the first hyperpolarizability are found to be interrelated through Δr; if β ∼ (Δr)(k), then roughly, δ(TPA) ∼ (Δr)(k+1). Second, a simple power relation between Δr and the molecular hyperpolarizabilities of push-pull systems offers the possibility of estimating properties for longer molecular chains without performing calculations of high-order response functions explicitly. We further demonstrate how to link the hyperpolarizabilities with the chain length of the push-pull π-conjugated systems through the metric of charge transfer.

  7. Modulation of the charge transfer and photophysical properties in non-fused tetrathiafulvalene-benzothiadiazole derivatives.

    Science.gov (United States)

    Pop, Flavia; Seifert, Sabine; Hankache, Jihane; Ding, Jie; Hauser, Andreas; Avarvari, Narcis

    2015-01-28

    Bis(thiomethyl)- and bis(thiohexyl)-tetrathiafulvalene-bromo-benzothiadiazoles, containing electron donor tetrathiafulvalene (TTF) and electron acceptor benzothiadiazole (BTD) units, have been prepared by Stille coupling reactions between the TTF-SnMe3 precursors and BTD-Br2. In another series of experiments, TTF-acetylene-BTD compounds have been synthesized by Sonogashira coupling between either TTF-acetylenes and BTD-Br2 in low yields, or TTF-iodine and BTD-acetylene in moderate yields. In the compound TTF-C≡C-BTD the TTF and BTD units are coplanar in the solid state, as shown by the single crystal X-ray structure, and there is segregation in the packing between the donor and acceptor units. All the derivatives have good electron donor properties, as determined by cyclic voltammetry measurements, and they can also be reversibly reduced thanks to the presence of the BTD moiety. UV-visible spectroscopy and photophysical investigations show the presence of an intramolecular charge transfer (ICT) band and an emission band originating from the charge transfer. Both the absorption and the emission are modulated by the substitution scheme and the insertion of the acetylenic bridge.

  8. Quantum dynamics of the charge transfer in C{sup +} + S at low collision energies

    Energy Technology Data Exchange (ETDEWEB)

    Chenel, Aurelie; Mangaud, Etienne; Justum, Yves; Desouter-Lecomte, Michele [Laboratoire de Chimie Physique, Bat 349, Univ-ParisSud et CNRS-UMR8000, F-91405 Orsay Cedex (France); Talbi, Dahbia [Groupe de Recherche en Astronomie et Astrophysique du Languedoc, Universite de Montpellier II et CNRS-UMR5024, Place Eugene Bataillon, F-34095 Montpellier Cedex 05 (France); Bacchus-Montabonel, Marie-Christine, E-mail: michele.desouter-lecomte@u-psud.f [Laboratoire de Spectrometrie Ionique et moleculaire, Universite de Lyon I et CNRS-UMR5579, 43 Bd du 11 Novembre 1918, F-69622 Villeurbanne Cedex (France)

    2010-12-28

    Following a recent semiclassical investigation by Bacchus-Montabonel and Talbi (2008 Chem. Phys. Lett. 467 28), the C{sup +}(2s{sup 2}2p){sup 2}P + S(3s{sup 2}3p{sup 4}){sup 3}P charge transfer process involved in the modellization of the interstellar medium chemistry and its reverse reaction are revisited by combining a wave packet approach and semiclassical dynamics in a quasimolecular approach for doublet and quartet states. New radial non-adiabatic coupling matrix elements have been calculated and the mixed treatment gives access to new precise values of the rate coefficients for the direct and reverse charge transfer processes. For this system, quantum and semiclassical results are in good agreement even at low collision kinetic energies. The dominance of the quartet states in the process is confirmed. In the quantum treatment, the collision matrix elements are extracted from wave packets by the flux method with an absorbing potential. The formation of resonances due to a centrifugal barrier is illustrated.

  9. Radiative charge transfer lifetime of the excited state of (NaCa)$^+$

    CERN Document Server

    Makarov, O P; Michels, H J; Smith, W W; Makarov, Oleg P.

    2003-01-01

    New experiments were proposed recently to investigate the regime of cold atomic and molecular ion-atom collision processes in a special hybrid neutral-atom--ion trap under high vacuum conditions. The collisional cooling of laser pre-cooled Ca$^+$ ions by ultracold Na atoms is being studied. Modeling this process requires knowledge of the radiative lifetime of the excited singlet A$^1\\Sigma^+$ state of the (NaCa)$^+$ molecular system. We calculate the rate coefficient for radiative charge transfer using a semiclassical approach. The dipole radial matrix elements between the ground and the excited states, and the potential curves were calculated using Complete Active Space Self-Consistent field and M\\"oller-Plesset second order perturbation theory (CASSCF/MP2) with an extended Gaussian basis, 6-311+G(3df). The semiclassical charge transfer rate coefficient was averaged over a thermal Maxwellian distribution. In addition we also present elastic collision cross sections and the spin-exchange cross section. The ra...

  10. Structure and dynamics of a dizinc metalloprotein: effect of charge transfer and polarization.

    Science.gov (United States)

    Li, Yong L; Mei, Ye; Zhang, Da W; Xie, Dai Q; Zhang, John Z H

    2011-08-25

    Structures and dynamics of a recently designed dizinc metalloprotein (DFsc) (J. Mol. Biol. 2003, 334, 1101) are studied by molecular dynamics simulation using a dynamically adapted polarized force field derived from fragment quantum calculation for protein in solvent. To properly describe the effect of charge transfer and polarization in the present approach, quantum chemistry calculation of the zinc-binding group is periodically performed (on-the-fly) to update the atomic charges of the zinc-binding group during the MD simulation. Comparison of the present result with those obtained from simulations under standard AMBER force field reveals that charge transfer and polarization are critical to maintaining the correct asymmetric metal coordination in the DFsc. Detailed analysis of the result also shows that dynamic fluctuation of the zinc-binding group facilitates solvent interaction with the zinc ions. In particular, the dynamic fluctuation of the zinc-zinc distance is shown to be an important feature of the catalytic function of the di-ion zinc-binding group. Our study demonstrates that the dynamically adapted polarization approach is computationally practical and can be used to study other metalloprotein systems.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-01-13

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

  12. The role of hydrogen bonding in excited state intramolecular charge transfer.

    Science.gov (United States)

    Chipem, Francis A S; Mishra, Anasuya; Krishnamoorthy, G

    2012-07-07

    Intramolecular charge transfer (ICT) that occurs upon photoexcitation of molecules is a vital process in nature and it has ample applications in chemistry and biology. The ICT process of the excited molecules is affected by several environmental factors including polarity, viscosity and hydrogen bonding. The effect of polarity and viscosity on the ICT processes is well understood. But, despite the fact that hydrogen bonding significantly influences the ICT process, the specific role of hydrogen bonding in the formation and stabilization of the ICT state is not unambiguously established. Some literature reports predicted that the hydrogen bonding of the solvent with a donor promotes the formation of a twisted intramolecular charge transfer (TICT) state. Some other reports stated that it inhibits the formation of the TICT state. Alternatively, it was proposed that the hydrogen bonding of the solvent with an acceptor favors the TICT state. It is also observed that a dynamic equilibrium is established between the free and the hydrogen bonded ICT states. This perspective focuses on the specific role played by hydrogen bonding of the solvent with the donor and the acceptor, and by proton transfer in the ICT process. The utility of such influence in molecular recognition and anion sensing is discussed with a few recent literature examples in the end.

  13. Excited State Structural Dynamics of Carotenoids and ChargeTransfer Systems

    Energy Technology Data Exchange (ETDEWEB)

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

    2006-01-01

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

  14. Colossal negative thermal expansion in BiNiO3 induced by intermetallic charge transfer

    Science.gov (United States)

    Azuma, Masaki; Chen, Wei-tin; Seki, Hayato; Czapski, Michal; Olga, Smirnova; Oka, Kengo; Mizumaki, Masaichiro; Watanuki, Tetsu; Ishimatsu, Naoki; Kawamura, Naomi; Ishiwata, Shintaro; Tucker, Matthew G.; Shimakawa, Yuichi; Attfield, J. Paul

    2011-01-01

    The unusual property of negative thermal expansion is of fundamental interest and may be used to fabricate composites with zero or other controlled thermal expansion values. Here we report that colossal negative thermal expansion (defined as linear expansion <−10−4 K−1 over a temperature range ~100 K) is accessible in perovskite oxides showing charge-transfer transitions. BiNiO3 shows a 2.6% volume reduction under pressure due to a Bi/Ni charge transfer that is shifted to ambient pressure through lanthanum substitution for Bi. Changing proportions of coexisting low- and high-temperature phases leads to smooth volume shrinkage on heating. The crystallographic linear expansion coefficient for Bi0.95La0.05NiO3 is −137×10−6 K−1 and a value of −82×10−6 K−1 is observed between 320 and 380 K from a dilatometric measurement on a ceramic pellet. Colossal negative thermal expansion materials operating at ambient conditions may also be accessible through metal-insulator transitions driven by other phenomena such as ferroelectric orders. PMID:21673668

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

    KAUST Repository

    Vandewal, Koen

    2013-11-17

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

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

    DEFF Research Database (Denmark)

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

    1975-01-01

    the inhibition intensifies and the quenching almost vanishes. The reaction constants between ortho-Ps and the acceptors were determinded to be: 1.5 × 1010 M−1 s−1 for SO2 in dioxane 3.7 × 1010 M−1 s−1 for SO2 in n-heptane, 3.4 × 1010 M−1 s−1 for tetracyanoquinodimethane in tetrahydrofurane and 1.6 × 1010 M−1 s−1...

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

    Science.gov (United States)

    2009-01-01

    number of intact Ru-peptides per QD-conjugate following enzymatic digestion. This also allowed the derivation of standard Michaelis - Menten kinetic values...in each case the kinetic data agreed reasonably with the expected val- ues.2 Conclusions: We combined the electrochemi- cal properties of redox...locity versus increasing chymotrypsin concentration in the presence and absence of a specific chymostatin inhibitor. The changes in kinetic parameters

  18. Conjugated polymer charge-transfer complexes : A new route to low-bandgap photostable materials

    NARCIS (Netherlands)

    Bakulin, Artem A.; Pshenichnikov, Maxim S.; Van Loosdrecht, Paul H M; Golovnin, Ilya V.; Paraschuk, Dmitry Yu

    2010-01-01

    Polymer solar cells have high potential to convert solar energy into electricity in a cost-effective way. To date, the best polymer solar cells show the efficiency about 5%, and significant efforts are underway to increase their efficiency to the level of practical applications. One of the key strat

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

    DEFF Research Database (Denmark)

    Zhang, Wenkai; Kjær, Kasper Skov; Alonso-Mori, Roberto

    2017-01-01

    ) 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...

  20. On the Complexity of Spill Everywhere under SSA Form

    CERN Document Server

    Bouchez, Florent; Rastello, Fabrice

    2007-01-01

    Compilation for embedded processors can be either aggressive (time consuming cross-compilation) or just in time (embedded and usually dynamic). The heuristics used in dynamic compilation are highly constrained by limited resources, time and memory in particular. Recent results on the SSA form open promising directions for the design of new register allocation heuristics for embedded systems and especially for embedded compilation. In particular, heuristics based on tree scan with two separated phases -- one for spilling, then one for coloring/coalescing -- seem good candidates for designing memory-friendly, fast, and competitive register allocators. Still, also because of the side effect on power consumption, the minimization of loads and stores overhead (spilling problem) is an important issue. This paper provides an exhaustive study of the complexity of the ``spill everywhere'' problem in the context of the SSA form. Unfortunately, conversely to our initial hopes, many of the questions we raised lead to NP-...

  1. A hermetic self-sustained microbial solar cell based on Chlorella vulgaris and a versatile charge transfer chain

    Science.gov (United States)

    Pan, Keliang; Zhou, Peijiang

    2015-10-01

    A hermetic noble-metal-free membrane-less microbial solar cell (MSC) is established. The substances decomposition and regeneration in this MSC are carried out only by Chlorella vulgaris simultaneously. The conversion of metabolism types of C. vulgaris is controlled only by illumination. By using a pleiotropic redox mediator and a cupric hexacyanoferrate modified cathode, a two-phase three-stage charge transfer chain is formed. Through this pathway, the one microorganism self-sustained system gets a long-term power output up to 0.04773 mW/cm2 at 0.423 V without any material exchange with external, which is 50 times higher than that obtained from the original system. Benefiting from this electron buffer system, the battery will achieve an electricity generation in both light and dark conditions. There is almost no consumption of any substrates throughout the stabilized process, and no more additions are required. This maintenance-free and extremely inexpensive reactor with a simple structure and a long service life demonstrates the possibility of combining the microbial, chemical and photo cells.

  2. Solid-state thermochromism and phase transitions of charge transfer 1,3-diamino-4,6-dinitrobenzene dyes.

    Science.gov (United States)

    Lee, Jong Hoon; Naumov, Pance; Chung, Ihn Hee; Lee, Sang Cheol

    2011-09-01

    The lower 1,3-bis(hydroxyalkylamino) homologues of the strong intramolecular X-type charge transfer (CT) system 1,3-diamino-4,6-dinitrobenzene (DADNB) exhibit reversible color change in the solid state from yellow at room temperature (RT) to orange and red at high temperature (HT). To investigate the structural prerequisites for occurrence of this phenomenon, we prepared 10 new derivatives of DADNB where the hydroxyalkyl arms at the amino groups were replaced with substituents having different electronic and steric profiles. Two of the new materials exhibit sharp and reversible thermochromic change in the solid state: when heated, the bis(aminoethyl) derivative (DADNB-1) undergoes color change from orange-red to brown, while one of the three polymorphs of the bisphenyl product (DADNB-2) changes its color from red to yellow. The physicochemical analysis and the crystal structures of seven of these compounds, one of which is trimorphic, confirmed that both phenomena are due to solid-solid phase transitions. The brown high-temperature phase of DADNB-1 presents the first example where the absorption is shifted beyond the red region. Form C of DADNB-2 is the first material of this group that exhibits "negative" thermochromism, where the high-temperature phase absorbs at lower wavelength than the low-temperature one. The results demonstrate the potentials of these simple and easily accessible organic molecular materials for thermal switching of the optical properties by utility of intermolecular interactions to modulate the intramolecular CT.

  3. Intervalence Charge Transfer luminescence: The anomalous luminescence of Cerium-doped Cs2LiLuCl6 elpasolite

    CERN Document Server

    Seijo, Luis

    2014-01-01

    The existence of intervalence charge transfer (IVCT) luminescence is reported. It is shown that the so called anomalous luminescence of Ce-doped elpasolite Cs2LiLuCl6, which is characterized mainly by a very large Stokes shift and a very large band width, corresponds to an IVCT emission in Ce3+-Ce4+ pairs, from the 5deg orbital of Ce3+ to 4f orbitals of Ce4+. Its Stokes shift is the sum of the large reorganization energies of the Ce4+ and Ce3+ centers formed after the fixed-nuclei electron transfer and it is equal to the energy of the IVCT absorption commonly found in mixed-valence compounds, which is predicted to exist in this material and to be slightly larger than 10000 cm-1. The large band width is the consequence of the large offset between the minima of the Ce3+-Ce4+ and Ce4+-Ce3+ pairs along the electron transfer reaction coordinate. This offset is approximately 2*sqrt(3) times the difference of Ce-Cl equilibrium distances in the Ce3+ and Ce4+ centers. It is shown that the energies of the peaks and the...

  4. Exchange bias effect in Au-Fe3O4 dumbbell nanoparticles induced by the charge transfer from gold

    Science.gov (United States)

    Feygenson, Mikhail; Bauer, John C.; Gai, Zheng; Marques, Carlos; Aronson, Meigan C.; Teng, Xiaowei; Su, Dong; Stanic, Vesna; Urban, Volker S.; Beyer, Kevin A.; Dai, Sheng

    2015-08-01

    We have studied the origin of the exchange bias effect in the Au-Fe3O4 dumbbell nanoparticles in two samples with different sizes of the Au seed nanoparticles (4.1 and 2.7 nm) and same size of Fe3O4 nanoparticles (9.8 nm). The magnetization, small-angle neutron-scattering, synchrotron x-ray diffraction, and scanning transmission electron microscope measurements determined the antiferromagnetic FeO wüstite phase within Fe3O4 nanoparticles, originating at the interface with the Au nanoparticles. The interface between antiferromagnetic FeO and ferrimagnetic Fe3O4 is giving rise to the exchange bias effect. The strength of the exchange bias fields depends on the interfacial area and lattice mismatch between both phases. We propose that the charge transfer from the Au nanoparticles is responsible for a partial reduction of the Fe3O4 into the FeO phase at the interface with Au nanoparticles. The Au-O bonds are formed, presumably across the interface to accommodate an excess of oxygen released during the reduction of magnetite.

  5. Exchange bias effect in Au-Fe3O4 dumbbell nanoparticles induced by the charge transfer from gold

    Energy Technology Data Exchange (ETDEWEB)

    Feygenson, Mikhail; Bauer, John C.; Gai, Zheng; Marques, Carlos; Aronson, Meigan C.; Teng, Xiaowei; Su, Dong; Stanic, Vesna; Urban, Volker S.; Beyer, Kevin A.; Dai, Sheng

    2015-08-10

    We have studied the origin of the exchange bias effect in the Au-Fe3O4 dumbbell nanoparticles in two samples with different sizes of the Au seed nanoparticles (4.1 and 2.7 nm) and same size of Fe3O4 nanoparticles (9.8 nm). The magnetization, small-angle neutron-scattering, synchrotron x-ray diffraction, and scanning transmission electron microscope measurements determined the antiferromagnetic FeO wustite phase within Fe3O4 nanoparticles, originating at the interface with the Au nanoparticles. The interface between antiferromagnetic FeO and ferrimagnetic Fe3O4 is giving rise to the exchange bias effect. The strength of the exchange bias fields depends on the interfacial area and lattice mismatch between both phases. We propose that the charge transfer from the Au nanoparticles is responsible for a partial reduction of the Fe3O4 into the FeO phase at the interface with Au nanoparticles. The Au-O bonds are formed, presumably across the interface to accommodate an excess of oxygen released during the reduction of magnetite

  6. Spectrophotometric studies on the charge-transfer interaction between p-nitroaniline with chloranilic acid as π-acceptor in different polar solvents

    Science.gov (United States)

    Singh, Neeti; Ahmad, Afaq

    2017-01-01

    The charge transfer interaction between the donor p-nitroaniline with the acceptor chloranilic acid has been studied spectrophotometrically in various solvents such as chloroform, ethanol, and methanol at room temperature. The results indicate that formation of CTC in non-polar solvent is high. The stoichiometry of the complex was found to be 1:1 ratio by straight-line method between donor and acceptor with maximum absorption bands. The data are discussed in terms of formation constant (KCT), molar extinction coefficient (εCT), standard free energy (ΔG), oscillator strength (f), transition dipole moment (μN), resonance energy (RN) and ionization potential (ID). The results indicate that the formation constant (KCT) for the complex was shown to be dependent upon the nature of electron acceptor, donor and polarity of solvents that were used. The formation of the complex has been confirmed by UV-visible, FT-IR, and 1H NMR techniques.

  7. Short-lived charge-transfer excitons in organic photovoltaic cells studied by high-field magneto-photocurrent.

    Science.gov (United States)

    Devir-Wolfman, Ayeleth H; Khachatryan, Bagrat; Gautam, Bhoj R; Tzabary, Lior; Keren, Amit; Tessler, Nir; Vardeny, Z Valy; Ehrenfreund, Eitan

    2014-07-29

    The main route of charge photogeneration in efficient organic photovoltaic cells based on bulk hetero-junction donor-acceptor blends involves short-lived charge-transfer excitons at the donor-acceptor interfaces. The cell efficiency is critically affected by the charge-transfer exciton recombination and dissociation processes. By measuring the magneto-photocurrent under ambient conditions at room temperature, we show here that magnetic field-induced spin-mixing among the charge-transfer exciton spin sublevels occurs in fields up to at least 8.5 Tesla. The resulting magneto-photocurrent increases at high fields showing non-saturating behaviour up to the highest applied field. We attribute the observed high-field spin-mixing mechanism to the difference in the donor-acceptor g-factors. The non-saturating magneto-photocurrent response at high field indicates that there exist charge-transfer excitons with lifetime in the sub-nanosecond time domain. The non-Lorentzian high-field magneto-photocurrent response indicates a dispersive decay mechanism that originates due to a broad distribution of charge-transfer exciton lifetimes.

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

    Science.gov (United States)

    Krapf, Sebastian; Koslowski, Thorsten; Steinbrecher, Thomas

    2010-08-28

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

  9. High-speed charge transfer pinned-photodiode for a CMOS time-of-flight range image sensor

    Science.gov (United States)

    Takeshita, Hiroaki; Sawada, Tomonari; Iida, Tetsuya; Yasutomi, Keita; Kawahito, Shoji

    2010-01-01

    This paper presents a structure and method of range calculation for CMOS time-of-flight(TOF) range image sensors using pinned photodiodes. In the proposed method, a LED light with short pulse width and small duty ratio irradiates the objects and a back-reflected light is received by the CMOS TOF range imager.Each pixel has a pinned photodiode optimized for high speed charge transfer and unwanted charge draining. In TOF range image sensors, high speed charge transfer from the light receiving part to a charge accumulator is essential.It was found that the fastest charge transfer can be realized when the lateral electric field along the axis of charge transfer is constant and this conditon is met when the shape of the diode exactly follows the relationship between the fully-depleted potential and width. A TOF range imager prototype is designed and implemented with 0.18um CMOS image sensor technology with pinned photodiode 4transistor(T) pixels. The measurement results show that the charge transfer time is a few ns from the pinned photodiode to a charge accumulator.

  10. Ground-state oxygen holes and the metal-insulator transition in the negative charge-transfer rare-earth nickelates

    Science.gov (United States)

    Bisogni, Valentina; Catalano, Sara; Green, Robert J.; Gibert, Marta; Scherwitzl, Raoul; Huang, Yaobo; Strocov, Vladimir N.; Zubko, Pavlo; Balandeh, Shadi; Triscone, Jean-Marc; Sawatzky, George; Schmitt, Thorsten

    2016-10-01

    The metal-insulator transition and the intriguing physical properties of rare-earth perovskite nickelates have attracted considerable attention in recent years. Nonetheless, a complete understanding of these materials remains elusive. Here we combine X-ray absorption and resonant inelastic X-ray scattering (RIXS) spectroscopies to resolve important aspects of the complex electronic structure of rare-earth nickelates, taking NdNiO3 thin film as representative example. The unusual coexistence of bound and continuum excitations observed in the RIXS spectra provides strong evidence for abundant oxygen holes in the ground state of these materials. Using cluster calculations and Anderson impurity model interpretation, we show that distinct spectral signatures arise from a Ni 3d8 configuration along with holes in the oxygen 2p valence band, confirming suggestions that these materials do not obey a conventional positive charge-transfer picture, but instead exhibit a negative charge-transfer energy in line with recent models interpreting the metal-insulator transition in terms of bond disproportionation.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-11-16

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

  12. Highly efficient ZnO/Au Schottky barrier dye-sensitized solar cells: Role of gold nanoparticles on the charge-transfer process

    Directory of Open Access Journals (Sweden)

    Tanujjal Bora

    2011-10-01

    Full Text Available Zinc oxide (ZnO nanorods decorated with gold (Au nanoparticles have been synthesized and used to fabricate dye-sensitized solar cells (DSSC. The picosecond-resolved, time-correlated single-photon-count (TCSPC spectroscopy technique was used to explore the charge-transfer mechanism in the ZnO/Au-nanocomposite DSSC. Due to the formation of the Schottky barrier at the ZnO/Au interface and the higher optical absorptions of the ZnO/Au photoelectrodes arising from the surface plasmon absorption of the Au nanoparticles, enhanced power-conversion efficiency (PCE of 6.49% for small-area (0.1 cm2 ZnO/Au-nanocomposite DSSC was achieved compared to the 5.34% efficiency of the bare ZnO nanorod DSSC. The TCSPC studies revealed similar dynamics for the charge transfer from dye molecules to ZnO both in the presence and absence of Au nanoparticles. A slower fluorescence decay associated with the electron recombination process, observed in the presence of Au nanoparticles, confirmed the blocking of the electron transfer from ZnO back to the dye or electrolyte by the Schottky barrier formed at the ZnO/Au interface. For large area DSSC (1 cm2, ~130% enhancement in PCE (from 0.50% to 1.16% was achieved after incorporation of the Au nanoparticles into the ZnO nanorods.

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

    Science.gov (United States)

    Zou, Yunlong; Holmes, Russell J

    2015-08-26

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

  14. Engineering high charge transfer n-doping of graphene electrodes and its application to organic electronics.

    Science.gov (United States)

    Sanders, Simon; Cabrero-Vilatela, Andrea; Kidambi, Piran R; Alexander-Webber, Jack A; Weijtens, Christ; Braeuninger-Weimer, Philipp; Aria, Adrianus I; Qasim, Malik M; Wilkinson, Timothy D; Robertson, John; Hofmann, Stephan; Meyer, Jens

    2015-08-14

    Using thermally evaporated cesium carbonate (Cs2CO3) in an organic matrix, we present a novel strategy for efficient n-doping of monolayer graphene and a ∼90% reduction in its sheet resistance to ∼250 Ohm sq(-1). Photoemission spectroscopy confirms the presence of a large interface dipole of ∼0.9 eV between graphene and the Cs2CO3/organic matrix. This leads to a strong charge transfer based doping of graphene with a Fermi level shift of ∼1.0 eV. Using this approach we demonstrate efficient, standard industrial manufacturing process compatible graphene-based inverted organic light emitting diodes on glass and flexible substrates with efficiencies comparable to those of state-of-the-art ITO based devices.

  15. Supercell convergence of charge-transfer energies in pentacene molecular crystals from constrained DFT

    CERN Document Server

    Turban, David H P; O'Regan, David D; Hine, Nicholas D M

    2016-01-01

    Singlet fission (SF) is a multi-exciton generation process that could be harnessed to improve the efficiency of photovoltaic devices. Experimentally, systems derived from the pentacene molecule have been shown to exhibit ultrafast SF with high yields. Charge-transfer (CT) configurations are likely to play an important role as intermediates in the SF process in these systems. In molecular crystals, electrostatic screening effects and band formation can be significant in lowering the energy of CT states, enhancing their potential to effectively participate in SF. In order to simulate these, it desirable to adopt a computational approach which is acceptably accurate, relatively inexpensive, which and scales well to larger systems, thus enabling the study of screening effects. We propose a novel, electrostatically-corrected constrained Density Functional Theory (cDFT) approach as a low-cost solution to the calculation of CT energies in molecular crystals such as pentacene. Here we consider an implementation in th...

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

    Directory of Open Access Journals (Sweden)

    Rebecca Boll

    2016-07-01

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

  17. Charge-Transfer Effects in Ligand Exchange Reactions of Au25 Monolayer-Protected Clusters.

    Science.gov (United States)

    Carducci, Tessa M; Blackwell, Raymond E; Murray, Royce W

    2015-04-16

    Reported here are second-order rate constants of associative ligand exchanges of Au25L18 nanoparticles (L = phenylethanethiolate) of various charge states, measured by proton nuclear magnetic resonance at room temperature and below. Differences in second-order rate constants (M(-1) s(-1)) of ligand exchange (positive clusters ∼1.9 × 10(-5) versus negative ones ∼1.2 × 10(-4)) show that electron depletion retards ligand exchange. The ordering of rate constants between the ligands benzeneselenol > 4-bromobenzene thiol > benzenethiol reveals that exchange is accelerated by higher acidity and/or electron donation capability of the incoming ligand. Together, these observations indicate that partial charge transfer occurs between the nanoparticle and ligand during the exchange and that this is a rate-determining effect in the process.

  18. A Model of Charge Transfer Excitons: Diffusion, Spin Dynamics, and Magnetic Field Effects

    CERN Document Server

    Lee, Chee Kong; Willard, Adam P

    2016-01-01

    In this letter we explore how the microscopic dynamics of charge transfer (CT) excitons are influenced by the presence of an external magnetic field in disordered molecular semiconductors. This influence is driven by the dynamic interplay between the spin and spatial degrees of freedom of the electron-hole pair. To account for this interplay we have developed a numerical framework that combines a traditional model of quantum spin dynamics with a coarse-grained model of stochastic charge transport. This combination provides a general and efficient methodology for simulating the effects of magnetic field on CT state dynamics, therefore providing a basis for revealing the microscopic origin of experimentally observed magnetic field effects. We demonstrate that simulations carried out on our model are capable of reproducing experimental results as well as generating theoretical predictions related to the efficiency of organic electronic materials.

  19. Optical switching of electric charge transfer pathways in porphyrin: a light-controlled nanoscale current router.

    Science.gov (United States)

    Thanopulos, Ioannis; Paspalakis, Emmanuel; Yannopapas, Vassilios

    2008-11-05

    We introduce a novel molecular junction based on a thiol-functionalized porphyrin derivative with two almost energetically degenerate equilibrium configurations. We show that each equilibrium structure defines a pathway of maximal electric charge transfer through the molecular junction and that these two conduction pathways are spatially orthogonal. We further demonstrate computationally how to switch between the two equilibrium structures of the compound by coherent light. The optical switching mechanism is presented in the relevant configuration subspace of the compound, and the corresponding potential and electric dipole surfaces are obtained by ab initio methods. The laser-induced isomerization takes place in two steps in tandem, while each step is induced by a two-photon process. The effect of metallic electrodes on the electromagnetic irradiation driving the optical switching is also investigated. Our study demonstrates the potential for using thiol-functionalized porphyrin derivatives for the development of a light-controlled nanoscale current router.

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

    Institute of Scientific and Technical Information of China (English)

    GUO Fu-Quan; YANG Jun; ZHANG Qi-Jin; MING Hai

    2005-01-01

    @@ We report on a novel organic chromophore with symmetric twisted intramolecular charge transfer (TICT) state on excitation. The properties of nonlinear transmission induced by three-photon absorption (3PA) are demonstrated pumped with nanosecond laser pulse. Large 3PA cross sections as high as the order of 10-74 cm6s2have been obtained for nanosecond and picosecond laser pulses at 1064 nm from intensity-dependent transmission measurements. Similar two emissive behaviours from one-photon and three-photon excited fluorescence spectra indicate that the linear and nonlinear fluorescences share the same TICT relaxation process from the excited states. The intensity dependence of upconversion fluorescence on the incident intensity obeys the cubic law that characterizes the three-photon absorption.