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Sample records for de-fg02-86er13504 photoinduced electron

  1. Photo-induced electron transfer method

    DOEpatents

    Wohlgemuth, R.; Calvin, M.

    1984-01-24

    The efficiency of photo-induced electron transfer reactions is increased and the back transfer of electrons in such reactions is greatly reduced when a photo-sensitizer zinc porphyrin-surfactant and an electron donor manganese porphyrin-surfactant are admixed into phospholipid membranes. The phospholipids comprising said membranes are selected from phospholipids whose head portions are negatively charged. Said membranes are contacted with an aqueous medium in which an essentially neutral viologen electron acceptor is admixed. Catalysts capable of transferring electrons from reduced viologen electron acceptor to hydrogen to produce elemental hydrogen are also included in the aqueous medium. An oxidizable olefin is also admixed in the phospholipid for the purpose of combining with oxygen that coordinates with oxidized electron donor manganese porphyrin-surfactant.

  2. Photo-induced electron transfer method

    DOEpatents

    Wohlgemuth, Roland; Calvin, Melvin

    1984-01-01

    The efficiency of photo-induced electron transfer reactions is increased and the back transfer of electrons in such reactions is greatly reduced when a photo-sensitizer zinc porphyrin-surfactant and an electron donor manganese porphyrin-surfactant are admixed into phospho-lipid membranes. The phospholipids comprising said membranes are selected from phospholipids whose head portions are negatively charged. Said membranes are contacted with an aqueous medium in which an essentially neutral viologen electron acceptor is admixed. Catalysts capable of transfering electrons from reduced viologen electron acceptor to hydrogen to produce elemental hydrogen are also included in the aqueous medium. An oxidizable olefin is also admixed in the phospholipid for the purpose of combining with oxygen that coordinates with oxidized electron donor manganese porphyrin-surfactant.

  3. Photoinduced electron transfer in ordered polymers

    SciTech Connect

    Jones, G. II.

    1991-12-01

    Long range photoinduced electron transfer between electron donor and acceptor groups is of considerable current interest in terms of strategies for artificial photosynthesis and studies regarding the redox properties of proteins. As part of an extensive study of long range electron transfer involving biopolymers, we have carried out this year investigations of the assembly of electron transfer agents in a system of model short peptides. Also studied is a polyelectrolyte that can adopt a helical conformation when electrostatically complexed with organic dye counter-ions. The principal interest in these systems has to do with the well ordered secondary structures adopted by peptide polymers, and the capabilities for synthetic modification of peptide side chains and end groups with chromophores or electroactive substituents. The present report gives a brief account of the following elements of work related to photochemical electron transfer themes: (1) the synthesis and photochemical characterization of chromophore-bound peptides and amino acid model compounds based on the amino acids, tryptophan and the spacer residue, alanine (Ala); (2) the study of binding of the cationic organic dye to a peptide electrolyte, for which cooperative dye loading and helix formation is important; and (3) completion of the synthesis of a new series of acridinium chromophores that have rod-like'' arrangements of inked aryl rings for assembly of electron donor-acceptor systems that will exhibit especially long lived charge separation.

  4. Photoinduced electron transfer across molecular bridges: electron- and hole-transfer superexchange pathways.

    PubMed

    Natali, Mirco; Campagna, Sebastiano; Scandola, Franco

    2014-06-21

    Photoinduced electron transfer plays key roles in many areas of chemistry. Superexchange is an effective model to rationalize photoinduced electron transfer, particularly when molecular bridges between donor and acceptor subunits are present. In this tutorial review we discuss, within a superexchange framework, the complex role played by the bridge, with an emphasis on differences between thermal and photoinduced electron transfer, oxidative and reductive photoinduced processes, charge separation and charge recombination. Modular bridges are also considered, with specific attention to the distance dependence of donor-acceptor electronic coupling and electron transfer rate constants. The possibility of transition, depending on the bridge energetics, from coherent donor-acceptor electron transfer to incoherent charge injection and hopping through the bridge is also discussed. Finally, conceptual analogies between bridge effects in photoinduced electron transfer and optical intervalence transfer are outlined. Selected experimental examples, instrumental to illustration of the principles, are discussed.

  5. Photo-induced electron-transfer reactions in heterogeneous media

    NASA Astrophysics Data System (ADS)

    Yang, J. M.

    1981-11-01

    The conversion of solar energy into chemical energy was pursued by two approaches. One is the photo-induced electron transfer reactions in heterogeneous media, and the other is the photo-decomposition of water with liquid-junction solar cells. Photo-induced electron-transfer reactions in heterogeneous media with colloidal silica or poly-acrylate were studied by flash photolysis. In an effort to illustrate that small band-gap semiconductors can be protected from photo-corrosion through surface modification, the surface of polycrystalline ZnO was chemically coated with zinc phthalocyanine and the electron-transfer process across the coated ZnO-electrolyte interface was studied by photo-electrochemical techniques.

  6. Ultrafast Photoinduced Electron Transfer from Peroxide Dianion.

    PubMed

    Anderson, Bryce L; Maher, Andrew G; Nava, Matthew; Lopez, Nazario; Cummins, Christopher C; Nocera, Daniel G

    2015-06-18

    The encapsulation of peroxide dianion by hexacarboxamide cryptand provides a platform for the study of electron transfer of isolated peroxide anion. Photoinitiated electron transfer (ET) between freely diffusing Ru(bpy)3(2+) and the peroxide dianion occurs with a rate constant of 2.0 × 10(10) M(-1) s(-1). A competing electron transfer quenching pathway is observed within an ion pair. Picosecond transient spectroscopy furnishes a rate constant of 1.1 × 10(10) s(-1) for this first-order process. A driving force dependence for the ET rate within the ion pair using a series of Ru(bpy)3(2+) derivatives allows for the electronic coupling and reorganization energies to be assessed. The ET reaction is nonadiabatic and dominated by a large inner-sphere reorganization energy, in accordance with that expected for the change in bond distance accompanying the conversion of peroxide dianion to superoxide anion.

  7. Photoinduced electron transfer in ordered polymers

    SciTech Connect

    Jones, G. II.

    1990-10-20

    Photochemical studies on organic polymers or biopolymers (particularly synthetic peptides) that have been modified by covalent attachment (or other means of binding) of organic chromophores and electron transfer agents are described. Specific projects involve are: peptide conjugates bearing electroactive residues such as tryptophan and specifically labeled at the N- or C-terminus of peptide chains; the electrostatic binding of organic dyes to poly-electrolytes (polyacrylates) for which the formation of dimeric aggregates of bound dye that display unusual photophysical and electron transfer properties is important; a study of the binding of dyes and electron transfer agents to the protein mimic,'' polyvinyl-2-pyrrolidinone (PVP), in hydrophobic domains that depend on specific H-bond interaction; and completion of an earlier study having to do with the triplet state properties of charge-transfer (CT) complexes of a high potential quinone and various electron donors (investigation of the properties of triplet (contact) radical-ion pairs). 13 refs., 5 figs., 2 tabs.

  8. Distance dependence in photo-induced intramolecular electron transfer

    NASA Astrophysics Data System (ADS)

    Larsson, Sven; Volosov, Andrey

    1986-09-01

    The distance dependence of the rate of photo-induced electron transfer reactions is studied. A quantum mechanical method CNDO/S is applied to a series of molecules recently investigated by Hush et al. experimentally. The calculations show a large interaction through the saturated bridge which connects the two chromophores. The electronic matrix element HAB decreases a factor 10 in about 4 Å. There is also a decrease of the rate due to less exothermicity for the longer molecule. The results are in fair agreement with the experimental results.

  9. Photoinduced electron transfer in ordered polymers

    SciTech Connect

    Jones, G. II.

    1993-01-01

    The present report gives a brief account of the following elements of work related to photochemical electron transfer themes: (1) the synthesis and Photochemical characterization of chromophore-bound peptides and amino acid model compounds based on the amino acids, tryptophan and the spacer residue, alanine (Ala); (2) the study of binding of cationic organic dyes to a peptide electrolyte, for which cooperative dye loading and helix formation is important; (3) the completion of work on a new series of acridinium chromophores that have rod-like'' arrangements of linked aryl rings for assembly of electron donor-acceptor systems that exhibit long lived charge separation; and (4) use of the modified form of the peptide, poly-L-histidine, as a template for sulfide oxidation.

  10. Photoinduced electron transfer between benzyloxy dendrimer phthalocyanine and benzoquinone

    NASA Astrophysics Data System (ADS)

    Zhang, Tiantian; Ma, Dongdong; Pan, Sujuan; Wu, Shijun; Jiang, Yufeng; Zeng, Di; Yang, Hongqin; Peng, Yiru

    2016-10-01

    Photo-induced electron transfer (PET) is an important and fundamental process in natural photosynthesis. To mimic such interesting PET process, a suitable donor and acceptor couple were properly chosen. Dendrimer phthalocyanines and their derivatives have emerged as promising materials for artificial photosynthesis systems. In this paper, the electron transfer between the light harvest dendrimer phthalocyanine (donor) and the 1,4-benzoquinone (acceptor) was studied by UV/Vis and fluorescence spectroscopic methods. It was found that fluorescence of phthalocyanine was quenched by benzoquinone (BQ) via excited state electron transfer, from the phthalocyanine to the BQ upon excitation at 610 nm. The Stern-Volmer constant (KSV) of electron transfer was calculated. Our study suggests that this dendritic phthalocyanine is an effective new electron donor and transmission complex and could be used as a potential artificial photosynthesis system.

  11. Photoinduced electron transfer based ion sensing within an optical fiber.

    PubMed

    Englich, Florian V; Foo, Tze Cheung; Richardson, Andrew C; Ebendorff-Heidepriem, Heike; Sumby, Christopher J; Monro, Tanya M

    2011-01-01

    We combine suspended-core microstructured optical fibers with the photoinduced electron transfer (PET) effect to demonstrate a new type of fluorescent optical fiber-dip sensing platform for small volume ion detection. A sensor design based on a simple model PET-fluoroionophore system and small core microstructured optical fiber capable of detecting sodium ions is demonstrated. The performance of the dip sensor operating in a high sodium concentration regime (925 ppm Na(+)) and for lower sodium concentration environments (18.4 ppm Na(+)) is explored and future approaches to improving the sensor's signal stability, sensitivity and selectivity are discussed.

  12. Photoinduced Electron Transfer Process Visualized on Single Silver Nanoparticles.

    PubMed

    Lei, Gang; Gao, Peng Fei; Yang, Tong; Zhou, Jun; Zhang, Hong Zhi; Sun, Shan Shan; Gao, Ming Xuan; Huang, Cheng Zhi

    2017-02-28

    Understanding the photoinduced electron transfer (PET) mechanism is vital to improving the photoelectric conversion efficiency for solar energy materials and photosensitization systems. Herein, we visually demonstrate the PET process by real-time monitoring the photoinduced chemical transformation of p-aminothiophenol (p-ATP), an important SERS signal molecule, to 4,4'-dimercaptoazobenzene on single silver nanoparticles (AgNPs) with a localized surface plasmon resonance (LSPR) spectroscopy coupled dark-field microscopy. The bidirectional LSPR scattering spectral shifts bathochromically at first and hypsochromically then, which are caused by the electron transfer delay of p-ATP, disclose the PET path from p-ATP to O2 through AgNPs during the reaction, and enable us to digitalize the corresponding electron loss and gain on the surface of AgNP at different time periods. This visualized PET process could provide a simple and efficient approach to explore the nature of PET and help to interpret the SERS mechanism in terms of p-ATP.

  13. DNA Intercalated Psoralen Undergoes Efficient Photoinduced Electron Transfer.

    PubMed

    Fröbel, Sascha; Reiffers, Anna; Torres Ziegenbein, Christian; Gilch, Peter

    2015-04-02

    The interaction of psoralens with DNA has been used for therapeutic and research purposes for decades. Still the photoinduced behavior of psoralens in DNA has never been observed directly. Femtosecond transient absorption spectroscopy is used here to gain direct insight into the photophysics of a DNA-intercalated psoralen (4'-aminomethyl-4,5',8-trimethyl-psoralen (AMT)). Intercalation reduces the excited singlet lifetime of AMT to 4 ps compared with 1400 ps for AMT in water. This singlet quenching prohibits the population of the triplet state that is accessed in free AMT. Instead, a DNA to AMT electron transfer takes place. The resulting radical pair decays primarily via charge recombination with a time constant of 30 ps. The efficient electron transfer observed here reveals a completely new aspect of the psoralen-DNA interaction.

  14. Electron Donor-Acceptor Quenching and Photoinduced Electron Transfer for Coumarin Dyes.

    DTIC Science & Technology

    1983-10-31

    Mechanism of cousarin photodegradation . Ithe behavior of eoiuma dyes is water ad In aqueous detergent media,. and the effsects of medism aud, additives on...D-i36 345 ELECTRON DONOR-ACCEPTOR UENCHING AND PHOTOINDUCED i/i Ai ELECTRON TRANSFER FOR COUMARIN DYES (U) BOSTON UNIY MR DEPT OF CHEMISTRY G JONES...TYPE OF REPORT & PEIOD COVERED Electron Donor-acceptor Quenching and Photo- Technical, 1/1/82-10/31/82 induced Electron Transfer for Coumarin Dyes S

  15. Photoinduced Bimolecular Electron Transfer from Cyano Anions in Ionic Liquids.

    PubMed

    Wu, Boning; Liang, Min; Maroncelli, Mark; Castner, Edward W

    2015-11-19

    Ionic liquids with electron-donating anions are used to investigate rates and mechanisms of photoinduced bimolecular electron transfer to the photoexcited acceptor 9,10-dicyanoanthracene (9,10-DCNA). The set of five cyano anion ILs studied comprises the 1-ethyl-3-methylimidazolium cation paired with each of these five anions: selenocyanate, thiocyanate, dicyanamide, tricyanomethanide, and tetracyanoborate. Measurements with these anions dilute in acetonitrile and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide show that the selenocyanate and tricyanomethanide anions are strong quenchers of the 9,10-DCNA fluorescence, thiocyanate is a moderately strong quencher, dicyanamide is a weak quencher, and no quenching is observed for tetracyanoborate. Quenching rates are obtained from both time-resolved fluorescence transients and time-integrated spectra. Application of a Smoluchowski diffusion-and-reaction model showed that the complex kinetics observed can be fit using only two adjustable parameters, D and V0, where D is the relative diffusion coefficient between donor and acceptor and V0 is the value of the electronic coupling at donor-acceptor contact.

  16. Hetero-cycloreversions mediated by photoinduced electron transfer.

    PubMed

    Pérez-Ruiz, Raúl; Jiménez, M Consuelo; Miranda, Miguel A

    2014-04-15

    Discovered more than eight decades ago, the Diels-Alder (DA) cycloaddition (CA) remains one of the most versatile tools in synthetic organic chemistry. Hetero-DA processes are powerful methods for the synthesis of densely functionalized six-membered heterocycles, ubiquitous substructures found in natural products and bioactive compounds. These reactions frequently employ azadienes and oxadienes, but only a few groups have reported DA processes with thiadienes. The electron transfer (ET) version of the DA reaction, though less investigated, has emerged as a subject of increasing interest. In the last two decades, researchers have paid closer attention to radical ionic hetero-cycloreversions, mainly in connection with their possible involvement in the repair of pyrimidine(6-4)pyrimidone photolesions in DNA by photolyases. In biological systems, these reactions likely occur through a reductive photosensitization mechanism. In addition, photooxidation can lead to cycloreversion (CR) reactions, and researchers can exploit this strategy for DNA repair therapies. In this Account, we discuss electron-transfer (ET) mediated hetero-CR reactions. We focus on the oxidative and reductive ET splitting of oxetanes, azetidines, and thietanes. Photoinduced electron transfer facilitates the splitting of a variety of four-membered heterocycles. In this context, researchers have commonly examined oxetanes, both experimentally and theoretically. Although a few studies have reported the cycloreversion of azetidines and thietanes carried out under electron transfer conditions, the number of examples remains limited. In general, the cleavage of the ionized four-membered rings appears to occur via a nonconcerted two-step mechanism. The trapping of the intermediate 1,4-radical ions and transient absorption spectroscopy data support this hypothesis, and it explains the observed loss of stereochemistry in the products. In the initial step, either C-C or C-X bond breaking may occur, and the

  17. Photoinduced bimolecular electron transfer kinetics in small unilamellar vesicles

    SciTech Connect

    Choudhury, Sharmistha Dutta; Kumbhakar, Manoj; Nath, Sukhendu; Pal, Haridas

    2007-11-21

    Photoinduced electron transfer (ET) from N,N-dimethylaniline to some coumarin derivatives has been studied in small unilamellar vesicles (SUVs) of the phospholipid, DL-{alpha}-dimyristoyl-phosphatidylcholine, using steady-state and time-resolved fluorescence quenching, both below and above the phase transition temperature of the vesicles. The primary interest was to examine whether Marcus inversion [H. Sumi and R. A. Marcus, J. Chem. Phys. 84, 4894 (1986)] could be observed for the present ET systems in these organized assemblies. The influence of the topology of SUVs on the photophysical properties of the reactants and consequently on their ET kinetics has also been investigated. Absorption and fluorescence spectral data of the coumarins in SUVs and the variation of their fluorescence decays with temperature indicate that the dyes are localized in the bilayer of the SUVs. Time-resolved area normalized emission spectra analysis, however, reveals that the dyes are distributed in two different microenvironments in the SUVs, which we attribute to the two leaflets of the bilayer, one toward bulk water and the other toward the inner water pool. The microenvironments in the two leaflets are, however, not indicated to be that significantly different. Time-resolved anisotropy decays were biexponential for all the dyes in SUVs, and this has been interpreted in terms of the compound motion model according to which the dye molecules can experience a fast wobbling-in-cone type of motion as well as a slow overall rotating motion of the cone containing the molecule. The expected bimolecular diffusion-controlled rates in SUVs, as estimated by comparing the microviscosities in SUVs (determined from rotational correlation times) and that in acetonitrile solution, are much slower than the observed fluorescence quenching rates, suggesting that reactant diffusion (translational) does not play any role in the quenching kinetics in the present systems. Accordingly, clear inversions are

  18. Revising Intramolecular Photoinduced Electron Transfer (PET) from First-Principles.

    PubMed

    Escudero, Daniel

    2016-09-20

    Photoinduced electron transfer (PET) plays relevant roles in many areas of chemistry, including charge separation processes in photovoltaics, natural and artificial photosynthesis, and photoluminescence sensors and switches. As in many other photochemical scenarios, the structural and energetic factors play relevant roles in determining the rates and efficiencies of PET and its competitive photodeactivation processes. Particularly, in the field of fluorescent sensors and switches, intramolecular PET is believed (in many cases without compelling experimental proof) to be responsible of the quench of fluorescence. There is an increasing experimental interest in fluorophore's molecular design and on achieving optimal excitation/emission spectra, excitation coefficients, and fluorescence quantum yields (importantly for bioimaging purposes), but less efforts are devoted to fundamental mechanistic studies. In this Account, I revise the origins of the fluorescence quenching in some of these systems with state-of-the-art quantum chemical tools. These studies go beyond the common strategy of analyzing frontier orbital energy diagrams and performing PET thermodynamics calculations. Instead, the potential energy surfaces (PESs) of the lowest-lying excited states are explored with time-dependent density functional theory (TD-DFT) and complete active space self-consistent field (CASSCF) calculations and the radiative and nonradiative decay rates from the involved excited states are computed from first-principles using a thermal vibration correlation function formalism. With such a strategy, this work reveals the real origins of the fluorescence quenching, herein entitled as dark-state quenching. Dark states (those that do not absorb or emit light) are often elusive to experiments and thus, computational investigations can provide novel insights into the actual photodeactivation mechanisms. The success of the dark-state quenching mechanism is demonstrated for a wide variety of

  19. Distance dependence in photoinduced intramolecular electron transfer. Additional remarks and calculations

    NASA Astrophysics Data System (ADS)

    Larsson, Sven; Volosov, Andrey

    1987-12-01

    Rate constants for photoinduced intramolecular electron transfer are calculated for four of the molecules studied by Hush et al. The electronic factor is obtained in quantum chemical calculations using the CNDO/S method. The results agree reasonably well with experiments for the forward reaction. Possible reasons for the disagreement for the charge recombination process are offered.

  20. Photoinduced electron transfer reaction in polymer-surfactant aggregates: Photoinduced electron transfer between N,N-dimethylaniline and 7-amino coumarin dyes

    SciTech Connect

    Chakraborty, Anjan; Seth, Debabrata; Setua, Palash; Sarkar, Nilmoni

    2008-05-28

    Photoinduced electron transfer between coumarin dyes and N,N-dimethylaniline has been investigated by using steady state and picosecond time resolved fluorescence spectroscopy in sodium dodecyl sulphate (SDS) micelles and PVP-polyvinyl pyrrolidone (SDS) polymer-surfactant aggregates. A slower rate of electron transfer is observed in PVP-SDS aggregates than in polymer-free SDS micelles. A Marcus type inversion is observed in the correlation of free energy change in comparison with the electron transfer rate. The careful investigation reveals that C-151 deviates from the normal Marcus inverted region compared to its analogs C-152 and C-481 due to slower rotational relaxation and smaller translational diffusion coefficient.

  1. Photoinduced electron transfer from rail to rung within a self-assembled oligomeric porphyrin ladder

    SciTech Connect

    She, Chunxing; Lee, Suk Joong; McGarrah, James E.; Vura-Weis, Josh; Wasielewski, Michael; Chen, Hanning; Schatz, George C.; Ratner, Mark A.; Hupp, Joseph T.

    2010-01-01

    Photoinduced electron transfer in a self-assembled supramolecular ladder structure comprising oligomeric porphyrin rails and ligated dipyridyltetrazine rungs was characterized by transient absorption spectroscopy and transient direct current photoconductivity to be mainly from an oligomer (rail) to the center of a terminal tetrazine (rung), with the remaining hole being delocalized on the oligomer and subsequent charge recombination in 0.19 ns.

  2. Photoinduced electron transfer processes in homogeneous and microheterogeneous solutions

    SciTech Connect

    Whitten, D.G.

    1991-10-01

    The focus of the work described in this report is on single electron transfer reactions of excited states which culminate in the formation of stable or metastable even electron species. For the most part the studies have involved even electron organic substrates which are thus converted photochemically to odd electron species and then at some stage reconvert to even electron products. These reactions generally fall into two rather different categories. In one set of studies we have examined reactions in which the metastable reagents generated by single electron transfer quenching of an excited state undergo novel fragmentation reactions, chiefly involving C-C bond cleavage. These reactions often culminate in novel and potentially useful chemical reactions and frequently have the potential for leading to new chemical products otherwise unaffordable by conventional reaction paths. In a rather different investigation we have also studied reactions in which single electron transfer quenching of an excited state is followed by subsequent reactions which lead reversibly to metastable two electron products which, often stable in themselves, can nonetheless be reacted with each other or with other reagents to regenerate the starting materials with release of energy. 66 refs., 9 figs., 1 tab.

  3. Photoinduced Electron Transfer in Ordered Macromolecular Assemblies. Final report for May 1, 1988 - June 30, 2002

    SciTech Connect

    Jones, G.

    2005-02-11

    The final report describes studies over a 13 year period having to do with photoinduced electron transfer for active chromophores and redox agents, including assembly of the components in water soluble polymers or polypeptides. The findings include observation of long range charge separation and electron transport using laser phototransient spectroscopy. The systems targeted in these studies include peptide assemblies for which helical conformations and aggregation are documented. Oligomeric peptides modified with non-native redox active groups were also selected for investigation. Highly charged polymers or peptides were investigated as host agents that resemble proteins. The overall goal of these investigations focused on the design and characterization of systems capable of artificial photosynthesis.

  4. Photoinduced electron transfer in rigidly linked dimethoxynapthalene-N-methylpyridinium donor-acceptor molecules

    NASA Astrophysics Data System (ADS)

    Clayton, Andrew H. A.; Ghiggino, Kenneth P.; Wilson, Gerard J.; Keyte, Peter J.; Paddon-Row, Michael N.

    1992-07-01

    Photoinduced electron transfer (ET) is studied in a series of novel molecules containing a dimethoxynaphthalene (DMN) donor and either a pyridine (P) or N-methylpyridinium (P-Me +) acceptor covalently linked via a rigid nonbornalogous bridge ( n sigma bonds in length). ET rates of the order of 10 10 s -1 were measured for the DMN- n-P-Me + series ( n = 4, 6), while no appreciable ET was observed for the DMN- n-P compounds. Electronic and nuclear factors are discussed and the results rationalized in terms of Marcus—Hush and non-adiabatic ET theories.

  5. Role of coherence and delocalization in photo-induced electron transfer at organic interfaces

    PubMed Central

    Abramavicius, V.; Pranculis, V.; Melianas, A.; Inganäs, O.; Gulbinas, V.; Abramavicius, D.

    2016-01-01

    Photo-induced charge transfer at molecular heterojunctions has gained particular interest due to the development of organic solar cells (OSC) based on blends of electron donating and accepting materials. While charge transfer between donor and acceptor molecules can be described by Marcus theory, additional carrier delocalization and coherent propagation might play the dominant role. Here, we describe ultrafast charge separation at the interface of a conjugated polymer and an aggregate of the fullerene derivative PCBM using the stochastic Schrödinger equation (SSE) and reveal the complex time evolution of electron transfer, mediated by electronic coherence and delocalization. By fitting the model to ultrafast charge separation experiments, we estimate the extent of electron delocalization and establish the transition from coherent electron propagation to incoherent hopping. Our results indicate that even a relatively weak coupling between PCBM molecules is sufficient to facilitate electron delocalization and efficient charge separation at organic interfaces. PMID:27605035

  6. Photoinduced Electron Accumulation of Titanium Dioxide Nanoparticles Modified Electrodes

    NASA Astrophysics Data System (ADS)

    Miyoshi, Hirokazu; Sakamoto, Kensho; Kurashina, Masaru; Kanezaki, Eiji

    Titanium dioxide (TiO2) nanoparticles (Nps) were prepared by the hydrolysis of titanium tetraisopropoxide (TTIP) in 2-propanol with different water contents (0.5 vol% to 7.2 vol%) at 45 °C. The diameter of the Nps was estimated to be 1.5±0.5 nm (L-TiO2) and 3.0±0.6 nm (S-TiO2) from the onset wavelength in the absorption spectra and by transmission electron microscopy (TEM). A modified Pt electrode with a three-layered sandwich structure was prepared; the outermost and innermost layers were composed of S-TiO2 and L-TiO2, respectively, and the middle layer contained 1, 1'-dimethyl-4,4'-bipyridyl (MV2+)/Nafion®. Irradiation by a 500 W superhigh-pressure mercury lamp produced electrons in the conduction band of TiO2. An anodic current was observed after turning off the light. The mechanism by which anodic current is generated after turning off the radiation involves the reduction of MV2+ to MV+. by photogenerated electrons on the Nps and the diffusion of MV+. in the middle layer. After turning off the irradiation, MV+. transferred an electron to the Pt electrode via holes in the innermost layer or the conduction band of S-TiO2 coincidentally localized on the Pt electrode, resulting in the generation of the anodic current. The generation of MV+. was confirmed by the absorption spectra of MV+.. As a sacrificial reagent, 2-propanol (0.1 M) was used.

  7. Photoinduced electron transfer from dialkyl nitroxides to halogenated solvents

    SciTech Connect

    Chateauneuf, J. ); Lusztyk, J.; Ingold, K.U. )

    1990-02-02

    Laser flash photolysis (LFP) at wavelengths within the charge-transfer absorption present in CCl{sub 4} solutions of 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) yields the oxoammonium chloride of TEMPO, 1 ({lambda}{sub max} = 460 nm), and the trichloromethyl radical in an essentially instantaneous ({le}18 ps) process. The primary photochemical event is an electron transfer from TEMPO to CCl{sub 4}, and this is followed by immediate decomposition of the CCl{sub 4}{sup {sm bullet}{minus}} radical anion to Cl{sup {minus}} and Cl{sub 3}C{sup {sm bullet}}. An independent synthesis of 1 confirmed that the absorption attributed to this species has been correctly assigned. The formation of Cl{sub 3}C{sup {sm bullet}} was inferred by its trapping by molecular oxygen. LFP of TEMPO in other halogenated solvents and of other nitroxides in halogenated solvents has confirmed the generality of these photoreactions.

  8. Molecular orbital assistance in the design of intramolecular and photoinduced electron transfer systems

    NASA Astrophysics Data System (ADS)

    Petsalakis, Ioannis D.; Theodorakopoulos, Giannoula

    2012-02-01

    A theoretical approach is described for the design of donor-acceptor intramolecular charge transfer (ICT) systems and for photoinduced electron transfer (PET) hybrids of fullerene, based on orbital level diagrams of the separate donor and acceptor moieties. Minimization of the HOMO-LUMO (highest occupied-lowest unoccupied orbital) gap in ICT systems, translates to a requirement for near degeneracy of the HOMO of the donor and LUMO of the acceptor, determined separately for the two moieties by density functional theory calculations. Similarly, near degeneracy of the LUMO of the donor and LUMO of the acceptor moieties would indicate the possibility of PET in the combined hybrid.

  9. Photoinduced electron transfer interaction of anthraquinones with aniline quenchers: Influence of methyl substitution in aniline donors

    NASA Astrophysics Data System (ADS)

    Sivakumar, V.; Ponnamma, Deepalekshmi; Hussein, Yasser H. A.

    2017-02-01

    Photoinduced electron transfer between triplet state of 9,10-anthraquinone (AQ) and its two derivatives: 2-chloro-9,10-anthraquinone (CAQ) and sodium anthraquinone-2-sulfonate (AQS) and ground state aniline (AN) and its dimethyl substitutions: 2,3-dimethylaniline (2,3-DMA), 2,6-dimethylaniline (2,6-DMA), 3,5-dimethylaniline (3,5-DMA) and N,N-dimethylaniline (N,N-DMA) is studied using nanosecond laser flash photolysis at room temperature. Detection of radical bands of quinone anions and aniline cations along with their formation and/or decay kinetics are used to confirm the electron transfer (ET) process. In MeCN medium, AN quenches the triplet state of CAQ (CAQT) but not the triplets AQT or AQST. However in aqueous medium, AN quenches AQST and forms radical ion pair. All the DMAs can react through ET with all the triplet quinones at different degrees of efficiency in MeCN medium. Noticeably, the ring substituted DMAs are less efficient in electron donation to AQT or AQST while the N,N-DMA shows high efficiency in donating electron to all triplet quinones in MeCN medium. Charge distribution of donor molecules, in MeCN medium is calculated using density functional theory (DFT), and shows an enhancement of electron density of the ring of N,N-DMA, making it an ideal electron donor for ET studies compared to other DMAs. This systematic selection and usage of anilines with electrochemically tunable quinones can be viewed as a working model of donor-acceptor system that can be utilized in photoinduced ET applications.

  10. Photoinduced 2-way electron transfer in composites of metal nanoclusters and semiconductor quantum dots

    NASA Astrophysics Data System (ADS)

    Mondal, Navendu; Paul, Sneha; Samanta, Anunay

    2016-07-01

    In order to explore the potential of nanocomposites comprising semiconductor quantum dots (QDs) and metal nanoclusters (NCs) in photovoltaic and catalytic applications, the interaction between CdTe QDs and gold NCs, Au10 and Au25, stabilized by histidine, bovine serum albumin (BSA) and glutathione, is studied by an ultrafast transient absorption (TA) technique. Temporal and spectral studies of the transients reveal photoinduced 2-way electron transfer between the two constituents of the nanocomposites, where Au NCs, which generally act as electron donors when used as photosensitizers, perform the role of the efficient electron acceptor. Interestingly, it is found that the electron transfer dynamics in these composites is governed not by the distance of separation of the constituents but by the nature of the surface capping ligands. Despite a large separation between the QDs and NCs in a giant BSA-capped system, a higher electron transfer rate in this composite suggests that unlike other smaller capping agents, which act more like insulators, BSA allows much better electron conduction, as indicated previously.In order to explore the potential of nanocomposites comprising semiconductor quantum dots (QDs) and metal nanoclusters (NCs) in photovoltaic and catalytic applications, the interaction between CdTe QDs and gold NCs, Au10 and Au25, stabilized by histidine, bovine serum albumin (BSA) and glutathione, is studied by an ultrafast transient absorption (TA) technique. Temporal and spectral studies of the transients reveal photoinduced 2-way electron transfer between the two constituents of the nanocomposites, where Au NCs, which generally act as electron donors when used as photosensitizers, perform the role of the efficient electron acceptor. Interestingly, it is found that the electron transfer dynamics in these composites is governed not by the distance of separation of the constituents but by the nature of the surface capping ligands. Despite a large separation

  11. Photoinduced field-assisted electron emission from dielectric-coated electrodes into gases

    NASA Astrophysics Data System (ADS)

    Josepson, R.; Laan, M.; Aarik, J.; Kasikov, A.

    2008-07-01

    A photoinduced non-self-sustained discharge in a point-plane gap at near-atmospheric pressures in nitrogen and nitrogen-oxygen mixture was studied. Molybdenum and platinum points were coated with thin layers of MgO and TiO2 of different thicknesses. Static current-voltage characteristics were recorded at different intensities of triggering light, layer thickness and gas pressure. The common regularities of current-voltage characteristics were independent of the electrode/coating combinations used. The studies showed that the field-assisted two-step model of emission describes the experimental findings. The electron emission is controlled by Schottky and Fowler-Nordheim mechanisms at the metal-dielectric interface and by a recombination of positive ions with 'hot' and free electrons near the dielectric-gas interface.

  12. Inter-Fullerene Electronic Coupling Controls the Efficiency of Photoinduced Charge Generation in Organic Bulk Heterojunctions

    SciTech Connect

    Larson, Bryon W.; Reid, Obadiah G.; Coffey, David C.; Avdoshenko, Stanislav M.; Popov, Alexey A.; Boltalina, Olga V.; Strauss, Steven H.; Kopidakis, Nikos; Rumbles, Garry

    2016-09-26

    Photoinduced charge generation (PCG) dynamics are notoriously difficult to correlate with specific molecular properties in device relevant polymer:fullerene organic photovoltaic blend films due to the highly complex nature of the solid state blend morphology. Here, this study uses six judiciously selected trifluoromethylfullerenes blended with the prototypical polymer poly(3-hexylthiophene) and measure the PCG dynamics in 50 fs-500 ns time scales with time-resolved microwave conductivity and femtosecond transient absorption spectroscopy. The isomeric purity and thorough chemical characterization of the fullerenes used in this study allow for a detailed correlation between molecular properties, driving force, local intermolecular electronic coupling and, ultimately, the efficiency of PCG yield. The findings show that the molecular design of the fullerene not only determines inter-fullerene electronic coupling, but also influences the decay dynamics of free holes in the donor phase even when the polymer microstructure remains unchanged.

  13. Configuration-Dependent Photoinduced Electron Transfer in Diastereomeric Naphthalene-Amino-Naphthalene Triads.

    PubMed

    Nuin, Edurne; Sastre, German; Pischel, Uwe; Andreu, Inmaculada; Miranda, Miguel A

    2015-09-07

    Novel diastereomeric triads containing two naphthalene chromophores have been designed in which an electron-donating amine moiety is covalently integrated into the connecting bridge. Photophysical studies (steady-state and time-resolved fluorescence) in solvents of different polarity have been performed. A remarkable stereodifferentiation in the intramolecular fluorescence quenching was found in acetonitrile. Laser flash photolysis gave rise to naphthalene-derived radical cations, which were also quenched by the amine with an even higher degree of stereodifferentiation. The results are in agreement with thermodynamic estimations and indicate that photoinduced electron transfer (PET) is the main quenching pathway. Furthermore, theoretical calculations have allowed us to explain the experimentally observed stereodifferentiation in PET quenching.

  14. Effect of temperature, energy gap, and distortion of potential surfaces on photoinduced intramolecular electron transfer

    SciTech Connect

    Islampour, R.; Alden, R.G.; Wu, G.Y.C.; Lin, S.H. )

    1993-07-01

    We report the quantitative examination of the effect of distortion of potential energy surfaces and the temperature effect on photoinduced intramolecular electron transfer (PIET) as a function of electronic energy gap. The results demonstrate the importance of distorted oscillators in determining the dependence of the rate of PIET on the energy gap. This phenomenon may in some cases lead to misinterpretations of experimental data, when undistorted oscillators are assumed to be involved in the PIET process. The condition for observing the linear (rather than parabolic) dependence of the ET rate will be determined using the multimode model. The inclusion of multivibrational modes in the nuclear factors results in energy gap behavior, which is markedly different from the single mode case. Finally, a comparison between PIET and internal conversion is discussed. 25 refs., 5 figs., 3 tabs.

  15. Directional photoinduced electron transfer in paraquat silicate thin films containing entrapped ruthenium(II)-tris(bathophenanthroline-disulfonate).

    PubMed

    Trammell, Scott A; Tsoi, Stanislav; Martin, Brett; Melde, Brian J; Moore, Martin M; Dressick, Walter J

    2011-10-28

    We have demonstrated directional photoinduced electron transfer in paraquat silicate thin films containing entrapped ruthenium(II)-tris(bathophenanthroline-disulfonate (RuBPS). The films were made by electrochemically-induced hydrolysis of a silane analogue of paraquat with ruthenium(II)-tris(bathophenanthroline-disulfonate as its ion pair.

  16. Photo-induced electronic properties in single quantum well system: effect of excitonic lifetime

    NASA Astrophysics Data System (ADS)

    Patwari, Jayita; Ghadi, Hemant; Sardar, Samim; Singhal, Jashan; Tongbram, Binita; Shyamal, Sanjib; Bhattacharya, Chinmoy; Chakrabarti, Subhananda; Pal, Samir Kumar

    2017-01-01

    In the present study, we have established a correlation between the photo-induced electronic phenomena and excited state lifetime of the photo generated carriers in double barrier Al0.3Ga0.7As\\GaAs quantum well (QW) structures. The excited state lifetime was measured experimentally by picosecond time resolved photoluminescence spectroscopy for two samples with different well widths (5.3 nm and 16.5 nm). The faster nonradiative decay time of the narrower well can be attributed to the facile escape of electrons from well to barrier due to lower associated energy compared to that of the thicker well which resembles the simulated results of the energy level distribution. The proposed mechanism of carrier escape is further proven from the higher value of unconventional excitonic capacitance value in the thicker well, measured by impedance spectroscopy. The dependence of photo-induced capacitance on well thickness is explained by the lifetime of the excited carriers in this study. Dependence of the photo-generated capacitance (C) on externally applied bias voltage (V) was also studied to quantitatively establish a proportional relation between the carrier holding capacity of the well and the excitonic lifetime. The higher accumulation of charge and lower ground state energy of the thicker well is evident from the higher tunnelling current found for the same in the photocurrent (I) versus voltage (V) measurement. Thus the escape of electrons from the well to barrier is the key factor affecting the photo generated charge accumulation and its holding capacity which in turn influences the device performances.

  17. Enhancing Photoinduced Electron Transfer Efficiency of Fluorescent pH-Probes with Halogenated Phenols

    PubMed Central

    2014-01-01

    Photoinduced electron transfer (PET), which causes pH-dependent quenching of fluorescent dyes, is more effectively introduced by phenolic groups than by amino groups which have been much more commonly used so far. That is demonstrated by fluorescence measurements involving several classes of fluorophores. Electrochemical measurements show that PET in several amino-modified dyes is thermodynamically favorable, even though it was not experimentally found, underlining the importance of kinetic aspects to the process. Consequently, the attachment of phenolic groups allows for fast and simple preparation of a wide selection of fluorescent pH-probes with tailor-made spectral properties, sensitive ranges, and individual advantages, so that a large number of applications can be realized. Fluorophores carrying phenolic groups may also be used for sensing analytes other than pH or molecular switching and signaling. PMID:25126834

  18. Photoinduced electron transfer in a protein-surfactant complex: probing the interaction of SDS with BSA.

    PubMed

    Chakraborty, Anjan; Seth, Debabrata; Setua, Palash; Sarkar, Nilmoni

    2006-08-24

    Photoinduced fluorescence quenching electron transfer from N,N-dimethyl aniline to different 7-amino coumarin dyes has been investigated in sodium dodecyl sulfate (SDS) micelles and in bovine serum albumin (BSA)-SDS protein-surfactant complexes using steady state and picosecond time resolved fluorescence spectroscopy. The electron transfer rate has been found to be slower in BSA-SDS protein-surfactant complexes compared to that in SDS micelles. This observation has been explained with the help of the "necklace-and-bead" structure formed by the protein-surfactant complex due to coiling of protein molecules around the micelles. In the correlation of free energy change to the fluorescence quenching electron transfer rate, we have observed that coumarin 151 deviates from the normal Marcus region, showing retardation in the electron transfer rate at higher negative free energy region. We endeavored to establish that the retardation in the fluorescence quenching electron transfer rate for coumarin 151 at higher free energy region is a result of slower rotational relaxation and slower translational diffusion of coumarin 151 (C-151) compared to its analogues coumarin 152 and coumarin 481 in micelles and in protein-surfactant complexes. The slower rotational relaxation and translational diffusion of C-151 are supposed to be arising from the different location of coumarin 151 compared to coumarin 152 and coumarin 481.

  19. Photoinduced phase transitions in vanadium dioxide revealed by ultrafast electron diffraction and mid-infrared spectroscopy

    NASA Astrophysics Data System (ADS)

    Tiwari, Kunal; Morrison, Vance; Chatelain, Robert; Hendaoui, Ali; Bruhacs, Andrew; Chaker, Mohamed; Siwick, Bradley

    2015-03-01

    The complex interplay between strong electron-electron correlations and structural distortions is thought to determine the electronic properties of many oxides, but the respective role of these two contributions is often difficult to determine. We report combined radio-frequency compressed ultrafast electron diffraction (RF-UED) and infrared transmissivity experiments in which we directly monitor and separate the lattice and charge density reorganizations associated with the optically induced semiconductor-to-metal phase transition in vanadium dioxide. These studies have uncovered a previously unreported photoinduced transition to a metastable phase retaining the periodic lattice distortion characteristic of the insulating phase, but differing by a reorganization of charge density along the vanadium dimer chains and a transition to metal-like mid IR optical properties. These results demonstrate that UED is able to follow details of both lattice and electronic structural dynamics on the ultrafast timescale. Supported by Natural Sciences and Engineering Research Council of Canada, the Canada Foundation for Innovation, the Canada Research Chairs program, NSERC PGS-D and CGS-D fellowships, and Fonds de Récherche du Québec-Nature et Technologies.

  20. Photoinduced electron transfer in layer-by-layer thin solid films containing cobalt oxide nanosheets, porphyrin, and methyl viologen.

    PubMed

    Sasai, R; Kato, Y; Soontornchaiyakul, W; Usami, H; Masumori, A; Norimatsu, W; Fujimura, T; Takagi, S

    2017-02-15

    The well-known layer-by-layer (LbL) method can be used to prepare solid thin films with a controlled electron transfer direction by appropriately stacking metal oxide nanosheets and functional organic ions. In this study, we prepared thin solid films consisting of cobalt oxide nanosheets (CoNSs) as the electron transfer medium, α,β,γ,δ-tetrakis(1-methylpyridinium-4-yl)porphyrin (TMPyP) as the electron donor, and 1,1'-dimethyl-4,4'-bipyridinium or methyl viologen (MV) as the electron acceptor. We investigated the photoinduced electron transfer phenomenon in these films by irradiating them with 450 nm light. Irradiating the LbL thin solid films prepared with the CoNS/TMPyP/CoNS/MV/CoNS sequence under reduced pressure led to the production of a one-electron reduction compound of MV. Hence, photoinduced electron transfer from TMPyP to MV bound to CoNSs occurred in these LbL thin solid films. However, the conduction band of CoNSs, as determined by the photoabsorption spectral and photoelectrochemical measurements, was much higher than the lowest unoccupied molecular orbital level of TMPyP. Our findings indicate that the observed equipotential photoinduced electron transfer was caused by the metallic electron conductivity of CoNSs, which show a unique charge arrangement of Co(3+) and Co(4+). Moreover, it was also found that the observed photoinduced charge separation state has a longer life-time (>5 h) under the reduced conditions.

  1. pH Dependence of Photoinduced Electron Transfer with [Ru(TAP)3](2).

    PubMed

    Troian-Gautier, Ludovic; Mugeniwabagara, Epiphanie; Fusaro, Luca; Moucheron, Cécile; Kirsch-De Mesmaeker, Andrée; Luhmer, Michel

    2017-02-20

    The quenching of the excited state of [Ru(TAP)3](2+) (TAP = 1,4,5,8-tetraazaphenanthrene) by guanosine-5'-monophosphate (GMP), N-acetyltyrosine (N-Ac-Tyr), and hydroquinone (H2Q) has been studied in aqueous solution over a wide range of pH values including, for the first time, strongly acidic media. This quenching by electron transfer was examined by steady-state (1)H photochemically induced dynamic nuclear polarization (photo-CIDNP) as well as by more conventional techniques, among which are pulsed laser-induced transient absorption and emission experiments. A deeper knowledge of the photochemical behavior of [Ru(TAP)3](2+) has been gained thanks to the combined use of these two approaches, photo-CIDNP and electronic spectroscopies, highlighting their complementarity. In contrast to what was believed, it is found that the protonated excited state of [Ru(TAP)3](2+) may give rise to an electron transfer with N-Ac-Tyr and H2Q. Such a photoinduced electron transfer does not occur with protonated GMP, however. (1)H photo-CIDNP experiments are expected to be particularly promising for characterization of the reductive quenching of excited-state ruthenium(II) polypyridyl complexes comprising several nonequivalent protonation sites.

  2. A femtosecond study of photoinduced electron transfer from dimethylaniline to coumarin dyes in a cetyltrimethylammonium bromide micelle

    SciTech Connect

    Ghosh, Subhadip; Sahu, Kalyanasis; Mondal, Sudip Kumar; Sen, Pratik; Bhattacharyya, Kankan

    2006-08-07

    Ultrafast photoinduced electron transfer (PET) from N,N-dimethylaniline to coumarin dyes in cetyltrimethylammonium bromide (CTAB) micelle is studied using femtosecond upconversion spectroscopy. The rate of PET in a CTAB micelle is found to be highly nonexponential with components much faster ({approx}10 ps) than the slow components of solvation dynamics. The ultrafast components of electron transfer exhibits a bell-shaped dependence on the free energy change which is similar to the Marcus inversion.

  3. Bimolecular Photoinduced Electron Transfer in Static Quenching Regime: Illustration of Marcus Inversion in Micelle.

    PubMed

    Mukherjee, Puspal; Das, Aritra; Sengupta, Arunava; Sen, Pratik

    2017-02-23

    Ultrafast bimolecular photoinduced electron transfer (PET) between six coumarin dyes and four viologen molecules in the stern layer of sodium dodecyl sulfate micelle have been studied using femtosecond broadband transient absorption spectroscopy and femtosecond fluorescence up-conversion spectroscopy over a broad reaction exergonicity (ΔG(0)). Emanating the formation of radical cation intermediates of viologen molecules using the transient absorption and the fast decay component of coumarins using the fluorescence up-conversion studies the forward bimolecular electron transfer rate (ket) have been measured with high accuracy. The relationship of ket with ΔG(0) found to follow a Marcus type bell-shaped dependence with an inversion at -1.10 eV. In this report, we have studied PET reaction using ultrafast spectroscopy at the quencher concentration where static quenching regime prevails. Moreover, the incompetency of Stern-Volmer experiments in studying ultrafast PET has been revealed. In contrary to previous claims, here we found that the ket is lower for lower lifetime coumarins, indicating that static, nonstationary and stationary regime of quenching have the minimal role to play to in the bimolecular electron transfer process. By far, this report is believed to be the most efficient and immaculate way of approaching Marcus inverted region problem in the case of bimolecular PET and settles the long-lasting debate of whether the same can be observed in micellar systems.

  4. Blue bottle light: lecture demonstrations of homogeneous and heterogeneous photo-induced electron transfer reactions.

    PubMed

    Mills, Andrew; Lawrie, Katherine; McFarlane, Michael

    2009-03-01

    The classic, non-photochemical blue bottle experiment involves the reaction of methylene blue (MB) with deprotonated glucose, to form a bleached form of the dye, leuco-methylene blue (LMB), and subsequent colour recovery by shaking with air. This reaction is a popular demonstrator of key principles in kinetics and reaction mechanisms. Here it is modified so as to highlight features of homogenous and heterogeneous photoinduced electron transfer (PET) (Pure Appl. Chem., 2007, 79, 293-465) reactions, i.e.blue bottle light experiments. The homogeneous blue bottle light experiment uses methylene blue, MB, as the photo-sensitizer and triethanolamine as the sacrificial electron donor. Visible light irradiation of this system leads to its rapid bleaching, followed by the ready restoration of its original colour upon shaking away from the light source. The heterogeneous blue bottle light experiment uses titania as the photo-sensitizer, MB as a redox indicator and glucose as the sacrificial electron donor. UVA light irradiation of this system leads to the rapid bleaching of the MB and the gradual restoration of its original colour with shaking and standing. The latter 'dark' step can be made facile and more demonstrator-friendly by using platinised titania particles. These two photochemical versions of the blue bottle experiment are used to explore the factors which underpin homogeneous and heterogeneous PET reactions and provide useful demonstrations of homogeneous and heterogeneous photochemistry.

  5. Electron spectrometer in adjustable triode configuration for photo-induced field emission measurements

    NASA Astrophysics Data System (ADS)

    Bornmann, B.; Mingels, S.; Dams, F.; Prommesberger, C.; Schreiner, R.; Lützenkirchen-Hecht, D.; Müller, G.

    2012-01-01

    We have constructed a new ultrahigh vacuum apparatus with a triode configuration for the systematic investigation of photo-induced field emission (PFE) from metallic or semiconducting cathodes. These are exposed to electric fields up to 400 MV/m and laser irradiation by means of hole or mesh gates. Cathodes and gates are in situ exchangeable and adjustable with high precision to ensure a homogeneous extraction of electrons which are partially transmitted to the fixed electron spectrometer. Its hemispherical sector analyzer provides an energy resolution limit of 8 meV. The commissioning of the measurement system has been performed with a tungsten needle. Its temperature showed up in the high-energy tail of the electron spectrum, while its work function was derived from the spectral low-energy part combined with the integral current-voltage curve. First PFE measurements on B-doped Si-tip arrays yielded a small field emission current increase under green laser illumination. A shift and splitting of the energy spectra was observed which revealed different emission regimes as well as the photosensitivity of the cathode due to carrier excitation into the conduction band. For the full exploitation of the PFE system, a tunable laser over a wide eV-range is required.

  6. Classical molecular dynamics simulation of the photoinduced electron transfer dynamics of plastocyanin.

    PubMed Central

    Ungar, L W; Scherer, N F; Voth, G A

    1997-01-01

    Classical molecular dynamics simulations are used to investigate the nuclear motions associated with photoinduced electron transfer in plastocyanin. The blue copper protein is modeled using a molecular mechanics potential; potential parameters for the copper-protein interactions are determined using an x-ray crystallographic structure and absorption and resonance Raman spectra. Molecular dynamics simulations yield a variety of information about the ground (oxidized) and optically excited (charge-transfer) states: 1) The probability distribution of the potential difference between the states, which is used to determine the coordinate and energy displacements, places the states well within the Marcus inverted region. 2) The two-time autocorrelation function of the difference potential in the ground state and the average of the difference potential after instantaneous excitation to the excited state are very similar (confirming linear response in this system); their decay indicates that vibrational relaxation occurs in about 1 ps in both states. 3) The spectral densities of various internal coordinates begin to identify the vibrations that affect the optical transition; the spectral density of the difference potential correlation function should also prove useful in quantum simulations of the back electron transfer. 4) Correlation functions of the protein atomic motions with the difference potential show that the nuclear motions are correlated over a distance of more than 20 A, especially along proposed electron transport paths. Images FIGURE 1 FIGURE 7 PMID:8994588

  7. Electron spectrometer in adjustable triode configuration for photo-induced field emission measurements

    SciTech Connect

    Bornmann, B.; Mingels, S.; Luetzenkirchen-Hecht, D.; Mueller, G.; Dams, F.; Prommesberger, C.; Schreiner, R.

    2012-01-15

    We have constructed a new ultrahigh vacuum apparatus with a triode configuration for the systematic investigation of photo-induced field emission (PFE) from metallic or semiconducting cathodes. These are exposed to electric fields up to 400 MV/m and laser irradiation by means of hole or mesh gates. Cathodes and gates are in situ exchangeable and adjustable with high precision to ensure a homogeneous extraction of electrons which are partially transmitted to the fixed electron spectrometer. Its hemispherical sector analyzer provides an energy resolution limit of 8 meV. The commissioning of the measurement system has been performed with a tungsten needle. Its temperature showed up in the high-energy tail of the electron spectrum, while its work function was derived from the spectral low-energy part combined with the integral current-voltage curve. First PFE measurements on B-doped Si-tip arrays yielded a small field emission current increase under green laser illumination. A shift and splitting of the energy spectra was observed which revealed different emission regimes as well as the photosensitivity of the cathode due to carrier excitation into the conduction band. For the full exploitation of the PFE system, a tunable laser over a wide eV-range is required.

  8. Electron spectrometer in adjustable triode configuration for photo-induced field emission measurements.

    PubMed

    Bornmann, B; Mingels, S; Dams, F; Prommesberger, C; Schreiner, R; Lützenkirchen-Hecht, D; Müller, G

    2012-01-01

    We have constructed a new ultrahigh vacuum apparatus with a triode configuration for the systematic investigation of photo-induced field emission (PFE) from metallic or semiconducting cathodes. These are exposed to electric fields up to 400 MV∕m and laser irradiation by means of hole or mesh gates. Cathodes and gates are in situ exchangeable and adjustable with high precision to ensure a homogeneous extraction of electrons which are partially transmitted to the fixed electron spectrometer. Its hemispherical sector analyzer provides an energy resolution limit of 8 meV. The commissioning of the measurement system has been performed with a tungsten needle. Its temperature showed up in the high-energy tail of the electron spectrum, while its work function was derived from the spectral low-energy part combined with the integral current-voltage curve. First PFE measurements on B-doped Si-tip arrays yielded a small field emission current increase under green laser illumination. A shift and splitting of the energy spectra was observed which revealed different emission regimes as well as the photosensitivity of the cathode due to carrier excitation into the conduction band. For the full exploitation of the PFE system, a tunable laser over a wide eV-range is required.

  9. Influence of donor-acceptor distance variation on photoinduced electron and proton transfer in rhenium(I)-phenol dyads.

    PubMed

    Kuss-Petermann, Martin; Wolf, Hilke; Stalke, Dietmar; Wenger, Oliver S

    2012-08-01

    A homologous series of four molecules in which a phenol unit is linked covalently to a rhenium(I) tricarbonyl diimine photooxidant via a variable number of p-xylene spacers (n = 0-3) was synthesized and investigated. The species with a single p-xylene spacer was structurally characterized to get some benchmark distances. Photoexcitation of the metal complex in the shortest dyad (n = 0) triggers release of the phenolic proton to the acetonitrile/water solvent mixture; a H/D kinetic isotope effect (KIE) of 2.0 ± 0.4 is associated with this process. Thus, the shortest dyad basically acts like a photoacid. The next two longer dyads (n = 1, 2) exhibit intramolecular photoinduced phenol-to-rhenium electron transfer in the rate-determining excited-state deactivation step, and there is no significant KIE in this case. For the dyad with n = 1, transient absorption spectroscopy provided evidence for release of the phenolic proton to the solvent upon oxidation of the phenol by intramolecular photoinduced electron transfer. Subsequent thermal charge recombination is associated with a H/D KIE of 3.6 ± 0.4 and therefore is likely to involve proton motion in the rate-determining reaction step. Thus, some of the longer dyads (n = 1, 2) exhibit photoinduced proton-coupled electron transfer (PCET), albeit in a stepwise (electron transfer followed by proton transfer) rather than concerted manner. Our study demonstrates that electronically strongly coupled donor-acceptor systems may exhibit significantly different photoinduced PCET chemistry than electronically weakly coupled donor-bridge-acceptor molecules.

  10. Photoinduced electron transfer in ruthenium(II)/Tin(IV) multiporphyrin arrays.

    PubMed

    Indelli, M Teresa; Chiorboli, Claudio; Ghirotti, Marco; Orlandi, Michele; Scandola, Franco; Kim, Hyun Jung; Kim, Hee-Joon

    2010-11-18

    The photophysical behavior of a series of heterometallic arrays made of a central Sn(IV) porphyrin connected, respectively, to two (SnRu(2)), four (SnRu(4)), or six (SnRu(6)) ruthenium porphyrin units has been studied in dichloromethane. Two different motifs connect the ruthenium porphyrin units to central tin porphyrin core, axial coordination via ditopic bridging ligands and/or coordination to peripheral pyridyl groups of the central porphyrin ring. A remarkable number of electron transfer processes (photoinduced charge separation and recombination processes) have been time-resolved using a combination of emission spectroscopy and fast (nanosecond) and ultrafast (femtosecond) absorption techniques. In these systems both types of molecular components can be selectively populated by light absorption. In all the arrays, the local excited states of these units (the tin porphyrin singlet excited state and the ruthenium porphyrin triplet state) are quenched by electron transfer leading to a charge-separated state where the ruthenium porphyrin unit is oxidized and the tin porphyrin unit is reduced. For each array, the two forward electron transfer processes, as well as the charge recombination process leading back to the ground state, have been kinetically resolved. The rate constants obey standard free-energy correlations with the forward processes lying in the normal free-energy regime and the back reactions in the Marcus inverted region. The comparison between the trimeric (SnRu(2)) and pentameric (SnRu(4)) arrays shows that all the electron transfer processes are faster in the latter than in the former system. This can be rationalized in terms of differences in electronic factors (due to the different connecting motifs) and driving force. In less polar solvents, such as toluene, the energy of the charge-separated states is substantially lifted, leading to a switch (from electron transfer to triplet energy transfer) in the deactivation mechanism of the excited

  11. Transient electronic structure of the photoinduced phase of Pr0.7Ca0.3MnO3 probed with soft x-ray pulses

    SciTech Connect

    Rini, M.; Zhu, Y.; Wall, S.; Tobey, R. I.; Ehrke, H.; Garl, T.; Freeland, J. W.; Tomioka, Y.; Tokura, Y.; Cavalleri, A.; Schoenlein, R. W.

    2009-04-01

    We use time-resolved x-ray absorption near-edge structure spectroscopy to investigate the electronic dynamics associated with the photoinduced insulator-to-metal phase transition in the colossal magnetoresistive manganite Pr{sub 0.7}Ca{sub 0.3}MnO{sub 3}. Absorption changes at the O K and Mn L edges directly monitor the evolution of the density of unoccupied states in the transient photoinduced phase. We show that the electronic structure of the photoinduced phase is remarkably similar to that of the ferromagnetic metallic phase reached in related manganites upon cooling below the Curie temperature.

  12. Ultrafast photoinduced charge transfer in pi-conjugated electron systems: Effects of structure, delocalization, and energetics (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Schanze, Kirk S.; Jones, Austin; Gish, Melissa; Zeman, Charles J.; Alsam, Amani A.; Aly, Shawkat M.; Papanikolas, John M.; Mohammed, Omar F.

    2016-09-01

    Photoinduced charge transfer is a key step in the mechanism of charge generation in organic solar cells. Charge transfer typically occurs from a photoexcited conjugated polymer donor to an electron acceptor. In an effort to better understand the primary events in solar cells, we have investigated photoinduced charge transfer in model donor-acceptor systems consisting of pi-conjugated oligomer donors that are covalently linked to diimide electron acceptors. These studies utilized oligo(thiophene), oligo(phenylene ethynylene) and oligo(fluorene) pi-conjugated systems with lengths varying from 4 to 12 repeat units linked to naphthalene diimide electron acceptors. Excitation with 100 femtosecond pulses at wavelengths correspoinding to the conjugated oligomer absorption band(s) leads to rapid photoinduced charge transfer to produce a charge separated state, (oligomer+)-(NDI-), which subsequently decays on timescales ranging from 100 ps to 5 ns. The dynamics of the forward and reverse electron transfer reactions depend strongly on the structure and length of the pi-conjugated oligomers, with the fastest rates occurring for oligo(thiophene)s, and considerably slower rates for oligo(phenylene ethynylene)s. The talk will discuss the structure-property relationships and energetic correlations that control the dynamics of charge separation and recombination.

  13. Photoinduced electron transfer and geminate recombination in the group head region of micelles

    NASA Astrophysics Data System (ADS)

    Glusac, Ksenija; Goun, Alexei; Fayer, M. D.

    2006-08-01

    A pump-probe spectroscopic study of photoinduced forward electron transfer and geminate recombination between donors and acceptors located in the head group regions of micelles is presented. The hole donor is octadecyl-rhodamine B (ODRB) and the hole acceptor is N,N-dimethyl-aniline (DMA). The experiments are conducted as a function of the DMA concentration in the dodecyltrimethylammonium bromide and tetradecyltrimethylammonium bromide micelles. In spite of the fact that the absorptions of both the ODRB radical and ground state bleach spectrally overlap with the ODRB excited state absorption, a procedure that makes it possible to determine the geminate recombination dynamics is presented. These experiments are the first to measure the dynamics of geminate recombination in micelles, and the experiments have two orders of magnitude better time resolution than previous studies of forward transfer. The experimental data are compared to statistical mechanics theoretical calculations of both the forward transfer and the geminate recombination. The theory includes important aspects of the topology of the micelle and the diffusion of the donor-acceptors in the micelle head group region. A semiquantitative but nonquantitative agreement between theory and experiments is achieved.

  14. Photoinduced electron transfer in a monolayer at the air-water interface

    SciTech Connect

    Matsumoto, Mutsuyoshi; Ahuja, R.C.; Moebius, D.

    1992-07-09

    Photoinduced electron transfer from the amphiphilic oxacyanine (donor) to the amphiphilic viologen (acceptor) embedded on a DMPC matrix is investigated in the monolayer. Steady-state fluorescence intensity-area isotherms were measured simultaneously with surface pressure-area isotherms. In the absence of the acceptor, the fluorescence intensity normalized to surface density increased with an increase in surface pressure, which was suggested to be due to an increase in the lifetime of the excited state of the donor. Dimer formation of the donor is not found in the present case even at the donor density of 0.22 nm{sup {minus}2}, contrary to the LB film case where it is found at donor densities as low as 0.01 nm{sup {minus}2} with cadmium arachidate/methyl arachidate = 1/1 as a matrix. This shows the important role of the matrix in this type of work. In the presence of the acceptor, the relative fluorescence intensity decreases strongly with increasing surface pressure and molar fraction of the acceptor. This is due to the electron transfer from the excited state of the donor to the ground state of the acceptor. The relative fluorescence intensity depends on the densities of the donor and the acceptor and also on the lifetime of the excited state of the donor. The critical distance for the electron transfer is 0.9 nm at 2 mN m{sup {minus}1} and 1.5 nm at 40 mN m{sup {minus}1}. The close match between the observed and simulated values shows that the energy delocalization via incoherent exciton hopping is not significant in the present monolayer case as opposed to the LB film systems where the donor and acceptor are localized at the same interface. The discrepancy may be due to the larger values of the donor-to-acceptor ratio in the LB film case. 24 refs., 6 figs.

  15. Photoinduced Electron Transfer from Various Aniline Derivatives to Graphene Quantum Dots.

    PubMed

    Ghosh, Tufan; Chatterjee, Swarupa; Prasad, Edamana

    2015-12-10

    The present study utilizes the luminescence nature of the graphene quantum dots (GQDs) to analyze the mechanistic aspects of the photoinduced electron transfer (PET) processes between GQDs and aniline derivatives. A systematic investigation of PET from various aniline derivatives to GQDs has been presented. Solution-processable GQDs have been synthesized from graphene oxide (GO) at 200 °C. The as-synthesized GQDs exhibit a strong green luminescence at 510 nm, upon photoexcitation at 440 nm. Various aniline derivatives (aniline, N-methylaniline, N,N'-dimethylaniline, N-ethylaniline, N,N'-diethylaniline, and N,N'-diphenylaniline) have been utilized as electron donors to probe the PET process. Results from UV-visible absorption and steady-state and time-resolve luminescence spectroscopy suggest that the GQDs interact with the aniline derivatives in the excited state, which results in a significant luminescence quenching of the GQDs. The bimolecular rate constants of the dynamic quenching have been deduced for various donor-acceptor systems, and the values are in the range of (1.06-2.68) × 10(9) M(-1) s(-1). The negative values of the free energy change of the electron transfer process suggest that PET from aniline derivatives to GQDs is feasible and could be responsible for the luminescence quenching. The PET has been confirmed by detecting radical cations for certain aniline derivatives, using a nanosecond laser flash photolysis setup. The present study shows that among the various types of graphene systems, GQDs are better candidates for understanding the mechanism of PET in graphene-based donor-acceptor systems.

  16. Nonadiabatic dynamics of photoinduced proton-coupled electron transfer in a solvated phenol-amine complex.

    PubMed

    Goyal, Puja; Schwerdtfeger, Christine A; Soudackov, Alexander V; Hammes-Schiffer, Sharon

    2015-02-12

    Photoinduced concerted electron-proton transfer (EPT), denoted photo-EPT, is important for a wide range of energy conversion processes. Transient absorption and Raman spectroscopy experiments on the hydrogen-bonded p-nitrophenylphenol-t-butylamine complex, solvated in 1,2-dichloroethane, suggested that this complex may undergo photo-EPT. The experiments probed two excited electronic states that were interpreted as an intramolecular charge transfer (ICT) state and an EPT state. Herein mixed quantum mechanical/molecular mechanical nonadiabatic surface hopping dynamics is used to investigate the relaxation pathways following photoexcitation. The potential energy surface is generated on the fly with a semiempirical floating occupation molecular orbital complete active space configuration interaction method for the solute molecule and a molecular mechanical force field for the explicit solvent molecules. The free energy curves along the proton transfer coordinate illustrate that proton transfer is thermodynamically and kinetically favorable on the lower-energy excited state but not on the higher-energy excited state, supporting the characterization of these states as EPT and ICT, respectively. The nonadiabatic dynamics simulations indicate that the population decays from the ICT state to the EPT state in ∼100 fs and from the EPT state to the ground state on the slower time scale of ∼1 ps, qualitatively consistent with the experimental measurements. For ∼54% of the trajectories, the proton transfers from the phenol to the amine in ∼400 fs on the EPT state and then transfers back to the phenol rapidly upon decay to the ground state. Thus, these calculations augment the original interpretation of the experimental data by providing evidence of proton transfer on the EPT state prior to decay to the ground state. The fundamental insights obtained from these simulations are also relevant to other photo-EPT processes.

  17. Coronenetetraimide-centered cruciform pentamers containing multiporphyrin units: synthesis and sequential photoinduced energy- and electron-transfer dynamics.

    PubMed

    Hasobe, Taku; Ida, Koichi; Sakai, Hayato; Ohkubo, Kei; Fukuzumi, Shunichi

    2015-07-27

    A series of coronenetetraimide (CorTIm)-centered cruciform pentamers containing multiporphyrin units, in which four porphyrin units are covalently linked to a CorTIm core through benzyl linkages, were designed and synthesized to investigate their structural, spectroscopic, and electrochemical properties as well as photoinduced electron- and energy-transfer dynamics. These systems afforded the first synthetic case of coroneneimide derivatives covalently linked with dye molecules. The steady-state absorption and electrochemical results indicate that a CorTIm and four porphyrin units were successfully characterized by the corresponding reference monomers. In contrast, the steady-state fluorescence measurements demonstrated that strong fluorescence quenching relative to the corresponding monomer units was observed in these pentamers. Nanosecond laser flash photolysis measurements revealed the occurrence of intermolecular electron transfer from triplet excited state of zinc porphyrins to CorTIm. Femtosecond laser-induced transient absorption measurements for excitation of the CorTIm unit clearly demonstrate the sequential photoinduced energy and electron transfer between CorTIm and porphyrins, that is, occurrence of the initial energy transfer from CorTIm (energy donor) to porphyrins (energy acceptor) and subsequent electron transfer from porphyrins (electron donor) to CorTIm (electron acceptor) in these pentamers, whereas only the electron-transfer process from porphyrins to CorTIm was observed when we mainly excite porphyrin units. Finally, construction of high-order supramolecular patterning of these pentamers was performed by utilizing self-assembly and physical dewetting during the evaporation of solvent.

  18. Ligand-controlled rates of photoinduced electron transfer in hybrid CdSe nanocrystal/poly(viologen) films.

    PubMed

    Tagliazucchi, Mario; Tice, Daniel B; Sweeney, Christina M; Morris-Cohen, Adam J; Weiss, Emily A

    2011-12-27

    This paper describes a study of the rates of photoinduced electron transfer (PET) from CdSe quantum dots (QDs) to poly(viologen) within thin films, as a function of the length of the ligands passivating the QDs. Ultrafast (<10 ps), quantitative PET occurs from CdSe QDs coated with HS-(CH(2))(n)-COOH for n = 1, 2, 5, and 7 to viologen units. The observed decrease in the magnitude of the PET rate constant with n is weaker than that expected from the decay of the electron tunneling probability across extended all-trans mercaptocarboxylic acids but well-described by electron tunneling across a collapsed ligand shell. The PET rate constants for films with n = 10 and 15 are much slower than those expected based on the trend for n = 1-7; this deviation is ascribed to the formation of bundles of ligands on the surface of the QD that make the tunneling process prohibitively slow by limiting access of the viologen units to the surfaces of the QDs. This study highlights the importance of molecular-level morphology of donor and acceptor materials in determining the rate and yield of interfacial photoinduced electron transfer in thin films.

  19. Effect of viscosity on photoinduced electron transfer reaction: An observation of the Marcus inverted region in homogeneous solvents

    NASA Astrophysics Data System (ADS)

    Saini, Rajesh Kumar; Kuchlyan, Jagannath; Sarkar, Nilmoni

    2016-09-01

    The viscosity effect of homogeneous solvents on the dynamics of photoinduced electron transfer (PET) reaction among the coumarins and N,N-dimethylaniline (DMA) is investigated using steady-state and time-resolved fluorescence spectroscopy. A bell shape Marcus inversion in the ET rates has been detected in the plot of ET rate constant (kq) with free energy change (ΔG0) in viscous solvents decanol and EG, but it is not observed in DMSO like low viscous solvent. We have also reported that there is no complex formation between the coumarin dye and DMA molecule by using fluorescence correlation spectroscopy.

  20. Interaction of fluorescence dyes with 5-fluorouracil: A photoinduced electron transfer study in bulk and biologically relevant water

    NASA Astrophysics Data System (ADS)

    Kuchlyan, Jagannath; Banik, Debasis; Kundu, Niloy; Roy, Arpita; Sarkar, Nilmoni

    2014-10-01

    The interactions of widely used chemotherapeutic drug, 5-fluorouracil (5FU) with coumarin dyes have been investigated for the first time using steady-state and time-resolved fluorescence spectroscopic measurements. The fluorescence quenching along with the decrease in lifetimes of excited state of coumarin derivatives with gradual addition of 5FU is explained by photoinduced electron transfer (PET) mechanism. Our studies were performed in bulk water and confined water of AOT (aerosol OT) reverse micelle to investigate the effect of confinement on PET dynamics. The feasibility of PET reaction for coumarin-5FU systems is investigated calculating the standard free energy changes using the Rehm-Weller equation.

  1. Photoinduced electron and energy transfer from coumarin 153 to perylenetetracarboxylic diimide in bmimPF6/TX-100/water microemulsions.

    PubMed

    Wu, Haixia; Wang, Haixia; Xue, Lin; Li, Xiyou

    2011-01-15

    A perylenetetracarboxylic diimide (PDI) compound with an attached hydrophilic polyoxyethylene group at the imide nitrogen position was designed and synthesized. Photoinduced electron and energy transfer between coumarin 153 (C-153) and PDI in a ternary microemulsion with an ionic liquid (bmimPF(6)/TX-100/H(2)O) were investigated by steady state electronic absorption and fluorescence spectroscopy. The results revealed that both PDI and C-153 resided at the interface between the surfactant TX-100 and the ionic liquid bmimPF(6) in the ternary microemulsions. The absorption spectra suggested no interactions between C-153 and PDI in the ground states, but the fluorescence spectra revealed the presence of an efficient electron transfer and a less efficient energy transfer from C-153 to PDI. Moreover, the electron transfer was much more efficient in microemulsions than that in homogeneous conventional organic solvents due to the unique micro-environment of the microemulsion.

  2. Effect of micellar environment on Marcus correlation curves for photoinduced bimolecular electron transfer reactions

    SciTech Connect

    Kumbhakar, Manoj; Nath, Sukhendu; Mukherjee, Tulsi; Pal, Haridas

    2005-07-15

    Photoinduced electron transfer (ET) between coumarin dyes and aromatic amine has been investigated in two cationic micelles, namely, cetyltrimethyl ammonium bromide (CTAB) and dodecyltrimethyl ammonium bromide (DTAB), and the results have been compared with those observed earlier in sodium dodecyl sulphate (SDS) and triton-X-100 (TX-100) micelles for similar donor-acceptor pairs. Due to a reasonably high effective concentration of the amines in the micellar Stern layer, the steady-state fluorescence results show significant static quenching. In the time-resolved (TR) measurements with subnanosecond time resolution, contribution from static quenching is avoided. Correlations of the dynamic quenching constants (k{sub q}{sup TR}), as estimated from the TR measurements, show the typical bell-shaped curves with the free-energy changes ({delta}G{sup 0}) of the ET reactions, as predicted by the Marcus outersphere ET theory. Comparing present results with those obtained earlier for similar coumarin-amine systems in SDS and TX-100 micelles, it is seen that the inversion in the present micelles occurs at an exergonicity (-{delta}G{sup 0}>{approx}1.2-1.3 eV) much higher than that observed in SDS and TX-100 micelles (-{delta}G{sup 0}>{approx}0.7 eV), which has been rationalized based on the relative propensities of the ET and solvation rates in different micelles. In CTAB and DTAB micelles, the k{sub q}{sup TR} values are lower than the solvation rates, which result in the full contribution of the solvent reorganization energy ({lambda}{sub s}) towards the activation barrier for the ET reaction. Contrary to this, in SDS and TX-100 micelles, k{sub q}{sup TR} values are either higher or comparable with the solvation rates, causing only a partial contribution of {lambda}{sub s} in these cases. Thus, Marcus inversion in present cationic micelles is inferred to be the true inversion, whereas that in the anionic SDS and neutral TX-100 micelles are understood to be the apparent

  3. Fluorescent Photoinduced Electron Transfer (PET) Logic Gates for Acidity (pH) and Redox Potential (pE).

    PubMed

    Magri, David C; Johnson, Alex D; Spiteri, Jake C

    2017-03-01

    This mini-review highlights the photophysical properties of fluorescent molecular logic gates responsive to acids and oxidants, particularly those developed in our laboratory the past few years. The review pays tribute to earlier developments that lay the foundation for this emerging class of molecules. The logic gates incorporate design concepts based on photoinduced electron transfer from the cross-fertilization of the fluorophore-spacer-receptor and fluorophore-spacer-electron-donor formats. The molecular logic gates explored in detail consist of anthracene and/or naphthalimide fluorophores, while the receptor and electron-donor are typically alkyl amines and ferrocene, respectively. This emerging class of molecule has numerous probable uses, most notably, in corrosion science, geochemistry, molecular cell biology and biomedical diagnostics.

  4. Light-Activated Protein Inhibition through Photoinduced Electron Transfer of a Ruthenium(II)–Cobalt(III) Bimetallic Complex

    PubMed Central

    Holbrook, Robert J.; Weinberg, David J.; Peterson, Mark D.; Weiss, Emily A.; Meade, Thomas J.

    2015-01-01

    We describe a mechanism of light activation that initiates protein inhibitory action of a biologically inert Co(III) Schiff base (Co(III)-sb) complex. Photoinduced electron transfer (PET) occurs from a Ru(II) bipyridal complex to a covalently attached Co(III) complex and is gated by conformational changes that occur in tens of nanoseconds. Reduction of the Co(III)-sb by PET initiates displacement of the inert axial imidazole ligands, promoting coordination to active site histidines of α-thrombin. Upon exposure to 455 nm light, the rate of ligand exchange with 4-methylimidazole, a histidine mimic, increases by approximately 5-fold, as observed by NMR spectroscopy. Similarly, the rate of α-thrombin inhibition increases over 5-fold upon irradiation. These results convey a strategy for light activation of inorganic therapeutic agents through PET utilizing redox-active metal centers. PMID:25671465

  5. Light-activated protein inhibition through photoinduced electron transfer of a ruthenium(II)–cobalt(III) bimetallic complex

    DOE PAGES

    Holbrook, Robert J.; Weinberg, David J.; Peterson, Mark D.; ...

    2015-02-11

    In this paper, we describe a mechanism of light activation that initiates protein inhibitory action of a biologically inert Co(III) Schiff base (Co(III)-sb) complex. Photoinduced electron transfer (PET) occurs from a Ru(II) bipyridal complex to a covalently attached Co(III) complex and is gated by conformational changes that occur in tens of nanoseconds. Reduction of the Co(III)-sb by PET initiates displacement of the inert axial imidazole ligands, promoting coordination to active site histidines of α-thrombin. Upon exposure to 455 nm light, the rate of ligand exchange with 4-methylimidazole, a histidine mimic, increases by approximately 5-fold, as observed by NMR spectroscopy. Similarly,more » the rate of α-thrombin inhibition increases over 5-fold upon irradiation. Finally, these results convey a strategy for light activation of inorganic therapeutic agents through PET utilizing redox-active metal centers.« less

  6. Light-activated protein inhibition through photoinduced electron transfer of a ruthenium(II)–cobalt(III) bimetallic complex

    SciTech Connect

    Holbrook, Robert J.; Weinberg, David J.; Peterson, Mark D.; Weiss, Emily A.; Meade, Thomas J.

    2015-02-11

    In this paper, we describe a mechanism of light activation that initiates protein inhibitory action of a biologically inert Co(III) Schiff base (Co(III)-sb) complex. Photoinduced electron transfer (PET) occurs from a Ru(II) bipyridal complex to a covalently attached Co(III) complex and is gated by conformational changes that occur in tens of nanoseconds. Reduction of the Co(III)-sb by PET initiates displacement of the inert axial imidazole ligands, promoting coordination to active site histidines of α-thrombin. Upon exposure to 455 nm light, the rate of ligand exchange with 4-methylimidazole, a histidine mimic, increases by approximately 5-fold, as observed by NMR spectroscopy. Similarly, the rate of α-thrombin inhibition increases over 5-fold upon irradiation. Finally, these results convey a strategy for light activation of inorganic therapeutic agents through PET utilizing redox-active metal centers.

  7. Photo-induced reactions from efficient molecular dynamics with electronic transitions using the FIREBALL local-orbital density functional theory formalism

    NASA Astrophysics Data System (ADS)

    Zobač, Vladimír; Lewis, James P.; Abad, Enrique; Mendieta-Moreno, Jesús I.; Hapala, Prokop; Jelínek, Pavel; Ortega, José

    2015-05-01

    The computational simulation of photo-induced processes in large molecular systems is a very challenging problem. Firstly, to properly simulate photo-induced reactions the potential energy surfaces corresponding to excited states must be appropriately accessed; secondly, understanding the mechanisms of these processes requires the exploration of complex configurational spaces and the localization of conical intersections; finally, photo-induced reactions are probability events, that require the simulation of hundreds of trajectories to obtain the statistical information for the analysis of the reaction profiles. Here, we present a detailed description of our implementation of a molecular dynamics with electronic transitions algorithm within the local-orbital density functional theory code FIREBALL, suitable for the computational study of these problems. As an example of the application of this approach, we also report results on the [2 + 2] cycloaddition of ethylene with maleic anhydride and on the [2 + 2] photo-induced polymerization reaction of two C60 molecules. We identify different deactivation channels of the initial electron excitation, depending on the time of the electronic transition from LUMO to HOMO, and the character of the HOMO after the transition.

  8. Photo-induced reactions from efficient molecular dynamics with electronic transitions using the FIREBALL local-orbital density functional theory formalism.

    PubMed

    Zobač, Vladimír; Lewis, James P; Abad, Enrique; Mendieta-Moreno, Jesús I; Hapala, Prokop; Jelínek, Pavel; Ortega, José

    2015-05-08

    The computational simulation of photo-induced processes in large molecular systems is a very challenging problem. Firstly, to properly simulate photo-induced reactions the potential energy surfaces corresponding to excited states must be appropriately accessed; secondly, understanding the mechanisms of these processes requires the exploration of complex configurational spaces and the localization of conical intersections; finally, photo-induced reactions are probability events, that require the simulation of hundreds of trajectories to obtain the statistical information for the analysis of the reaction profiles. Here, we present a detailed description of our implementation of a molecular dynamics with electronic transitions algorithm within the local-orbital density functional theory code FIREBALL, suitable for the computational study of these problems. As an example of the application of this approach, we also report results on the [2 + 2] cycloaddition of ethylene with maleic anhydride and on the [2 + 2] photo-induced polymerization reaction of two C60 molecules. We identify different deactivation channels of the initial electron excitation, depending on the time of the electronic transition from LUMO to HOMO, and the character of the HOMO after the transition.

  9. Visualizing the non-equilibrium dynamics of photoinduced intramolecular electron transfer with femtosecond X-ray pulses

    SciTech Connect

    Canton, Sophie E.; Kjær, Kasper S.; Vankó, György; van Driel, Tim B.; Adachi, Shin -ichi; Bordage, Amélie; Bressler, Christian; Chabera, Pavel; Christensen, Morten; Dohn, Asmus O.; Galler, Andreas; Gawelda, Wojciech; Gosztola, David; Haldrup, Kristoffer; Harlang, Tobias; Liu, Yizhu; Møller, Klaus B.; Németh, Zoltán; Nozawa, Shunsuke; Pápai, Mátyás; Sato, Tokushi; Sato, Takahiro; Suarez-Alcantara, Karina; Togashi, Tadashi; Tono, Kensuke; Uhlig, Jens; Vithanage, Dimali A.; Wärnmark, Kenneth; Yabashi, Makina; Zhang, Jianxin; Sundström, Villy; Nielsen, Martin M.

    2015-03-02

    Ultrafast photoinduced electron transfer preceding energy equilibration still poses many experimental and conceptual challenges to the optimization of photoconversion since an atomic-scale description has so far been beyond reach. Here we combine femtosecond transient optical absorption spectroscopy with ultrafast X-ray emission spectroscopy and diffuse X-ray scattering at the SACLA facility to track the non-equilibrated electronic and structural dynamics within a bimetallic donor–acceptor complex that contains an optically dark centre. Exploiting the 100-fold increase in temporal resolution as compared with storage ring facilities, these measurements constitute the first X-ray-based visualization of a non-equilibrated intramolecular electron transfer process over large interatomic distances. Thus experimental and theoretical results establish that mediation through electronically excited molecular states is a key mechanistic feature. The present study demonstrates the extensive potential of femtosecond X-ray techniques as diagnostics of non-adiabatic electron transfer processes in synthetic and biological systems, and some directions for future studies, are outlined.

  10. Visualizing the non-equilibrium dynamics of photoinduced intramolecular electron transfer with femtosecond X-ray pulses

    DOE PAGES

    Canton, Sophie E.; Kjær, Kasper S.; Vankó, György; ...

    2015-03-02

    Ultrafast photoinduced electron transfer preceding energy equilibration still poses many experimental and conceptual challenges to the optimization of photoconversion since an atomic-scale description has so far been beyond reach. Here we combine femtosecond transient optical absorption spectroscopy with ultrafast X-ray emission spectroscopy and diffuse X-ray scattering at the SACLA facility to track the non-equilibrated electronic and structural dynamics within a bimetallic donor–acceptor complex that contains an optically dark centre. Exploiting the 100-fold increase in temporal resolution as compared with storage ring facilities, these measurements constitute the first X-ray-based visualization of a non-equilibrated intramolecular electron transfer process over large interatomic distances.more » Thus experimental and theoretical results establish that mediation through electronically excited molecular states is a key mechanistic feature. The present study demonstrates the extensive potential of femtosecond X-ray techniques as diagnostics of non-adiabatic electron transfer processes in synthetic and biological systems, and some directions for future studies, are outlined.« less

  11. Visualizing the non-equilibrium dynamics of photoinduced intramolecular electron transfer with femtosecond X-ray pulses

    PubMed Central

    Canton, Sophie E.; Kjær, Kasper S.; Vankó, György; van Driel, Tim B.; Adachi, Shin-ichi; Bordage, Amélie; Bressler, Christian; Chabera, Pavel; Christensen, Morten; Dohn, Asmus O.; Galler, Andreas; Gawelda, Wojciech; Gosztola, David; Haldrup, Kristoffer; Harlang, Tobias; Liu, Yizhu; Møller, Klaus B.; Németh, Zoltán; Nozawa, Shunsuke; Pápai, Mátyás; Sato, Tokushi; Sato, Takahiro; Suarez-Alcantara, Karina; Togashi, Tadashi; Tono, Kensuke; Uhlig, Jens; Vithanage, Dimali A.; Wärnmark, Kenneth; Yabashi, Makina; Zhang, Jianxin; Sundström, Villy; Nielsen, Martin M.

    2015-01-01

    Ultrafast photoinduced electron transfer preceding energy equilibration still poses many experimental and conceptual challenges to the optimization of photoconversion since an atomic-scale description has so far been beyond reach. Here we combine femtosecond transient optical absorption spectroscopy with ultrafast X-ray emission spectroscopy and diffuse X-ray scattering at the SACLA facility to track the non-equilibrated electronic and structural dynamics within a bimetallic donor–acceptor complex that contains an optically dark centre. Exploiting the 100-fold increase in temporal resolution as compared with storage ring facilities, these measurements constitute the first X-ray-based visualization of a non-equilibrated intramolecular electron transfer process over large interatomic distances. Experimental and theoretical results establish that mediation through electronically excited molecular states is a key mechanistic feature. The present study demonstrates the extensive potential of femtosecond X-ray techniques as diagnostics of non-adiabatic electron transfer processes in synthetic and biological systems, and some directions for future studies, are outlined. PMID:25727920

  12. Incorporation of Water-Oxidation Catalysts into Photoinduced Electron Transfer Systems: Toward Solar Fuel Generation via Artificial Photosynthesis

    NASA Astrophysics Data System (ADS)

    Vagnini, Michael Thomas

    A key goal of artificial photosynthesis is to mimic the photochemistry of photosystem II and oxidize water using light energy, with the ultimate aim of using the liberated electrons for reductive, fuel-forming reactions. One of the more recent challenges in the field of solar fuels chemistry is the efficient activation of molecular water-oxidation catalysts with photoinduced electron transfer, an effort that would benefit from detailed knowledge of the energetics and kinetics of each electron transfer step in a light-driven catalytic cycle. The focus of this thesis is the synthesis and photophysical characterization of covalent assemblies comprising a redox-active organic chromophore and the iridium(III)-based water-oxidation catalyst Cp*Ir(ppy)Cl (ppy = 2-phenylpyridine), and the rates and pathways for photogeneration of higher-valence states of the catalyst are determined with femtosecond transient absorption spectroscopy and other time-resolved spectroscopic techniques. In linking the photooxidant perylene-3,4:9,10-bis (dicarboximide) (PDI) to the Ir(III) catalyst, fast photoinduced electron transfer from the metal complex to PDI outcompetes heavy-atom quenching of the dye excited state, and the catalytic integrity of the complex is retained, as determined by electrocatalysis experiments. Long-lived higher-valence states of the catalyst are necessary for the accumulation of oxidizing equivalents for oxygen evolution, and the lifetime of photogenerated Ir(IV) has been extended by over two orders of magnitude by catalyst incorporation into a covalent electron acceptor--chromophore--catalyst triad, in which the dye is perylene-3,4-dicarboximide (PMI). Time resolved X-ray absorption studies of the triad confirm the photogeneration of an Ir(IV) metal center, a species that is too unstable to observe with chemical or electrochemical oxidation methods. This approach to preparing higher-valence states of water-oxidation catalysts has great promise for deducing catalytic

  13. Magnetic field effect corroborated with docking study to explore photoinduced electron transfer in drug-protein interaction.

    PubMed

    Chakraborty, Brotati; Roy, Atanu Singha; Dasgupta, Swagata; Basu, Samita

    2010-12-30

    Conventional spectroscopic tools such as absorption, fluorescence, and circular dichroism spectroscopy used in the study of photoinduced drug-protein interactions can yield useful information about ground-state and excited-state phenomena. However, photoinduced electron transfer (PET) may be a possible phenomenon in the drug-protein interaction, which may go unnoticed if only conventional spectroscopic observations are taken into account. Laser flash photolysis coupled with an external magnetic field can be utilized to confirm the occurrence of PET and authenticate the spin states of the radicals/radical ions formed. In the study of interaction of the model protein human serum albumin (HSA) with acridine derivatives, acridine yellow (AY) and proflavin (PF(+)), conventional spectroscopic tools along with docking study have been used to decipher the binding mechanism, and laser flash photolysis technique with an associated magnetic field (MF) has been used to explore PET. The results of fluorescence study indicate that fluorescence resonance energy transfer takes place from the protein to the acridine-based drugs. Docking study unveils the crucial role of Ser 232 residue of HSA in explaining the differential behavior of the two drugs towards the model protein. Laser flash photolysis experiments help to identify the radicals/radical ions formed in the due course of PET (PF(•), AY(•-), TrpH(•+), Trp(•)), and the application of an external MF has been used to characterize their initial spin-state. Owing to its distance dependence, MF effect gives an idea about the proximity of the radicals/radical ions during interaction in the system and also helps to elucidate the reaction mechanisms. A prominent MF effect is observed in homogeneous buffer medium owing to the pseudoconfinement of the radicals/radical ions provided by the complex structure of the protein.

  14. BODIPY-based fluorescent thermometer as a lysosome-targetable probe: how the oligo(ethylene glycols) compete photoinduced electron transfer.

    PubMed

    Wang, Hua; Wu, Yongquan; Shi, Yanlin; Tao, Pan; Fan, Xing; Su, Xinyan; Kuang, Gui-Chao

    2015-02-16

    A novel BODIPY-based fluorescent thermometer, which shows a lysosome-targeting property, was successfully prepared. Due to the electron-donating ability of the oligo(ethylene glycols), the photoinduced electron-transfer pathway from morpholine to BODIPY dye is blocked. The fluorescence of the thermometer quenched by intramolecular rotation at room temperature was progressively enhanced during heating due to the increased microviscosity around the fluorophore.

  15. Fixed distance photoinduced electron transfer between Fe and Zn porphyrins encapsulated within the Zn HKUST-1 metal organic framework.

    PubMed

    Larsen, Randy W; Wojtas, Lukasz

    2015-02-21

    An attractive strategy for the development of photocatalytic metal organic framework (MOF) materials is to co-encapsulate a photoactive electron donor with a catalytic electron acceptor within the MOF. Here we report the co-encapsulation of both Zn(ii) tetrakis(tetra 4-sulphonatophenyl)porphyrin (Zn4SP) and Fe(iii) tetrakis(tetra 4-sulphonatophenyl)porphyrin (Fe4SP) into an HKUST-1 (Zn) MOF and demonstrate photoinduced electron transfer (ET) between the co-encapsulated guest. Photo-excitation of the Zn4SP results in fixed-distance inter-molecular ET between the encapsulated (3)Zn4SP and the Fe(iii)4SP as evident by the reduction in the encapsulated (3)Zn4SP lifetime from 890 μs (kobs = 1.1 × 10(3) s(-1)) to 83 μs (kobs = 1.2 × 10(4) s(-1)) in the presence of Fe4SP giving a kET ∼ 1.1 × 10(4) s(-1). The data are consistent with ET taking place between encapsulated porphyrins that are two cages apart in distance with a reorganizational energy of ∼1.65 eV, β = 1.25 and ΔG° = -0.97 eV (within a semi-classical Marcus theory framework).

  16. Free-Energy-Gap Law for Ultrafast Charge Recombination of Ion Pairs Formed by Intramolecular Photoinduced Electron Transfer.

    PubMed

    Nazarov, Alexey E; Malykhin, Roman; Ivanov, Anatoly I

    2017-01-26

    In this article, regularities of ultrafast charge recombination (CR) kinetics in photoinduced intramolecular electron transfer in polar solvents are studied. The kinetics of charge separation and ensuing ultrafast CR are simulated within the framework of the multichannel stochastic model. This model accounts for the reorganization of both the solvent and a number of intramolecular high-frequency vibrational modes. The solvent relaxation is described in terms of two relaxation modes. For ultrafast CR, the free-energy-gap law strongly depends on the parameters: the electronic coupling, reorganization energy of intramolecular high-frequency vibrational modes, and the vibrational and solvent relaxation times. The semilog dependence of the CR rate constant on the free-energy gap varies from a parabolic shape to a nearly linear one with increasing the electronic coupling and decreasing the vibrational relaxation time. The dynamic solvent effect in CR is predicted to be large in the area of strong exergonicity and small in the area of weak exergonicity. This regularity is opposite to that observed for the thermal reactions.

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

    PubMed

    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

  18. Ultrafast photoinduced electron transfer in the micelle and the gel phase of a PEO-PPO-PEO triblock copolymer

    SciTech Connect

    Mandal, Ujjwal; Ghosh, Subhadip; Dey, Shantanu; Adhikari, Aniruddha; Bhattacharyya, Kankan

    2008-04-28

    Ultrafast photoinduced electron transfer (PET) from N,N-dimethylaniline (DMA) to coumarin dyes is studied in the micelle and the gel phase of a triblock copolymer, (PEO){sub 20}-(PPO){sub 70}-(PEO){sub 20} (Pluronic P123) by picosecond and femtosecond emission spectroscopies. The rate of PET in a P123 micelle and gel is found to be nonexponential and faster than the slow components of solvation dynamics. In a P123 micelle and gel, PET occurs on multiple time scales ranging from a subpicosecond time scale to a few nanoseconds. In the gel phase, the highest rate constant (9.3x10{sup 9} M{sup -1} s{sup -1}) of ET for C152 is about two times higher than that (3.8x10{sup 9} M{sup -1} s{sup -1}) observed in micelle phase. The ultrafast components of electron transfer (ET) exhibits a bell shaped dependence with the free energy change which is similar to the Marcus inversion. Possible reasons for slower PET in P123 micelle compared to other micelles and relative to P123 gel are discussed.

  19. Ab initio characterization of electron transfer coupling in photoinduced systems: generalized Mulliken-Hush with configuration-interaction singles.

    PubMed

    Chen, Hung-Cheng; Hsu, Chao-Ping

    2005-12-29

    To calculate electronic couplings for photoinduced electron transfer (ET) reactions, we propose and test the use of ab initio quantum chemistry calculation for excited states with the generalized Mulliken-Hush (GMH) method. Configuration-interaction singles (CIS) is proposed to model the locally excited (LE) and charge-transfer (CT) states. When the CT state couples with other high lying LE states, affecting coupling values, the image charge approximation (ICA), as a simple solvent model, can lower the energy of the CT state and decouple the undesired high-lying local excitations. We found that coupling strength is weakly dependent on many details of the solvent model, indicating the validity of the Condon approximation. Therefore, a trustworthy value can be obtained via this CIS-GMH scheme, with ICA used as a tool to improve and monitor the quality of the results. Systems we tested included a series of rigid, sigma-linked donor-bridge-acceptor compounds where "through-bond" coupling has been previously investigated, and a pair of molecules where "through-space" coupling was experimentally demonstrated. The calculated results agree well with experimentally inferred values in the coupling magnitudes (for both systems studied) and in the exponential distance dependence (for the through-bond series). Our results indicate that this new scheme can properly account for ET coupling arising from both through-bond and through-space mechanisms.

  20. Photoinduced electron transfer between 2-methylanthraquinone and triethylamine in an ionic liquid: Time-resolved EPR and transient absorption spectroscopy study

    NASA Astrophysics Data System (ADS)

    Zhu, Guanglai; Wang, Yu; Fu, Haiying; Xu, Xinsheng; Cui, Zhifeng; Ji, Xuehan; Wu, Guozhong

    2015-02-01

    Photoinduced electron transfer between 2-methylanthraquinone (MeAQ) and triethylamine (TEA) in a room-temperature ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]), was investigated by comparing the time-resolved electron paramagnetic resonance (TR-EPR) spectroscopy and the transient absorption spectroscopy. The results of TR-EPR spectroscopy, in which MeAQ was 8 mmol L-1 and TEA was 150 mmol L-1, indicated that the transient radical would exist longer time in [bmim][PF6] than in acetonitrile. At the delay time of 8 μs after laser excitation, the TR-EPR signal transformed from an emissive peak into an absorptive peak when the experiment was performed in [bmim][PF6]. The results of the transient absorption spectroscopy, in which MeAQ was 0.1 mmol L-1 and TEA was 2.2 mmol L-1, showed that the efficiency and the rate of the photoinduced electron transfer reaction in [bmim][PF6] were obviously lower than that in acetonitrile. It was concluded that various factors, such as concentration, viscosity and local structural transformation of the solution, have an influence on the process of photoinduced electron transfer in [bmim][PF6].

  1. Vibrational dynamics in photoinduced electron transfer. Progress report, December 1, 1992--November 30, 1993

    SciTech Connect

    Spears, K.G.

    1993-09-08

    Objective is to perform a new type of measurement for optically excited electron transfer processes that can provide unique experimental insight into the molecular mechanism of electron transfer. Measurements of optically excited electron transfer are done with picosecond infrared (IR) absorption spectroscopy to monitor the vibrational motions of the molecules immediately after electron transfer. Theory and experiment suggest that molecular vibrations and distortions are important controlling elements for electron transfer, and direct information has yet to be obtained on these elements of electron transfer mechanisms. The second period of funding has been dedicated to finishing technique development and performing studies of electron transfer in ion pair systems to identify if vibrational dependent electron transfer rates are present in this system. We have succeeded in measuring, for the first time, electron transfer rates as a function of vibrational state in an ion pair complex in solution. In a different area of electron transfer research we have proposed a new mechanism of solvent gated electron transfer.

  2. Ru-TAP complexes and DNA: from photo-induced electron transfer to gene photo-silencing in living cells.

    PubMed

    Marcélis, Lionel; Moucheron, Cécile; Kirsch-De Mesmaeker, Andrée

    2013-07-28

    In this review, examples of applications of the photo-induced electron transfer (PET) process between photo-oxidizing Ru-TAP (TAP = 1,4,5,8-tetraazaphenanthrene) complexes and DNA or oligodeoxynucleotides (ODNs) are discussed. Applications using a free Ru-TAP complex (not chemically anchored to an ODN) are first considered. In this case, the PET gives rise to the production of an irreversible adduct of the Ru complex on a guanine (G) base, with formation of a covalent bond. After absorption of a second photon, this adduct can generate a bi-adduct, whereby the same complex binds to a second G moiety. These bi-adduct formations are responsible for photo-cross-linking between two strands of a duplex, each containing a G base, or between two G moieties of a single strand such as a telomeric sequence, as demonstrated by polyacrylamide gel electrophoresis analyses or mass spectrometry. Scanning force microscopy also allows the detection of such photobridgings with plasmid DNA. Other applications, for example with Ru-ODN, i.e. ODN with chemically anchored Ru-TAP complexes, are also discussed. It is shown that such Ru-ODN probes containing a G base in their own sequences are capable of photo-cross-linking selectively with their targeted complementary sequences, and, in the absence of such targets, they self-photo-inhibit. Such processes are applied successfully in gene photo-silencing of human papillomavirus cancer cells.

  3. A new fluorescence turn-on probe for biothiols based on photoinduced electron transfer and its application in living cells

    NASA Astrophysics Data System (ADS)

    Wang, Jianxi; Zhou, Cheng; Zhang, Jianjian; Zhu, Xinyue; Liu, Xiaoyan; Wang, Qin; Zhang, Haixia

    2016-09-01

    A new biothiol-selective fluorescent probe 1 based on photoinduced electron transfer (PET) mechanism was designed and synthesized. The UV-Vis absorption and fluorescent emission properties of probe 1 towards various analytes were studied in detail. The probe exhibited a large stokes shift (~ 200 nm) after reacted with biothiols and could selectively detect cysteine (Cys) in dimethyl sulfoxide (DMSO)/H2O solution (9:1, v/v, 10 mM phosphate buffer saline, pH 3.5) over glutathione (GSH), homocysteine (Hcy) and other analytes with a detection limit of 0.117 μM. In addition, probe 1 responded well to GSH, Hcy and Cys in the same above solution with pH 5.5 and got the detection limits of 0.151 μM, 0.128 μM and 0.037 μM, respectively. Probe 1 was of very low cytotoxicity and successfully applied for imaging of thiols in living cells.

  4. Photoinduced electron transfer from semiconductor quantum dots to metal oxide nanoparticles

    PubMed Central

    Tvrdy, Kevin; Frantsuzov, Pavel A.; Kamat, Prashant V.

    2011-01-01

    Quantum dot-metal oxide junctions are an integral part of next-generation solar cells, light emitting diodes, and nanostructured electronic arrays. Here we present a comprehensive examination of electron transfer at these junctions, using a series of CdSe quantum dot donors (sizes 2.8, 3.3, 4.0, and 4.2 nm in diameter) and metal oxide nanoparticle acceptors (SnO2, TiO2, and ZnO). Apparent electron transfer rate constants showed strong dependence on change in system free energy, exhibiting a sharp rise at small driving forces followed by a modest rise further away from the characteristic reorganization energy. The observed trend mimics the predicted behavior of electron transfer from a single quantum state to a continuum of electron accepting states, such as those present in the conduction band of a metal oxide nanoparticle. In contrast with dye-sensitized metal oxide electron transfer studies, our systems did not exhibit unthermalized hot-electron injection due to relatively large ratios of electron cooling rate to electron transfer rate. To investigate the implications of these findings in photovoltaic cells, quantum dot-metal oxide working electrodes were constructed in an identical fashion to the films used for the electron transfer portion of the study. Interestingly, the films which exhibited the fastest electron transfer rates (SnO2) were not the same as those which showed the highest photocurrent (TiO2). These findings suggest that, in addition to electron transfer at the quantum dot-metal oxide interface, other electron transfer reactions play key roles in the determination of overall device efficiency. PMID:21149685

  5. Mechanistic studies of photoinduced spin crossover and electron transfer in inorganic complexes.

    PubMed

    Zhang, Wenkai; Gaffney, Kelly J

    2015-04-21

    Electronic excited-state phenomena provide a compelling intersection of fundamental and applied research interests in the chemical sciences. This holds true for coordination chemistry, where harnessing the strong optical absorption and photocatalytic activity of compounds depends on our ability to control fundamental physical and chemical phenomena associated with the nonadiabatic dynamics of electronic excited states. The central events of excited-state chemistry can critically influence the dynamics of electronic excited states, including internal conversion (transitions between distinct electronic states) and intersystem crossing (transitions between electronic states with different spin multiplicities), events governed by nonadiabatic interactions between electronic states in close proximity to conical intersections, as well as solvation and electron transfer. The diversity of electronic and nuclear dynamics also makes the robust interpretation of experimental measurements challenging. Developments in theory, simulation, and experiment can all help address the interpretation and understanding of chemical dynamics in organometallic and coordination chemistry. Synthesis presents the opportunity to chemically engineer the strength and symmetry of the metal-ligand interactions. This chemical control can be exploited to understand the influence of electronic ground state properties on electronic excited-state dynamics. New time-resolved experimental methods and the insightful exploitation of established methods have an important role in understanding, and ideally controlling, the photophysics and photochemistry of transition metal complexes. Techniques that can disentangle the coupled motion of electrons and nuclear dynamics warrant emphasis. We present a review of electron localization dynamics in charge transfer excited states and the dynamics of photoinitiated spin crossover dynamics. Both electron localization and spin crossover have been investigated by

  6. Photoinduced bimolecular electron transfer from aromatic amines to pentafluorophenyl porphyrin combined with ultrafast charge recombination persistence with Marcus inverted region.

    PubMed

    Venkatesh, Yeduru; Munisamy, Venkatesan; Ramakrishna, Bheerappagari; Kumar, Pippara Hemant; Mandal, Haraprasad; Bangal, Prakriti Ranjan

    2017-02-15

    The dynamics of photoinduced bimolecular reductive electron transfer between meso-tetrakis(pentafluorophenyl)porphyrin (H2F20TPP), an acceptor (A), and five aromatic amines (donor (D)) with varying oxidation potentials (aniline (AN), N-methylaniline (MAN), N-ethylaniline (EAN), N,N-dimethylaniline (DMAN) and N,N-diethylaniline (DEAN)) in dichloromethane (DCM) as a solvent as well as in neat donor solvents were investigated by employing nanosecond to femtosecond time-resolved fluorescence spectroscopy and femtosecond time-resolved transient absorption spectroscopy upon S2 excitation of H2F20TPP. Systematic studies of time-resolved fluorescence quenching dependent on the donor concentration in the concentration range of 0.01-2 M and finally in neat donor solvents broadly enabled us to determine the electron transfer dynamics in three regimes of electron transfer: stationary or diffusion-controlled electron transfer, non-stationary electron transfer and intrinsic or ultrafast electron transfer. Depending upon the electron-donating ability of the studied donors, intrinsic electron transfer was found to occur in the time domain of ∼1-9 ps and diffusion-controlled ET dynamics was observed in the time domain of 200-500 ps, whereas the maximum limit of non-stationary electron transfer could be observed in the time domain of 15-50 ps. Femtosecond transient absorption studies together with global and target analysis helped to identify the spectral signature of the (H2F20TPP˙(-)) radical anion as the product of ET. To the best of our knowledge, this is the first ever evidence that shows the spectra of an anion as the product of ET for any porphyrin-based electron transfer dynamics. However, transient absorption measurements confirm that intrinsic ET occurs in the Qy state, whereas diffusion-controlled ET occurs in the hot Qx as well as in the thermal equilibrium Qx state. The most remarkable fact derived from the measurements of transient absorption was that the rate of

  7. Photo-induced regeneration of hormones by electron transfer processes: Potential biological and medical consequences

    NASA Astrophysics Data System (ADS)

    Getoff, Nikola; Hartmann, Johannes; Schittl, Heike; Gerschpacher, Marion; Quint, Ruth Maria

    2011-08-01

    Based on the previous results concerning electron transfer processes in biological substances, it was of interest to investigate if hormone transients resulting by e.g. electron emission can be regenerated. The presented results prove for the first time that the hormone transients originating by the electron emission process can be successfully regenerated by the transfer of electrons from a potent electron donor, such as vitamin C (VitC). Investigations were performed using progesterone (PRG), testosterone (TES) and estrone (E1) as representatives of hormones. By irradiation with monochromatic UV light (λ=254 nm) in a media of 40% water and 60% ethanol, the degradation as well as the regeneration of the hormones was studied with each hormone individually and in the mixture with VitC as a function of the absorbed UV dose, using HPLC. Calculated from the obtained initial yields, the determined regeneration of PRG amounted to 52.7%, for TES to 58.6% and for E1 to 90.9%. The consumption of VitC was determined in the same way. The reported results concerning the regeneration of hormones by the transfer of electrons from an electron donor offer a new, promising method for the therapy with hormones. As a consequence of the regeneration of hormones, a decreased formation of carcinogenic metabolites is expected.

  8. Cationic dye-sensitized degradation of sodium hyaluronate through photoinduced electron transfer in the upper excited state.

    PubMed

    Kojima, M; Takahashi, K; Nakamura, K

    2001-09-01

    The formation of ground-state complexes of methylene blue (MB) and thionine (TN) with sodium hyaluronate (NaHA) was clearly observed by means of absorption spectra in aqueous solution. Irradiation of the complexes using 313 nm light caused significant degradation of NaHA under oxygen and argon. However, the use of visible light over 400 nm, which gives the lowest excited singlet state of the cationic dyes, caused no degradation. MB and TN were more efficient sensitizers for the degradation of NaHA than rose bengal (RB), although RB is a more efficient singlet oxygen (1O2) sensitizer than the cationic dyes. Under similar conditions the polysaccharides with carboxyl groups, such as alginic acid and polygalacturonic acid, also photodecomposed. However, the polysaccharides without carboxyl groups, such as pullulan and methyl cellulose, did not. The irradiation of the polysaccharides in the presence of powdered titanium dioxide as a photocatalyst to generate the hydroxyl radical (.OH) in aerated aqueous solution caused the fragmentation of all the polymers. It was confirmed that methyl viologen, an electron-accepting sensitizer, formed a charge-transfer complex with NaHA, the irradiation of which caused the efficient degradation of NaHA. In the presence of beta- and gamma-cyclodextrins the MB- and TN-sensitized photodegradation of NaHA was markedly suppressed. This was probably due to the formation of the inclusion complexes comprising the cationic dyes and the cyclodextrins. On the basis of the results obtained we propose that the cationic dye-sensitized degradation of NaHA involves a photoinduced electron-transfer process between the upper excited dyes and the ground-state NaHA and that .OH and 1O2 do not participate in the degradation.

  9. Self-amplified photo-induced gap quenching in a correlated electron material.

    PubMed

    Mathias, S; Eich, S; Urbancic, J; Michael, S; Carr, A V; Emmerich, S; Stange, A; Popmintchev, T; Rohwer, T; Wiesenmayer, M; Ruffing, A; Jakobs, S; Hellmann, S; Matyba, P; Chen, C; Kipp, L; Bauer, M; Kapteyn, H C; Schneider, H C; Rossnagel, K; Murnane, M M; Aeschlimann, M

    2016-10-04

    Capturing the dynamic electronic band structure of a correlated material presents a powerful capability for uncovering the complex couplings between the electronic and structural degrees of freedom. When combined with ultrafast laser excitation, new phases of matter can result, since far-from-equilibrium excited states are instantaneously populated. Here, we elucidate a general relation between ultrafast non-equilibrium electron dynamics and the size of the characteristic energy gap in a correlated electron material. We show that carrier multiplication via impact ionization can be one of the most important processes in a gapped material, and that the speed of carrier multiplication critically depends on the size of the energy gap. In the case of the charge-density wave material 1T-TiSe2, our data indicate that carrier multiplication and gap dynamics mutually amplify each other, which explains-on a microscopic level-the extremely fast response of this material to ultrafast optical excitation.

  10. Self-amplified photo-induced gap quenching in a correlated electron material

    NASA Astrophysics Data System (ADS)

    Mathias, S.; Eich, S.; Urbancic, J.; Michael, S.; Carr, A. V.; Emmerich, S.; Stange, A.; Popmintchev, T.; Rohwer, T.; Wiesenmayer, M.; Ruffing, A.; Jakobs, S.; Hellmann, S.; Matyba, P.; Chen, C.; Kipp, L.; Bauer, M.; Kapteyn, H. C.; Schneider, H. C.; Rossnagel, K.; Murnane, M. M.; Aeschlimann, M.

    2016-10-01

    Capturing the dynamic electronic band structure of a correlated material presents a powerful capability for uncovering the complex couplings between the electronic and structural degrees of freedom. When combined with ultrafast laser excitation, new phases of matter can result, since far-from-equilibrium excited states are instantaneously populated. Here, we elucidate a general relation between ultrafast non-equilibrium electron dynamics and the size of the characteristic energy gap in a correlated electron material. We show that carrier multiplication via impact ionization can be one of the most important processes in a gapped material, and that the speed of carrier multiplication critically depends on the size of the energy gap. In the case of the charge-density wave material 1T-TiSe2, our data indicate that carrier multiplication and gap dynamics mutually amplify each other, which explains--on a microscopic level--the extremely fast response of this material to ultrafast optical excitation.

  11. Exploring Autoionization and Photoinduced Proton-Coupled Electron Transfer Pathways of Phenol in Aqueous Solution.

    PubMed

    Oliver, Thomas A A; Zhang, Yuyuan; Roy, Anirban; Ashfold, Michael N R; Bradforth, Stephen E

    2015-10-15

    The excited state dynamics of phenol in water have been investigated using transient absorption spectroscopy. Solvated electrons and vibrationally cold phenoxyl radicals are observed upon 200 and 267 nm excitation, but with formation time scales that differ by more than 4 orders of magnitude. The impact of these findings is assessed in terms of the relative importance of autoionization versus proton-coupled electron transfer mechanisms in this computationally tractable model system.

  12. Photoinduced Interfacial Electron Injection Dynamics in Dye-Sensitized Solar Cells under Photovoltaic Operating Conditions.

    PubMed

    Teuscher, Joël; Décoppet, Jean-David; Punzi, Angela; Zakeeruddin, Shaik M; Moser, Jacques-E; Grätzel, Michael

    2012-12-20

    We report a pump-probe spectroscopy study of electron injection rates in dye-sensitized solar cell (DSSC) devices. We examine the case of working devices employing an N719 ruthenium sensitizer and an iodide electrolyte. Electron injection is found to occur mainly on a sub-100 fs time scale, followed by a slower component with a lifetime of 26.9 ps, in accordance with previous reports on model samples. The amplitude of this latter component varies with electrolyte composition from 25 to 9%. The appearance of slower components in the electron injection dynamics may be attributed to an aggregated or weakly bound state of the surface-adsorbed N719 sensitizer. Further measurements are reported varying the cell light bias and load conditions, revealing no influence on electron injection dynamics. No other electron injection event is found to occur up to 1 ns. These results show no evidence for a slowdown of electron injection under working conditions compared to model systems for the electrolytes examined in this study.

  13. Photoinduced Electron Transfer in DNA: Charge Shift Dynamics Between 8-Oxo-Guanine Anion and Adenine.

    PubMed

    Zhang, Yuyuan; Dood, Jordan; Beckstead, Ashley A; Li, Xi-Bo; Nguyen, Khiem V; Burrows, Cynthia J; Improta, Roberto; Kohler, Bern

    2015-06-18

    Femtosecond time-resolved IR spectroscopy is used to investigate the excited-state dynamics of a dinucleotide containing an 8-oxoguanine anion at the 5'-end and neutral adenine at the 3'-end. UV excitation of the dinucleotide transfers an electron from deprotonated 8-oxoguanine to its π-stacked neighbor adenine in less than 1 ps, generating a neutral 8-oxoguanine radical and an adenine radical anion. These species are identified by the excellent agreement between the experimental and calculated IR difference spectra. The quantum efficiency of this ultrafast charge shift reaction approaches unity. Back electron transfer from the adenine radical anion to the 8-oxguanine neutral radical occurs in 9 ps, or approximately 6 times faster than between the adenine radical anion and the 8-oxoguanine radical cation (Zhang, Y. et al. Proc. Natl. Acad. Sci. U.S.A. 2014, 111, 11612-11617). The large asymmetry in forward and back electron transfer rates is fully rationalized by semiclassical nonadiabatic electron transfer theory. Forward electron transfer is ultrafast because the driving force is nearly equal to the reorganization energy, which is estimated to lie between 1 and 2 eV. Back electron transfer is highly exergonic and takes place much more slowly in the Marcus inverted region.

  14. Ultrafast Photoinduced Symmetry-Breaking Charge Separation and Electron Sharing in Perylenediimide Molecular Triangles.

    PubMed

    Wu, Yilei; Young, Ryan M; Frasconi, Marco; Schneebeli, Severin T; Spenst, Peter; Gardner, Daniel M; Brown, Kristen E; Würthner, Frank; Stoddart, J Fraser; Wasielewski, Michael R

    2015-10-21

    We report on a visible-light-absorbing chiral molecular triangle composed of three covalently linked 1,6,7,12-tetra(phenoxy)perylene-3,4:9,10-bis(dicarboximide) (PDI) units. The rigid triangular architecture reduces the electronic coupling between the PDIs, so ultrafast symmetry-breaking charge separation is kinetically favored over intramolecular excimer formation, as revealed by femtosecond transient absorption spectroscopy. Photoexcitation of the PDI triangle dissolved in CH2Cl2 gives PDI(+•)-PDI(-•) in τCS = 12.0 ± 0.2 ps. Fast subsequent intramolecular electron/hole hopping can equilibrate the six possible energetically degenerate ion-pair states, as suggested by electron paramagnetic resonance/electron-nuclear double resonance spectroscopy, which shows that one-electron reduction of the PDI triangle results in complete electron sharing among the three PDIs. Charge recombination of PDI(+•)-PDI(-•) to the ground state occurs in τCR = 1.12 ± 0.01 ns with no evidence of triplet excited state formation.

  15. Photoinduced diffusion molecular transport

    NASA Astrophysics Data System (ADS)

    Rozenbaum, Viktor M.; Dekhtyar, Marina L.; Lin, Sheng Hsien; Trakhtenberg, Leonid I.

    2016-08-01

    We consider a Brownian photomotor, namely, the directed motion of a nanoparticle in an asymmetric periodic potential under the action of periodic rectangular resonant laser pulses which cause charge redistribution in the particle. Based on the kinetics for the photoinduced electron redistribution between two or three energy levels of the particle, the time dependence of its potential energy is derived and the average directed velocity is calculated in the high-temperature approximation (when the spatial amplitude of potential energy fluctuations is small relative to the thermal energy). The thus developed theory of photoinduced molecular transport appears applicable not only to conventional dichotomous Brownian motors (with only two possible potential profiles) but also to a much wider variety of molecular nanomachines. The distinction between the realistic time dependence of the potential energy and that for a dichotomous process (a step function) is represented in terms of relaxation times (they can differ on the time intervals of the dichotomous process). As shown, a Brownian photomotor has the maximum average directed velocity at (i) large laser pulse intensities (resulting in short relaxation times on laser-on intervals) and (ii) excited state lifetimes long enough to permit efficient photoexcitation but still much shorter than laser-off intervals. A Brownian photomotor with optimized parameters is exemplified by a cylindrically shaped semiconductor nanocluster which moves directly along a polar substrate due to periodically photoinduced dipole moment (caused by the repetitive excited electron transitions to a non-resonant level of the nanocylinder surface impurity).

  16. Photoinduced electron transfer and solvation in iodide-doped acetonitrile clusters.

    PubMed

    Ehrler, Oli T; Griffin, Graham B; Young, Ryan M; Neumark, Daniel M

    2009-04-02

    We have used ultrafast time-resolved photoelectron imaging to measure charge transfer dynamics in iodide-doped acetonitrile clusters I(-)(CH(3)CN)(n) with n = 5-10. Strong modulations of vertical detachment energies were observed following charge transfer from the halide, allowing interpretation of the ongoing dynamics. We observe a sharp drop in the vertical detachment energy (VDE) within 300-400 fs, followed by a biexponential increase that is complete by approximately 10 ps. Comparison to theory suggests that the iodide is internally solvated and that photodetachment results in formation of a diffuse electron cloud in a confined cavity. We interpret the initial drop in VDE as a combination of expansion of the cavity and localization of the excess electron on one or two solvent molecules. The subsequent increase in VDE is attributed to a combination of the I atom leaving the cavity and rearrangement of the acetonitrile molecules to solvate the electron. The n = 5-8 clusters then show a drop in VDE of around 50 meV on a much longer time scale. The long-time VDEs are consistent with those of (CH(3)CN)(n)(-) clusters with internally solvated electrons. Although the excited-state created by the pump pulse decays by emission of a slow electron, no such decay is seen by 200 ps.

  17. Photoinduced direct electron transfer from InSe to GaSe semiconductor nanoparticles.

    PubMed

    Tu, Haohua; Kelley, David F

    2006-01-01

    Direct electron transfer from InSe nanoparticles to GaSe nanoparticles in mixed solution-phase aggregates has been found to occur upon photoexcitation. Mixed aggregates exhibit a strong charge-transfer absorption band at an energy slightly higher than the InSe band gap. Photoexcitation of this band results in a polarized transient absorption spectrum and transient absorption kinetics characteristic of InSe valence-band holes and GaSe conduction-band electrons. The kinetics indicate that charge separation persists for at least several hundred picoseconds.

  18. Photoinduced Electronic Energy Transfer: Theoretical and Experimental Issues for Light Harvesting Applications

    DTIC Science & Technology

    2013-10-21

    harvesting systems. Summary of key results: 1. Coherence in photosynthetic light harvesting (experiment) The initial step in photosynthesis...involves the capture of energy from sunlight. Specialized pigment -protein complexes, called light-harvesting antenna complexes, have evolved for this...ours) have reported the observation of oscillations in 2DES attributed to the coherent evolution of electronic excitations in photosynthetic

  19. Photoinduced electron transfer between Fe(III) and adenosine triphosphate-BODIPY conjugates: Application to alkaline-phosphatase-linked immunoassay.

    PubMed

    Lin, Jia-Hui; Yang, Ya-Chun; Shih, Ya-Chen; Hung, Szu-Ying; Lu, Chi-Yu; Tseng, Wei-Lung

    2016-03-15

    Fluorescent boron dipyrromethene (BODIPY) analogs are often used as sensors for detecting various species because of their relatively high extinction coefficients, outstanding fluorescence quantum yields, photostability, and pH-independent fluorescence. However, there is little-to-no information in the literature that describes the use of BODIPY analogs for detecting alkaline phosphatase (ALP) activity and inhibition. This study discovered that the fluorescence of BODIPY-conjugated adenosine triphosphate (BODIPY-ATP) was quenched by Fe(III) ions through photoinduced electron transfer. The ALP-catalyzed hydrolysis of BODIPY-ATP resulted in the formation of BODIPY-adenosine and phosphate ions. The fluorescence of the generated BODIPY-adenosine was insensitive to the change in the concentration of Fe(III) ions. Thus, the Fe(III)-induced fluorescence quenching of BODIPY-ATP can be paired with its ALP-mediated dephosphorylation to design a turn-on fluorescence probe for ALP sensing. A method detection limit at a signal-to-noise ratio of 3 for ALP was estimated to be 0.02 units/L (~6 pM; 1 ng/mL). This probe was used for the screening of ALP inhibitors, including Na3VO4, imidazole, and arginine. Because ALP is widely used in enzyme-linked immunosorbent assays, the probe was coupled to an ALP-linked immunosorbent assay for the sensitive and selective detection of immunoglobulin G (IgG). The lowest detectable concentration for IgG in this system was 5 ng/mL. Compared with the use of 3,6-fluorescein diphosphate as a signal reporter in an ALP-linked immunosorbent assay, the proposed system provided comparable sensitivity, large linear range, and high stability over temperature and pH changes.

  20. Ultrafast photo-induced electron-transfer from coumarin dyes adsorbed on semiconductor nanoclusters surfaces

    SciTech Connect

    Castner, E.W. Jr.; Murakoshi, Kei; Yanagida, Shozo

    1997-12-31

    Photosensitizers adsorbed directly on semiconductor surfaces provide the basis for solar photoelectrochemical devices. Semiconductor nanoclusters in solution allow for simple preparation of the photosensitized surface, with very large surface area. To optimize the efficiency of the photoelectrochemical cycle, one must know the rates of forward and reverse electron-transfer from the excited state dye to the semiconductor conduction band. We present measurements of the ultrafast forward electron-transfer rates for three coumarin dyes (Coumarins 343, D-1421, and D-126) bound by the carboxylic acid group to the metal cationic sites of TiO{sub 2} and ZnO semiconductor nanocluster surfaces. These rates are obtained directly from the ultrafast fluorescence dynamics, measured using the femotosecond upconversion technique. Coumarins 343 and D-1421 on TiO{sub 2} nanoclusters in aqueous solution display very rapid forward electron-transfer with rate constants exceeding 10{sup 13} s{sup -1}. Substantially slower rates are observed for the same coumarin TiO{sub 2} systems in methanol solution.

  1. Photo-induced electron detachment of protein polyanions in the VUV range.

    PubMed

    Brunet, Claire; Antoine, Rodolphe; Dugourd, Philippe; Canon, Francis; Giuliani, Alexandre; Nahon, Laurent

    2013-02-14

    Biomolecular polyanions mainly relax by electron emission after UV excitation. Here, we study photodetachment of protein polyanions in the 6-16 eV VUV range by coupling a linear quadrupole ion trap with a synchrotron beamline. Gas-phase VUV action spectra of electrospray-produced multiply deprotonated insulin (5.6 kDa) and myoglobin (16.7 kDa) proteins are reported, which significantly increases the amount of data available on the optical response of proteins in the VUV. The influence of the protein charge and oxidation state upon the electron detachment efficiency is discussed. For small protein such as insulin, it appears that higher charge states produce higher detachment yields. Investigations on oxidized species show that the nature of the groups bearing the negative charges has an influence on the yields. For larger proteins, comparison of two forms of myoglobin clearly indicate that the three-dimensional structure does not impact much on the shape and the magnitude of the photodetachment spectra, in spite of a slight shift for the first electronic excited states.

  2. Photo-induced electron detachment of protein polyanions in the VUV range

    SciTech Connect

    Brunet, Claire; Antoine, Rodolphe; Dugourd, Philippe; Canon, Francis; Nahon, Laurent; Giuliani, Alexandre

    2013-02-14

    Biomolecular polyanions mainly relax by electron emission after UV excitation. Here, we study photodetachment of protein polyanions in the 6-16 eV VUV range by coupling a linear quadrupole ion trap with a synchrotron beamline. Gas-phase VUV action spectra of electrospray-produced multiply deprotonated insulin (5.6 kDa) and myoglobin (16.7 kDa) proteins are reported, which significantly increases the amount of data available on the optical response of proteins in the VUV. The influence of the protein charge and oxidation state upon the electron detachment efficiency is discussed. For small protein such as insulin, it appears that higher charge states produce higher detachment yields. Investigations on oxidized species show that the nature of the groups bearing the negative charges has an influence on the yields. For larger proteins, comparison of two forms of myoglobin clearly indicate that the three-dimensional structure does not impact much on the shape and the magnitude of the photodetachment spectra, in spite of a slight shift for the first electronic excited states.

  3. Photo-induced electron detachment of protein polyanions in the VUV range

    NASA Astrophysics Data System (ADS)

    Brunet, Claire; Antoine, Rodolphe; Dugourd, Philippe; Canon, Francis; Giuliani, Alexandre; Nahon, Laurent

    2013-02-01

    Biomolecular polyanions mainly relax by electron emission after UV excitation. Here, we study photodetachment of protein polyanions in the 6-16 eV VUV range by coupling a linear quadrupole ion trap with a synchrotron beamline. Gas-phase VUV action spectra of electrospray-produced multiply deprotonated insulin (5.6 kDa) and myoglobin (16.7 kDa) proteins are reported, which significantly increases the amount of data available on the optical response of proteins in the VUV. The influence of the protein charge and oxidation state upon the electron detachment efficiency is discussed. For small protein such as insulin, it appears that higher charge states produce higher detachment yields. Investigations on oxidized species show that the nature of the groups bearing the negative charges has an influence on the yields. For larger proteins, comparison of two forms of myoglobin clearly indicate that the three-dimensional structure does not impact much on the shape and the magnitude of the photodetachment spectra, in spite of a slight shift for the first electronic excited states.

  4. Coherent control of long-range photoinduced electron transfer by stimulated X-ray Raman processes

    PubMed Central

    Dorfman, Konstantin E.; Zhang, Yu; Mukamel, Shaul

    2016-01-01

    We show that X-ray pulses resonant with selected core transitions can manipulate electron transfer (ET) in molecules with ultrafast and atomic selectivity. We present possible protocols for coherently controlling ET dynamics in donor–bridge–acceptor (DBA) systems by stimulated X-ray resonant Raman processes involving various transitions between the D, B, and A sites. Simulations presented for a Ru(II)–Co(III) model complex demonstrate how the shapes, phases and amplitudes of the X-ray pulses can be optimized to create charge on demand at selected atoms, by opening up otherwise blocked ET pathways. PMID:27559082

  5. Photoinduced electron transfer from triplet fullerene, [sup 3]C[sub 60], to tetracyanoethylene. Fourier transform electron paramagnetic resonance study

    SciTech Connect

    Michaeli, S.; Meiklyar, V.; Levanon, H. ); Schulz, M.; Moebius, K. )

    1994-08-04

    Fourier transform EPR spectroscopy was employed in studying the electron transfer (ET) and the quenching mechanisms of the photoexcited triplet state of C[sub 60] (electron donor) in the presence of the electron acceptor tetracyanoethylene (TCNE) in a benzonitrile solution. The ET reaction product, which is the stable anion radical TCNE[sup [minus

  6. Controlling Photoinduced Electron Transfer Via Defects Self-Organization for Novel Functional Macromolecular Systems

    PubMed Central

    Campi, Gaetano; Ciasca, Gabriele; Poccia, Nicola; Ricci, Alessandro; Fratini, Michela; Bianconi, Antonio

    2014-01-01

    The electrons transfer (ET) from an atom or a molecule, donor (D), to another, acceptor (A) is the basis of many fundamental chemical and physical processes. The ET mechanism is controlled by spatial arrangements of donor and acceptors: it’s the particular spatial arrangement and thus the particular distance and the orientation between the electron donors and acceptors that controls the efficiency in charge separation processes in nature. Here, we stress the importance of this concept reviewing how spatial distribution of atomic and molecular self-assembly can determine the quality and physical features of ET process from biology to material science. In this context, we propose novel lab-on-chip techniques to be used to control spatial distribution of molecules at nanoscale. Synchrotron source brightness jointly to focusing optics fabrication allows one nowadays to monitor and visualize structures with sub-micrometric spatial resolution. This can give us a new powerful tool to set up sophisticated X-ray imaging techniques as well as spectroscopic elemental and chemical mapping to investigate the structure-function relationship controlling the spatial arrangement of the molecules at nanoscale. Finally, we report intriguing recent case studies on the possibility to manipulate and control this spatial distribution and material functionality at nanoscale by using X ray illumination.

  7. Photoinduced electron-transfer from imidazole derivative to nano-semiconductors.

    PubMed

    Karunakaran, C; Jayabharathi, J; Jayamoorthy, K; Devi, K Brindha

    2012-04-01

    Bioactive imidazole derivative absorbs in the UV region at 305 nm. The interaction of imidazole derivative with nanoparticulate WO3, Fe2O3, Fe3O4, CuO, ZrO2 and Al2O3 has been studied by UV-visible absorption, FT-IR and fluorescence spectroscopies. The imidazole derivative adsorbs strongly on the surfaces of nanosemiconductor, the apparent binding constants for the association between nanomaterials and imidazole derivative have been determined from the fluorescence quenching. In the case of nanocrystalline insulator, fluorescence quenching through electron transfer from the excited state of the imidazole derivative to alumina is not possible. However, a possible mechanism for the quenching of fluorescence by the insulator is energy transfer, that is, energy transferred from the organic molecule to the alumina lattice. Based on Forster's non-radiation energy transfer theory, the distance between the imidazole derivative and nanoparticles (r0∼2.00 nm) as well as the critical energy transfer distance (R0∼1.70 nm) has been calculated. The interaction between the imidazole derivative and nanosurfaces occurs through static quenching mechanism. The free energy change (ΔGet) for electron transfer process has been calculated by applying Rehm-Weller equation.

  8. Controlling photoinduced electron transfer via defects self-organization for novel functional macromolecular systems.

    PubMed

    Campi, Gaetano; Ciasca, Gabriele; Poccia, Nicola; Ricci, Alessandro; Fratini, Michela; Bianconi, Antonio

    2014-01-01

    The electrons transfer (ET) from an atom or a molecule, donor (D), to another, acceptor (A) is the basis of many fundamental chemical and physical processes. The ET mechanism is controlled by spatial arrangements of donor and acceptors: it's the particular spatial arrangement and thus the particular distance and the orientation between the electron donors and acceptors that controls the efficiency in charge separation processes in nature. Here, we stress the importance of this concept reviewing how spatial distribution of atomic and molecular self-assembly can determine the quality and physical features of ET process from biology to material science. In this context, we propose novel lab-on-chip techniques to be used to control spatial distribution of molecules at nanoscale. Synchrotron source brightness jointly to focusing optics fabrication allows one nowadays to monitor and visualize structures with sub-micrometric spatial resolution. This can give us a new powerful tool to set up sophisticated X-ray imaging techniques as well as spectroscopic elemental and chemical mapping to investigate the structure-function relationship controlling the spatial arrangement of the molecules at nanoscale. Finally, we report intriguing recent case studies on the possibility to manipulate and control this spatial distribution and material functionality at nanoscale by using X ray illumination.

  9. All-optical photochromic spatial light modulators based on photoinduced electron transfer in rigid matrices

    NASA Technical Reports Server (NTRS)

    Beratan, David N. (Inventor); Perry, Joseph W. (Inventor)

    1991-01-01

    A single material (not a multi-element structure) spatial light modulator may be written to, as well as read out from, using light. The device has tailorable rise and hold times dependent on the composition and concentration of the molecular species used as the active components. The spatial resolution of this device is limited only by light diffraction as in volume holograms. The device may function as a two-dimensional mask (transmission or reflection) or as a three-dimensional volume holographic medium. This device, based on optically-induced electron transfer, is able to perform incoherent to coherent image conversion or wavelength conversion over a wide spectral range (ultraviolet, visible, or near-infrared regions).

  10. Photoinduced biphasic hydrogen evolution: decamethylosmocene as a light-driven electron donor.

    PubMed

    Ge, Peiyu; Olaya, Astrid J; Scanlon, Micheál D; Hatay Patir, Imren; Vrubel, Heron; Girault, Hubert H

    2013-07-22

    Excitation of the weak electron donor decamethylosmocene on illumination with white light produces an excited-state species capable of reducing organically solubilized protons under biphasic conditions. Insight into the mechanism and kinetics of light-driven biphasic hydrogen evolution are obtained by analysis with gas chromatography, cyclic voltammetry, and UV/Vis and (1)H NMR spectroscopy. Formation of decamethylosmocenium hydride, which occurs prior to hydrogen evolution, is a rapid step relative to hydrogen release and takes place independently of light activation. Remarkably, hydride formation occurs with greater efficiency (ca. 90% conversion) under biphasic conditions than when the reaction is carried out in an acidified single organic phase (ca. 20% conversion). Cyclic voltammetry studies reveal that decamethylosmocene has a higher proton affinity than either decamethylferrocene or osmocene.

  11. Donor–acceptor graphene-based hybrid materials facilitating photo-induced electron-transfer reactions

    PubMed Central

    Stergiou, Anastasios; Pagona, Georgia

    2014-01-01

    Summary Graphene research and in particular the topic of chemical functionalization of graphene has exploded in the last decade. The main aim is to increase the solubility and thereby enhance the processability of the material, which is otherwise insoluble and inapplicable for technological applications when stacked in the form of graphite. To this end, initially, graphite was oxidized under harsh conditions to yield exfoliated graphene oxide sheets that are soluble in aqueous media and amenable to chemical modifications due to the presence of carboxylic acid groups at the edges of the lattice. However, it was obvious that the high-defect framework of graphene oxide cannot be readily utilized in applications that are governed by charge-transfer processes, for example, in solar cells. Alternatively, exfoliated graphene has been applied toward the realization of some donor–acceptor hybrid materials with photo- and/or electro-active components. The main body of research regarding obtaining donor–acceptor hybrid materials based on graphene to facilitate charge-transfer phenomena, which is reviewed here, concerns the incorporation of porphyrins and phthalocyanines onto graphene sheets. Through illustrative schemes, the preparation and most importantly the photophysical properties of such graphene-based ensembles will be described. Important parameters, such as the generation of the charge-separated state upon photoexcitation of the organic electron donor, the lifetimes of the charge-separation and charge-recombination as well as the incident-photon-to-current efficiency value for some donor–acceptor graphene-based hybrids, will be discussed. PMID:25247140

  12. Electron donor-acceptor quenching and photoinduced electron transfer for coumarin dyes. Technical report, 1 January-31 October 1982

    SciTech Connect

    Jones, G. II; Griffin, S.F.; Choi, C.; Bergmark, W.R.

    1983-10-31

    The fluorescence of 7-aminocoumarins is quenched by a variety of organic electron donors or acceptors in acetonitrile. In general, donors with half-wave oxidation potentials less positive than 1.0 V vs SCE and acceptors with reduction potentials less negative than -1.5 V vs SCE are candidates for diffusion limited quenching of coumarin singlet states. Profiles of quenching rates are consistent with calculated free energies for electron transfer between excited coumarins and donors or acceptors. In flash photolysis experiments electron transfer for several dyes and quenchers (e.g., methyl viologen) is demonstrated. Relatively low yields of net electron transfer are consistently obtained due to inefficient ionic photodissociation via singlet quenching or a low yield of more photoactive coumarin triplets. Electrochemical properties of the coumarins have been investigated by cyclic voltammetry with the indications of reversible oxidation and irreversible reduction as important processes.

  13. Multifractal analysis of photoinduced cooperative phenomena

    NASA Astrophysics Data System (ADS)

    Ishida, Kunio; Nasu, Keiichiro

    2008-01-01

    We study the multifractal properties of the geometrical patterns which appear in the initial processes of photoinduced structural change. Employing a model of localized electrons coupled with a single-phonon mode, we calculate the Lipschitz-Hölder exponent α and singularity spectrum f(α) on the distribution of excited electronic states and molecular distortion by using the box-counting method, and discuss the temporal behavior of photoinduced domains.

  14. Photoinduced electron transfer in an imidazolium ionic liquid and in its binary mixtures with water, methanol, and 2-propanol: appearance of Marcus-type of inversion.

    PubMed

    Sarkar, Souravi; Mandal, Sarthak; Ghatak, Chiranjib; Rao, Vishal Govind; Ghosh, Surajit; Sarkar, Nilmoni

    2012-02-02

    The photoinduced electron transfer (PET) reaction has been investigated in a room temperature imidazolium ionic liquid (RTIL), 1-ethyl-3-methylimidazolium ethyl sulfate ([Emim][EtSO(4)]) and also in [Emim][EtSO(4)]-co-solvents mixtures from N,N-dimethyl aniline (DMA) to different Coumarin dyes using steady state and time-resolved fluorescence quenching measurements. We have used water and methanol and 2-propanol as the cosolvents of RTILs for the PET study. On going from neat ionic liquid to the RTIL-co-solvents mixtures the electron transfer rate has been largely enhanced. In neat RTIL as well as in [Emim][EtSO(4)]-co-solvents mixtures, a Marcus type of inversion in the PET rate have been observed.

  15. An attempt at a product vibrational analysis of a photo-induced chemical reaction by means of time-resolved (e, 2e) electron momentum spectroscopy

    NASA Astrophysics Data System (ADS)

    Yamazaki, M.; Nakazawa, H.; Zhu, C. Y.; Takahashi, M.

    2015-09-01

    We report on a new attempt at an analysis of the vibrational state distributions in the products of a photo-induced chemical reaction. The experiment was performed by using time- resolved electron momentum spectroscopy (TR-EMS) for the products produced by the three- body photodissociation dynamics of the deuterated acetone molecule at 195 nm. It has been found from a comparison between the experiment and associated theoretical calculations that future TR-EMS measurements with improved statistics could be useful for the vibrational analysis of reaction products, in cases when effects of molecular vibration on their electron momentum densities are large enough so as to be noticeable in the binding energy spectra.

  16. Thermodynamic control over the competitive anchoring of N719 dye on nanocrystalline TiO2 for improving photoinduced electron generation.

    PubMed

    Lim, Jongchul; Kwon, Young Soo; Park, Sung-Hae; Song, In Young; Choi, Jongmin; Park, Taiho

    2011-12-06

    TiO(2) electrodes, sensitized with the N719 dye at high immersion temperatures during the sensitization process, were found to have large fractions of weakly bound N719 on the electrode surface, which resulted in dye aggregation and decreased device longevity. These disadvantages were ameliorated using a low-temperature stearic acid (SA)-assisted anchoring method described here. The activation energy (ΔE(NS)(++)) and relative fraction of strongly bound N719 were twice as large as the respective values obtained without the use of SA. Slowing of adsorption, both by thermal means and through SA-mediated processes, effectively controlled the binding mode of N719 on the surface of TiO(2). The resulting sensitized electrodes displayed enhanced device longevity and improved generation of photoinduced electrons.

  17. Fluoride anion sensing mechanism of 2-ureido-4[1H]-pyrimidinone quadruple hydrogen-bonded supramolecular assembly: photoinduced electron transfer and partial configuration change.

    PubMed

    Chen, Jun-Sheng; Zhou, Pan-Wang; Li, Guang-Yue; Chu, Tian-Shu; He, Guo-Zhong

    2013-05-02

    The fluoride anion sensing mechanism of 6-methyl-5-(9-methylene-anthracene)-(2-butylureido-4[1H]-pyrimidinone) (AnUP) has been investigated using the DFT/TDDFT method. The theoretical results indicate that the proton of the N3-H3 group in pyrimidine moiety is captured by the added fluoride anion and then deprotonated. The calculated vertical excitation energies of AnUP-dimer and its deprotonated form agree well with the experimental results. The molecular orbital analysis demonstrates that the first excited state (S1) of AnUP-dimer is a local excited state with a π-π* transition, whereas for the deprotonated form, S1 is a completely charge-separation state and is responsible for the photoinduced electron transfer (PET) process. The PET process from anthracene to the pyrimidine moiety leads to the fluorescence quenching.

  18. Micellar control over tautomerization and photo-induced electron transfer of Lumichrome in the presence of aliphatic and aromatic amines: a transient absorption study

    NASA Astrophysics Data System (ADS)

    Sengupta, Chaitrali; Sarangi, Manas Kumar; Sau, Abhishek; Basu, Samita

    2017-03-01

    Lumichrome (Lc), a molecule consisting of a trinuclear alloxazine moiety is our present subject of interest. This molecule is subjected to tautomerization in the presence of pyridine, acetic acid, etc, through the formation of an eight-membered ring. In our present contribution, we have attempted to analyze the influence of the presence of an aliphatic amine, triethylamine (TEA) and an aromatic amine, N,N-dimethylaniline (DMA) in the double proton transfer step of the tautomerization as well as the photo-induced electron transfer (PET) from those amines to Lc. We have studied these phenomena within micelles, anionic and neutral, to observe the effect of confinement. Through our experiments, it could be stated that along with tautomerization and proton transfer, there is also evidence of PET in triplet excited state.

  19. Photoinduced intercomponent excited-state decays in a molecular dyad made of a dinuclear rhenium(I) chromophore and a fullerene electron acceptor unit.

    PubMed

    Nastasi, Francesco; Puntoriero, Fausto; Natali, Mirco; Mba, Miriam; Maggini, Michele; Mussini, Patrizia; Panigati, Monica; Campagna, Sebastiano

    2015-05-01

    A novel molecular dyad, 1, made of a dinuclear {[Re2(μ-X)2(CO)6(μ-pyridazine)]} component covalently-linked to a fullerene unit by a carbocyclic molecular bridge has been prepared and its redox, spectroscopic, and photophysical properties - including pump-probe transient absorption spectroscopy in the visible and near-infrared region - have been investigated, along with those of its model species. Photoinduced, intercomponent electron transfer occurs in 1 from the thermally-equilibrated, triplet metal/ligand-to-ligand charge-transfer ((3)MLLCT) state of the dinuclear rhenium(I) subunit to the fullerene acceptor, with a time constant of about 100 ps. The so-formed triplet charge-separated state recombines in a few nanoseconds by a spin-selective process yielding, rather than the ground state, the locally-excited, triplet fullerene state, which finally decays to the ground state by intersystem crossing in about 290 ns.

  20. Engaging Copper(III) Corrole as an Electron Acceptor: Photoinduced Charge Separation in Zinc Porphyrin-Copper Corrole Donor-Acceptor Conjugates.

    PubMed

    Ngo, Thien H; Zieba, David; Webre, Whitney A; Lim, Gary N; Karr, Paul A; Kord, Scheghajegh; Jin, Shangbin; Ariga, Katsuhiko; Galli, Marzia; Goldup, Steve; Hill, Jonathan P; D'Souza, Francis

    2016-01-22

    An electron-deficient copper(III) corrole was utilized for the construction of donor-acceptor conjugates with zinc(II) porphyrin (ZnP) as a singlet excited state electron donor, and the occurrence of photoinduced charge separation was demonstrated by using transient pump-probe spectroscopic techniques. In these conjugates, the number of copper corrole units was varied from 1 to 2 or 4 units while maintaining a single ZnP entity to observe the effect of corrole multiplicity in facilitating the charge-separation process. The conjugates and control compounds were electrochemically and spectroelectrochemically characterized. Computational studies revealed ground state geometries of the compounds and the electron-deficient nature of the copper(III) corrole. An energy level diagram was established to predict the photochemical events by using optical, emission, electrochemical, and computational data. The occurrence of charge separation from singlet excited zinc porphyrin and charge recombination to yield directly the ground state species were evident from the diagram. Femtosecond transient absorption spectroscopy studies provided spectral evidence of charge separation in the form of the zinc porphyrin radical cation and copper(II) corrole species as products. Rates of charge separation in the conjugates were found to be of the order of 10(10)  s(-1) and increased with increasing multiplicity of copper(III) corrole entities. The present study demonstrates the importance of copper(III) corrole as an electron acceptor in building model photosynthetic systems.

  1. Influence of π-conjugation structural changes on intramolecular charge transfer and photoinduced electron transfer in donor-π-acceptor dyads.

    PubMed

    Kim, So-Yoen; Cho, Yang-Jin; Lee, Ah-Rang; Son, Ho-Jin; Han, Won-Sik; Cho, Dae Won; Kang, Sang Ook

    2016-12-21

    The influence of π-conjugation structural changes on photoinduced electron transfer (PET) and intramolecular charge transfer (ICT) processes in π-conjugated donor (D)-acceptor (A) dyads (D-π-A) was investigated. Three types of D-π-A dyads were prepared through the modification of the structure of their π-conjugated linker, including D-π-A (1) and D-πtw-A (2) having a twisted π-conjugation, and D-π-Si-π-A (3) with a π-conjugation severed by a Si-atom. In these dyads, carbazole (Cz) and oxadiazole (Oz) moieties act as an electron donor and acceptor, respectively. The emission maxima of dyads 1 and 3 red-shifted with the increase in polarity, which could be attributed to the ICT process. The fluorescence lifetimes of dyads 1 and 3 were 2.64 and 4.29 ns in CH2Cl2, respectively. In contrast, dyad 2 showed dual emission at 350 and 470 nm in CH2Cl2. The emission of dyad 2 at 380 nm corresponded to the monomer fluorescence in the locally excited state. Moreover, the emission at 470 nm increased simultaneously with the diminishing of the fluorescence at 380 nm. This emission band can be assigned as the intramolecular exciplex emission, and showed a strong solvatochromic shift. The low emission quantum yield (<3%) of dyad 2 is due to the PET process. In dyad 2, the cationic and anionic radical species generated by the PET process were confirmed by femtosecond transient absorption (fs-TA) spectroscopy. Upon photoexcitation at 290 or 340 nm, the A or D moieties can be selectively excited. Upon excitation at 290 nm, the acceptor moiety can be excited to the (1)A* state, thus the photoinduced hole transfer (PHT) takes place from (1)A* to D through the HOMO levels within a few picoseconds. On the other hand, when the donor moiety is excited at 340 nm, the PET process occurs from (1)D* to A. Based on the fs-TA studies, it was found that the dynamics and mechanisms for the electron (or charge) transfer were strongly affected by the variation of the π-conjugation of the

  2. Influences of acid on molecular forms of fluorescein and photoinduced electron transfer in fluorescein-dispersing sol-gel titania films.

    PubMed

    Nishikiori, Hiromasa; Setiawan, Rudi Agus; Miyashita, Kyohei; Teshima, Katsuya; Fujii, Tsuneo

    2014-01-01

    Fluorescein-dispersing titania gel films were prepared by the acid-catalyzed sol-gel reaction using a titanium alkoxide solution containing fluorescein. The molecular forms of fluorescein in the films, depending on its acid-base equilibria, and the complex formation and photoinduced electron transfer process between the dye and titania surface were investigated by fluorescence and photoelectric measurements. The titanium species were coordinated to the carboxylate and phenolate-like groups of the fluorescein species. The quantum efficiencies of the fluorescence quenching and photoelectric conversion were higher upon excitation of the dianion species interacting with the titania, i.e. the dye-titania complex. This result indicated that the dianion form was the most favorable for formation of the dye-titania complex exhibiting the highest electron transfer efficiency. Using nitric acid as the catalyst, the titania surface bonded to the fluorescein instead of the adsorbed nitrate ion during the steam treatment. The dye-titania complex formation played an important role in the electron injection from the dye to the titania conduction band.

  3. Photodissociation and ab initio studies of Mg+(NH3)n, n=1-4: Electronic structure and photoinduced reaction

    NASA Astrophysics Data System (ADS)

    Yoshida, Shinji; Daigoku, Kota; Okai, Nobuhiro; Takahata, Akihiro; Sabu, Akiyoshi; Hashimoto, Kenro; Fuke, Kiyokazu

    2002-11-01

    Photodissociation spectra of Mg+(NH3)n (n=1-4) cluster ions are examined in the wavelength region of 240-1200 nm. From the comparison with the results of ab initio calculations for the structure and the excitation energies of these clusters, the observed absorption bands are assigned to the transitions derived from the 2P-2S transition of Mg+ ion. The extensive redshift of the observed spectra is ascribed to the formation of a one-center ion-pair state. In the photolysis of Mg+NH3, NH3+ and Mg+NH2 ions are produced via photoinduced charge transfer and intracluster reaction processes, respectively, in addition to the Mg+ ion generated by the evaporation of ammonia molecules. For n=2, both the intracluster reaction and evaporation are dominant decay processes, while the evaporation is the sole photodissociation channel for larger clusters. The branching fractions of these processes are found to depend strongly on the solvation number n and also on the photolysis wavelength. The energetics and the dynamics of the dissociation processes are discussed in relation to the redox reaction of metal ions.

  4. Energetic comparison between photoinduced electron-transfer reactions from NADH model compounds to organic and inorganic oxidants and hydride-transfer reactions from NADH model compounds to p-benzoquinone derivatives

    SciTech Connect

    Fukuzumi, S.; Koumitsu, S.; Hironaka, K.; Tanaka, T.

    1987-01-21

    Kinetic studies on photoinduced electron-transfer reactions from dihydropyridine compounds (PyH/sub 2/) as being NADH model compounds to organic and inorganic oxidants and hydride-transfer reactions from PyH/sub 2/ to p-benzoquinone derivatives (Q) in the absence and presence of Mg/sup 2 +/ ion are reported by determining over 150 rate constants. These results, combined with the values of Gibbs energy change of the photoinduced electron-transfer reactions as well as those of each step of the hydride-transfer reactions as being the e/sup -/-H/sup +/-e/sup -/ sequence, which are determined independently, revealed that the rate constants of the photoinduced electron-transfer reactions obey the Rehm-Weller-Gibbs energy relationship and that the activation barrier of the hydride-transfer reactions from PyH/sub 2/ to Q is dependent solely on the Gibbs energy changes of the initial electron transfer from PyH/sub 2/ to Q and the following proton transfer from PyH/sub 2//sup .+/ to Q/sup .-/ and thus independent of the Gibbs energy change of the final electron transfer from PyH/sup ./ to QH/sup ./. The retarding effect of Mg/sup 2 +/ ion observed on the photoinduced electron transfer and hydride-transfer reactions of PyH/sub 2/ is ascribed to the positive shifts of the redox potentials of the ground and excited states of PyH/sub 2/ due to the complex formation with Mg/sup 2 +/ ion.

  5. Sensitive fast electron spectrometer in adjustable triode configuration with pulsed tunable laser for research on photo-induced field emission cathodes

    SciTech Connect

    Mingels, S. Porshyn, V.; Bornmann, B.; Lützenkirchen-Hecht, D.; Müller, G.

    2015-04-15

    We have completed an ultra-high vacuum system for sensitive fast electron spectroscopy from cold cathodes in triode configuration under high electric fields E (<100 MV/m) and pulsed tunable laser illumination (3.5 ns, 10 Hz, hν = 0.5-5.9 eV, and 0.3-17 mJ). The cathodes are prepared and inserted under clean room conditions and can be precisely 3D-positioned, cooled or heated (77-400 K). Commissioning results with the upgraded system are presented. Field emission measurements with a W tip yielded an energy resolution of 14 meV at 4 eV pass energy and a precise determination of the emitter work function, size, and temperature. Photoemission spectroscopy of short electron bunches from a virgin and laser-ablated S-GaP crystal and quantum efficiency measurements revealed surface states, energy relaxation, and band structure effects. In conclusion, this novel system is ready now for the development and characterization of photo-induced field emission cathodes.

  6. Sensitive fast electron spectrometer in adjustable triode configuration with pulsed tunable laser for research on photo-induced field emission cathodes.

    PubMed

    Mingels, S; Porshyn, V; Bornmann, B; Lützenkirchen-Hecht, D; Müller, G

    2015-04-01

    We have completed an ultra-high vacuum system for sensitive fast electron spectroscopy from cold cathodes in triode configuration under high electric fields E (<100 MV/m) and pulsed tunable laser illumination (3.5 ns, 10 Hz, hν = 0.5-5.9 eV, and 0.3-17 mJ). The cathodes are prepared and inserted under clean room conditions and can be precisely 3D-positioned, cooled or heated (77-400 K). Commissioning results with the upgraded system are presented. Field emission measurements with a W tip yielded an energy resolution of 14 meV at 4 eV pass energy and a precise determination of the emitter work function, size, and temperature. Photoemission spectroscopy of short electron bunches from a virgin and laser-ablated S-GaP crystal and quantum efficiency measurements revealed surface states, energy relaxation, and band structure effects. In conclusion, this novel system is ready now for the development and characterization of photo-induced field emission cathodes.

  7. Donor-Acceptor Interaction Determines the Mechanism of Photoinduced Electron Injection from Graphene Quantum Dots into TiO2: π-Stacking Supersedes Covalent Bonding.

    PubMed

    Long, Run; Casanova, David; Fang, Wei-Hai; Prezhdo, Oleg V

    2017-02-22

    Interfacial electron transfer (ET) constitutes the key step in conversion of solar energy into electricity and fuels. Required for fast and efficient charge separation, strong donor-acceptor interaction is typically achieved through covalent chemical bonding and leads to fast, adiabatic ET. Focusing on interfaces of pyrene, coronene, and a graphene quantum dot (GQD) with TiO2, we demonstrate the opposite situation: covalent bonding leads to weak coupling and nonadiabatic (NA) ET, while through-space π-electron interaction produces adiabatic ET. Using real-time time-dependent density functional theory combined with NA molecular dynamics, we simulate photoinduced ET into TiO2 from flat and vertically placed molecules and GQD containing commonly used carboxylic acid linkers. Both arrangements can be achieved experimentally with GQDs and other two-dimensional materials, such as MoS2. The weak through-bond donor-acceptor coupling is attributed to the π-electron withdrawing properties of the carboxylic acid group. The calculated ET time scales are in excellent agreement with pump-probe optical experiments. The simulations show that the ET proceeds faster than energy relaxation. The electron couples to a broad spectrum of vibrational modes, ranging from 100 cm(-1) large-scale motions to 1600 cm(-1) C-C stretches. Compared to graphene/TiO2 heterojunctions, the molecule/TiO2 and GQD/TiO2 systems exhibit energy gaps, allowing for longer-lived excited states and hot electron injection, facilitating charge separation and higher voltage. The reported state-of-the-art simulations generate a detailed time-domain, atomistic description of the interfacial charge and energy transfer and relaxation processes, and demonstrate that the fundamental principles leading to efficient charge separation in nanoscale materials depend strongly and often unexpectedly on the type of donor-acceptor interaction. Understanding these principles is critical to the development of highly efficient

  8. Controlling photoinduced electron transfer from PbS@CdS core@shell quantum dots to metal oxide nanostructured thin films.

    PubMed

    Zhao, H; Fan, Z; Liang, H; Selopal, G S; Gonfa, B A; Jin, L; Soudi, A; Cui, D; Enrichi, F; Natile, M M; Concina, I; Ma, D; Govorov, A O; Rosei, F; Vomiero, A

    2014-06-21

    N-type metal oxide solar cells sensitized by infrared absorbing PbS quantum dots (QDs) represent a promising alternative to traditional photovoltaic devices. However, colloidal PbS QDs capped with pure organic ligand shells suffer from surface oxidation that affects the long term stability of the cells. Application of a passivating CdS shell guarantees the increased long term stability of PbS QDs, but can negatively affect photoinduced charge transfer from the QD to the oxide and the resulting photoconversion efficiency (PCE). For this reason, the characterization of electron injection rates in these systems is very important, yet has never been reported. Here we investigate the photoelectron transfer rate from PbS@CdS core@shell QDs to wide bandgap semiconducting mesoporous films using photoluminescence (PL) lifetime spectroscopy. The different electron affinity of the oxides (SiO2, TiO2 and SnO2), the core size and the shell thickness allow us to fine tune the electron injection rate by determining the width and height of the energy barrier for tunneling from the core to the oxide. Theoretical modeling using the semi-classical approximation provides an estimate for the escape time of an electron from the QD 1S state, in good agreement with experiments. The results demonstrate the possibility of obtaining fast charge injection in near infrared (NIR) QDs stabilized by an external shell (injection rates in the range of 110-250 ns for TiO2 films and in the range of 100-170 ns for SnO2 films for PbS cores with diameters in the 3-4.2 nm range and shell thickness around 0.3 nm), with the aim of providing viable solutions to the stability issues typical of NIR QDs capped with pure organic ligand shells.

  9. Selective fluorescence sensing of Cu(II) and Zn(II) using a simple Schiff base ligand: Naked eye detection and elucidation of photoinduced electron transfer (PET) mechanism

    NASA Astrophysics Data System (ADS)

    Ganguly, Aniruddha; Ghosh, Soumen; Kar, Samiran; Guchhait, Nikhil

    2015-05-01

    A simple Schiff base compound 2-((cyclohexylmethylimino)-methyl)-naphthalen-1-ol (2CMIMN1O) has been synthesized and characterized by 1H NMR, 13C NMR and FT-IR spectroscopic techniques. A significantly low emission yield of the compound has been rationalized in anticipation with photo-induced electron transfer (PET) from the imine receptor moiety to the naphthalene fluorophore unit. Consequently, an evaluation of the transition metal ion-induced modification of the fluorophore-receptor communication reveals the promising prospect of the title compound to function as a chemosensor for Cu2+ and Zn2+ ions selectively, through remarkable fluorescence enhancement as well as visual changes. While perturbation of the PET process has been argued to be the plausible mechanism behind the fluorescence enhancement, the selectivity for these two metal ions has been interpreted on the grounds of an appreciably strong binding interaction. Particularly notable aspects regarding the chemosensory activity of the compound is its ability to detect the aforesaid transition metal ions down to the level of micromolar concentration (detection limit being 2.74 and 2.27 ppm respectively), along with a simple and efficient synthetic procedure.

  10. Photoinduced reactions of both 2-formyl-2H-azirine and isoxazole: A theoretical study based on electronic structure calculations and nonadiabatic dynamics simulations

    SciTech Connect

    Cao, Jun

    2015-06-28

    In the present work, the combined electronic structure calculations and dynamics simulations have been performed to explore photocleavages of 2-formyl-2H-azirine and isoxazole in the gas phase and the subsequent rearrangement reactions. The carbonyl n → π{sup *} transition induces a cleavage of the C—N single bond of 2-formyl-2H-azirine to yield β-formylvinylnitrene in open-shell singlet state. However, the n → π{sup *} excitation of the imine chromophore results in a cleavage of the C—C single bond, producing a nitrile ylide intermediate through an internal conversion to the ground state. β-formylvinylnitrene and nitrile ylide with the carbonyl group are easily transformed into 2-formyl-2H-azirine and oxazole, respectively. The N—O bond cleavages on both S{sub 1}({sup 1}ππ{sup *}) and S{sub 2}({sup 1}n{sub N}π{sup *}) of isoxazole are ultrafast processes, and they give products of 2-formyl-2H-azirine, 3-formylketenimine, HCN + CHCHO, and HCO + CHCHN. Both 2H-azirines and ketenimines were suggested to be formed from the triplet vinylnitrenes by intersystem crossing in the previous studies. However, our calculations show that the singlet β-formylvinylnitrene is responsible for the formation of 2-formyl-2H-azirine and 3-formylketenimine, and the singlet vinylnitrenes can play a key role in the photoinduced reactions of both 2H-azirines and isoxazoles.

  11. Molecular analysis by electron microscopy of the removal of psoralen-photoinduced DNA cross-links in normal and Fanconi's anemia fibroblasts

    SciTech Connect

    Rousset, S.; Nocentini, S.; Revet, B.; Moustacchi, E. )

    1990-04-15

    The induction and fate of psoralen-photoinduced DNA interstrand cross-links in the genome of Fanconi's anemia (FA) fibroblasts of complementation groups A and B, and of normal human fibroblasts, were investigated by quantitative analysis of totally denatured DNA fragments visualized by electron microscopy. 8-Methoxypsoralen (5 x 10(-5) M) interstrand cross-links were induced as a function of the near ultraviolet light dose. With time of postexposure incubation, a fraction of interstrand cross-links disappeared in all cell lines. However, 24 h after treatment, this removal was significantly lower in the two FA group A cell lines examined (34-39%) than in the FA group B and normal cell lines (43-53 and 47-57%, respectively). These data indicate that FA cells are at least able to recognize and incise interstrand cross-links, as normal cells do, although group A cells seem somewhat hampered in this process. This is in accord with data obtained on the same cell lines using another biochemical assay. Since the fate of cross-links in FA constituted a controversial matter, it is important to stress that two different methodologies applied to genetically well defined cell lines led to the same conclusions.

  12. Quencher-Free Fluorescence Method for the Detection of Mercury(II) Based on Polymerase-Aided Photoinduced Electron Transfer Strategy

    PubMed Central

    Liu, Haisheng; Ma, Linbin; Ma, Changbei; Du, Junyan; Wang, Meilan; Wang, Kemin

    2016-01-01

    A new quencher-free Hg2+ ion assay method was developed based on polymerase-assisted photoinduced electron transfer (PIET). In this approach, a probe is designed with a mercury ion recognition sequence (MRS) that is composed of two T-rich functional areas separated by a spacer of random bases at the 3′-end, and a sequence of stacked cytosines at the 5′-end, to which a fluorescein (FAM) is attached. Upon addition of Hg2+ ions into this sensing system, the MRS folds into a hairpin structure at the 3′-end with Hg2+-mediated base pairs. In the presence of DNA polymerase, it will catalyze the extension reaction, resulting in the formation of stacked guanines, which will instantly quench the fluorescence of FAM through PIET. Under optimal conditions, the limit of detection for Hg2+ ions was estimated to be 5 nM which is higher than the US Environmental Protection Agency (EPA) standard limit. In addition, no labeling with a quencher was requiring, and the present method is fairly simple, fast and low cost. It is expected that this cost-effective fluorescence method might hold considerable potential in the detection of Hg2+ ions in real biological and environmental samples. PMID:27869723

  13. Photoinduced reactions of both 2-formyl-2H-azirine and isoxazole: A theoretical study based on electronic structure calculations and nonadiabatic dynamics simulations

    NASA Astrophysics Data System (ADS)

    Cao, Jun

    2015-06-01

    In the present work, the combined electronic structure calculations and dynamics simulations have been performed to explore photocleavages of 2-formyl-2H-azirine and isoxazole in the gas phase and the subsequent rearrangement reactions. The carbonyl n → π* transition induces a cleavage of the C—N single bond of 2-formyl-2H-azirine to yield β-formylvinylnitrene in open-shell singlet state. However, the n → π* excitation of the imine chromophore results in a cleavage of the C—C single bond, producing a nitrile ylide intermediate through an internal conversion to the ground state. β-formylvinylnitrene and nitrile ylide with the carbonyl group are easily transformed into 2-formyl-2H-azirine and oxazole, respectively. The N—O bond cleavages on both S1(1ππ*) and S2(1nNπ*) of isoxazole are ultrafast processes, and they give products of 2-formyl-2H-azirine, 3-formylketenimine, HCN + CHCHO, and HCO + CHCHN. Both 2H-azirines and ketenimines were suggested to be formed from the triplet vinylnitrenes by intersystem crossing in the previous studies. However, our calculations show that the singlet β-formylvinylnitrene is responsible for the formation of 2-formyl-2H-azirine and 3-formylketenimine, and the singlet vinylnitrenes can play a key role in the photoinduced reactions of both 2H-azirines and isoxazoles.

  14. Photoinduced Electron Transfer and Fluorophore Motion as a Probe of the Conformational Dynamics of Membrane Proteins: Application to the Influenza A M2 Proton Channel

    PubMed Central

    Rogers, Julie M. G.; Polishchuk, Alexei L.; Guo, Lin; Wang, Jun; DeGrado, William F.; Gai, Feng

    2011-01-01

    The structure and function of the Influenza A M2 proton channel have been the subject of intensive investigations in recent years because of its critical role in the life cycle of the Influenza virus. Using a truncated version of the M2 proton channel (i.e., M2TM) as a model, here we show that fluctuations in the fluorescence intensity of a dye reporter that arise from both fluorescence quenching via the mechanism of photoinduced electron transfer (PET) by an adjacent tryptophan (Trp) residue and local motions of the dye molecule can be used to probe the conformational dynamics of membrane proteins. Specifically, we find that the dynamics of the conformational transition between the N-terminally-open and C-terminally-open states of the M2TM channel occur on a timescale of about 500 μs and that binding of either amantadine or rimantadine does not inhibit the pH-induced structural equilibrium of the channel. These results are consistent with the direct occluding mechanism of inhibition which suggests that the antiviral drugs act by sterically occluding the channel pore. PMID:21401044

  15. Potency of photoinduced electron transfer and antioxidant efficacy of pyrrole and pyridine based Cu(II)-Schiff complexes while binding with CT-DNA.

    PubMed

    Koley Seth, Banabithi; Ray, Aurkie; Saha, Arpita; Saha, Partha; Basu, Samita

    2014-03-05

    Here we report a systematic and comparative study to define a correlation between the structure and function of a series of simple, biologically active small inorganic Schiff base copper complexes for the occurrence of charge transfer phenomenon in calf thymus DNA (CT-DNA) using transient absorption spectroscopy corroborated with magnetic field effect. Four copper(II) Schiff base complexes with differently substituted heterocyclic ligands with antioxidant activity have been used. The binding constants of the order of ∼ 10(4) support the moderate binding affinity of the complexes towards CT-DNA. The methyl-substituted pyrrole complex shows maximum binding affinity (Kb: 8.33 × 10(4)) compared to others. The occurrence of photoinduced electron transfer (PET) from CT-DNA to pyrrole containing complexes has been confirmed by identifying the corresponding transient radical ions whereas the extent of PET with pyridine substituted complexes is too small to be observed. The increase of the yield of radical ions in presence of magnetic field depicts that the initial spin correlation in geminate radical ion pair is triplet. The difference between experimental and calculated B½ values, the measure of hyperfine interactions (HFI) present in the system, arises due to hole hopping through intrastrand and interstrand DNA bases. The unsubstituted pyrrole complexes cleave DNA much more than the methyl-substituted one. Therefore, the probability of intrastrand superexchange increases with methyl-substituted complexes, that reduces the rate of hole hopping and hence the B½ value.

  16. Novel intramolecular photoinduced electron transfer-based probe for the Human Ether-a-go-go-Related Gene (hERG) potassium channel.

    PubMed

    Liu, Zhenzhen; Zhou, Yubin; Du, Lupei; Li, Minyong

    2015-12-21

    Drug induced long QT syndrome is a high risk event in clinic, which mainly results from their high affinity to the Human Ether-a-go-go-Related Gene (hERG) potassium channel. Therefore, evaluation of the drug's inhibitory activity against the hERG potassium channel is a required step in drug discovery and development. In this study, we developed a series of novel conformation-mediated intramolecular photoinduced electron transfer fluorogenic probes for the hERG potassium channel. After careful evaluation, probes N4 and N6 showed good activity and may have a promising application in the cell-based hERG potassium channel inhibitory activity assay, as well as potential hERG-associated cardiotoxicity evaluation. Compared with other assay methods, such as patch clamp assay, radio-ligand competitive binding assay, fluorescence polarization and potential-sensitive fluorescent probes, this method is convenient and can also selectively measure the inhibitory activity in the native state of the hERG potassium channel. Meanwhile, these probes can also be used for hERG potassium channel imaging without complex washing steps.

  17. Photoinduced electron transfer of platinum(II) bipyridine diacetylides linked by triphenylamine- and naphthaleneimide-derivatives and their application to photoelectric conversion systems.

    PubMed

    Suzuki, Shuichi; Matsumoto, Yuma; Tsubamoto, Mai; Sugimura, Ryoji; Kozaki, Masatoshi; Kimoto, Kenshi; Iwamura, Munetaka; Nozaki, Koichi; Senju, Naoki; Uragami, Chiasa; Hashimoto, Hideki; Muramatsu, Yohei; Konno, Akinori; Okada, Keiji

    2013-06-07

    The recently reported efficient charge-separated system based on bipyridine-diacetylide platinum(ii) complexes was applied to photoelectric conversion systems herein, based on the design and synthesis of two triads: MTA-Pt-NDISAc (3, MTA: dimethoxytriphenylamine, Pt: platinum(ii) complex, NDISAc: thioacetate derivative linked to naphthalenediimide) and MTA-Pt-MNICOOH (4, MNICOOH: naphthaleneimide-4-carboxylic acid). The charge-separated (CS) states of triads 3 and 5 (MOM-protected 4) were effectively generated by photo-induced electron transfer in both THF and toluene, although the rate of formation of the CS state from 5 was relatively slow in toluene. The lifetimes of these CS states were determined to be 730 ns in toluene and 61 ns (70%) and 170 ns (30%) as a double exponential decay in THF for 3, and 600 ns in toluene and 170 ns in THF for 5. The acetylthio group of triad 3 was exploited in the preparation of a self-assembled monolayer (SAM) on a gold surface. Photocurrent was detected upon irradiation of an electrochemical cell comprising Au/3/Na ascorbate/Pt, which was ascribed to the platinum(ii) complex based on the action spectrum. The carboxylic acid group of triad 4 facilitated adsorption on the TiO2 surface, and a dye-sensitized solar cell constructed based on FTO/TiO2/4/electrolyte (LiI-I2)/Pt exhibited a poor energy conversion efficiency (η = 0.20%) based on the incident photon-to-current conversion efficiency spectrum and the I-V curve. This poor efficiency may be derived from the bent molecular shape of 4, or may be due to a possible high energy barrier in the electron injection process through the adsorption site.

  18. [Photoinduced electron transfer between [Ru(bpy)3]2+ and copper(II) ion in composite films mediated by DNA].

    PubMed

    Jiang, Zhen-shen; Chen, Min-jian; Li, Hong

    2013-09-01

    An orange-red [Ru(bpy)3]2+ -DNA-CU2 composite film (bpy = 2,2'-bipyridine) was fabricated on an indium-tin (ITO) surface based on electrostatic interactions among [Ru(bpy)3]2+, DNA and Cu2+ by using self-standing cast methods. The photoinduced electron transfer (PET) properties of the resultant composite film mediated by DNA were studied by means of steady-state and time-resolved fluorescence spectroscopy, UV-visible absorption spectroscopy, fluorescence microscopic imaging and scan electron microscopy. The [Ru(bpy)3]2+ -DNA-Cu2+ composite film with molar ratio of 10:20:1 shows an obvious absorption band (450 nm) and an intense emission peak (lamda(em) = 595 nm), whose emission exhibits a single-exponential decay with tau = 188.6 ns and is quenched by Cu2+ via DNA-mediated PET mechanism, indicating that the quenching constant is 6.94 x 10(3) L x mol(-1) and quenching rate constant is 3.80 x 10(10) L x mol(-1) x s(-1). The increasing molar ratio of Cu2+ in composite films (10-fold) leads to an 11 nm blue-shift of the emission peak, which is dramatically weakened by Cu2+ via a static quenching mechanism. In addition, compared with the emission quenching of DNA-[Ru(bpy)2 (tatp)]2+ (tatp = 1, 4, 8, 9-tetra-aza-triphenylene) tuned by Cu2+, which is present either in solutions or in composite films, Cu2+ only quenches the emission of [Ru(bpy)3]2+ bound to DNA via an electrostatic interaction mode in composite films.

  19. Microwave-enhanced photocatalysis on CdS quantum dots - Evidence of acceleration of photoinduced electron transfer

    PubMed Central

    Kishimoto, Fuminao; Imai, Takashi; Fujii, Satoshi; Mochizuki, Dai; Maitani, Masato M.; Suzuki, Eiichi; Wada, Yuji

    2015-01-01

    The rate of electron transfer is critical in determining the efficiency of photoenergy conversion systems and is controlled by changing the relative energy gap of components, their geometries, or surroundings. However, the rate of electron transfer has not been controlled by the remote input of an external field without changing the geometries or materials of the systems. We demonstrate here that an applied microwave field can enhance the photocatalytic reduction of bipyridinium ion using CdS quantum dots (QDs) by accelerating electron transfer. Analysis of the time-resolved emission decay profiles of CdS quantum dots immersed in aqueous solutions of bipyridinium exhibited the shortening of their emission lifetimes, because of the accelerated electron transfer from QDs to bipyridinium under microwave irradiation. This discovery leads us to a new methodology using microwaves as an external field to enhance photocatalytic reactions. PMID:26080653

  20. Synthesis, Characterization and Photoinduced Electron Transfer in a Supramolecular Tetrakis(ruthenium (II) phthalocyanine)-perylenediimide Pentad

    SciTech Connect

    Jiménez, Angel J.; Grimm, Bruno; Gunderson, Victoria; Vagnini, Michael T.; Calderon, Sandra K.; Rodríguez-Morgade, M. S.; Wasielewski, Michael R.; Guldi, Dirk M.; Torres, Tomas

    2011-03-22

    Metal coordination was probed as a versatile approach for designing a novel electron donor/acceptor hybrid [PDIpy4{Ru(CO)Pc}4] (1), in which four pyridines placed at the bay region of a perylenediimides (PDIpy4) coordinate with four ruthenium phthalocyanine units [Ru(CO)Pc]. This structural motif was expected to promote strong electronic coupling between the electron donors and the electron acceptor, a hypothesis that was confirmed in a full-fledged physicochemical investigation focusing on the ground and excited state reactivities. As far as the ground state is concerned, absorption and electrochemical assays indeed reveal a notable redistribution of electron density, that is, from the electron-donating [Ru(CO)Pc] to the electron-accepting PDIpy4. The most important thing to note in this context is that both the [Ru(CO)Pc] oxidation and the PDIpy4 reduction are rendered more difficult in 1 than in the individual building blocks. Likewise, in the excited state, strong electronic communication is the inception for a rapid charge-transfer process in photoexcited 1. Regardless of exciting [Ru(CO)Pc] or PDIpy4, spectral characteristics of the [RuPc] radical cation (broad absorptive features from 425 to 600 nm with a maximum at 575 nm, as well as a band centered at 725 nm) and of the PDI radical anion (780 nm maximum) emerge. The correspondingly formed radical ion pair state lasts for up to several hundred picoseconds in toluene, for example. On the other hand, employing more polar solvents, such as dichloromethane, destabilizes the radical ion pair state.

  1. An efficient carbonyl-alkene metathesis of bicyclic oxetanes: photoinduced electron transfer reduction of the Paternò-Büchi adducts from 2,3-dihydrofuran and aromatic aldehydes.

    PubMed

    Pérez-Ruiz, Raúl; Miranda, Miguel A; Alle, Ronald; Meerholz, Klaus; Griesbeck, Axel G

    2006-01-01

    The bicyclic oxetanes and resulting from photocycloaddition of aromatic aldehydes to 2,3-dihydrofuran, were efficiently cleaved by means of electron-transfer reduction, photoinduced by the electronically excited reductants 1-methoxynaphthalene (MN) and 2,7-dimethoxynaphthalene (DMN) in acetonitrile. The fluorescence quenching rates of DMN/MN by and were determined by static methods, the triplet quenching rates were determined by means of laser flash photolysis (LFP). The product analysis established a "photo-photo metathesis" where both cycloaddition and cycloreversion processes are induced by photochemical processes.

  2. Mapping of the photoinduced electron traps in TiO₂ by picosecond X-ray absorption spectroscopy.

    PubMed

    Rittmann-Frank, M Hannelore; Milne, Chris J; Rittmann, Jochen; Reinhard, Marco; Penfold, Thomas J; Chergui, Majed

    2014-06-02

    Titanium dioxide (TiO2) is the most popular material for applications in solar-energy conversion and photocatalysis, both of which rely on the creation, transport, and trapping of charges (holes and electrons). The nature and lifetime of electron traps at room temperature have so far not been elucidated. Herein, we use picosecond X-ray absorption spectroscopy at the Ti K-edge and the Ru L3-edge to address this issue for photoexcited bare and N719-dye-sensitized anatase and amorphous TiO2 nanoparticles. Our results show that 100 ps after photoexcitation, the electrons are trapped deep in the defect-rich surface shell in the case of anatase TiO2, whereas they are inside the bulk in the case of amorphous TiO2. In the case of dye-sensitized anatase or amorphous TiO2, the electrons are trapped at the outer surface. Only two traps were identified in all cases, with lifetimes in the range of nanoseconds to tens of nanoseconds.

  3. Direct observation of hole shift and characterization of spin states in radical ion pairs generated from photoinduced electron transfer of (phenothiazine)(n)-anthraquinone (n = 1, 3) dyads.

    PubMed

    Karimata, Ayumu; Suzuki, Shuichi; Kozaki, Masatoshi; Kimoto, Kenshi; Nozaki, Koichi; Matsushita, Hironori; Ikeda, Noriaki; Akiyama, Kimio; Kosumi, Daisuke; Hashimoto, Hideki; Okada, Keiji

    2014-11-26

    Photoinduced intramolecular electron transfer of dyad PTZ3-PTZ2-PTZ1-B-AQ consisting of phenothiazine trimer (PTZ3-PTZ2-PTZ1), bicyclo[2.2.2]octane (B), and anthraquinone (AQ) was investigated. After excitation (∼20 ps) of the AQ moiety in THF, a metastable radical ion pair (RIP) PTZ3-PTZ2-PTZ1(+)-B-AQ(-) appeared at ∼620 nm. From 500 ps to 6 ns the spectrum changed to a new absorption (∼950 nm), which was assigned to the hole-shifted stable RIP state PTZ3-PTZ2(+)-PTZ1-B-AQ(-). The time constant of the hole-shift process was determined to be 6.0 ns. The hole-shifted RIP state had a lifetime (τ) of 250 ns and was characterized by spin-polarized signals as a spin-correlated radical pair (SCRP) by means of time-resolved ESR. These results were compared with those for the phenothiazine monomer analog PTZ-B-AQ, which also produced the RIP state PTZ(+)-B-AQ(-) with τ = 1.9 μs. Time-resolved ESR showed an all emission signal pattern showing the triplet mechanism of PTZ-B-(3)AQ* → (3)[PTZ(+)-B-AQ(-)]. The origin of the difference in the lifetimes between the trimer and the monomer RIP states was discussed from various points of view, including free energy difference in the RIP states, reorganization energy difference in the charge recombination process, and the spin-state difference. Of these, the spin-state difference effect provided the most reasonable explanation.

  4. Modeling the current-voltage characteristics of thin-film silicon solar cells based on photo-induced electron transfer processes.

    PubMed

    Isoda, Satoru

    2013-12-01

    Power conversion efficiency of p-i-n type macrocrystalline silicon (µc-Si:H) solar cells has been analyzed in terms of sequential processes of photo-induced electron transfer. The effect of the excitonic state on the charged carrier generation has been studied compared to a conventional scheme in which only charged carriers are taken into account for the operation of the solar cells. A numerical model has been developed to calculate current-voltage characteristics of solar cells on the basis of two types of charged carrier generation processes (exciton process and charged carrier process). The light trapping effect due to a textured back surface reflector (BSR) was embedded in the numerical model by using the effective medium theory in combination with the matrix method in the field of the electromagnetic theory of light. As an application of this modeling, it was found that the reported data of the power conversion efficiency were not explained by the conventional charged carrier process model and that the combined model of the charged carrier process with the exciton process well explains the performance of the p-i-n type μc-Si:H solar cells. In this way, the typical power conversion efficiencies were estimated to be 10.5% for the device (i-layer thickness: 1.8 μm) with the BSR (period: 600 nm; height: 250 nm) and 8.6% for the device with the flat reflector under the condition that the fractions of the exciton process and charged carrier process were 60% and 40%, respectively.

  5. Photoinduced electron donor/acceptor processes in colloidal II-VI semiconductor quantum dots and nitroxide free radicals

    NASA Astrophysics Data System (ADS)

    Dutta, Poulami

    Electron transfer (ET) processes are one of the most researched topics for applications ranging from energy conversion to catalysis. An exciting variation is utilizing colloidal semiconductor nanostructures to explore such processes. Semiconductor quantum dots (QDs) are emerging as a novel class of light harvesting, emitting and charge-separation materials for applications such as solar energy conversion. Detailed knowledge of the quantitative dissociation of the photogenerated excitons and the interfacial charge- (electron/hole) transfer is essential for optimization of the overall efficiency of many such applications. Organic free radicals are the attractive counterparts for studying ET to/from QDs because these undergo single-electron transfer steps in reversible fashion. Nitroxides are an exciting class of stable organic free radicals, which have recently been demonstrated to be efficient as redox mediators in dye-sensitized solar cells, making them even more interesting for the aforementioned studies. This dissertation investigates the interaction between nitroxide free radicals TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl), 4-amino-TEMPO (4-amino- 2,2,6,6-tetramethylpiperidine-1-oxyl) and II-VI semiconductor (CdSe and CdTe) QDs. The nature of interaction in these hybrids has been examined through ground-state UV-Vis absorbance, steady state and time-resolved photoluminescence (PL) spectroscopy, transient absorbance, upconversion photoluminescence spectroscopy and electron paramagnetic resonance (EPR). The detailed analysis of the PL quenching indicates that the intrinsic charge transfer is ultrafast however, the overall quenching is still limited by the lower binding capacities and slower diffusion related kinetics. Careful analysis of the time resolved PL decay kinetics reveal that the decay rate constants are distributed and that the trap states are involved in the overall quenching process. The ultrafast hole transfer from CdSe QDs to 4-Amino TEMPO observed

  6. Dimensionality of nanoscale TiO2 determines the mechanism of photoinduced electron injection from a CdSe nanoparticle

    DOE PAGES

    Tafen, De Nyago; Long, Run; Prezhdo, Oleg V.

    2014-03-10

    Assumptions about electron transfer (ET) mechanisms guide design of catalytic, photovoltaic, and electronic systems. We demonstrate that the mechanism of ET from a CdSe quantum dot (QD) into nanoscale TiO2 depends on TiO2 dimensionality. The injection into a TiO2 QD is adiabatic due to strong donor–acceptor coupling, arising from unsaturated chemical bonds on the QD surface, and low density of acceptor states. In contrast, the injection into a TiO2 nanobelt (NB) is nonadiabatic, because the state density is high, the donor–acceptor coupling is weak, and multiple phonons accommodate changes in the electronic energy. The CdSe adsorbant breaks symmetry of delocalizedmore » TiO2 NB states, relaxing coupling selection rules, and generating more ET channels. Both mechanisms can give efficient ultrafast injection. Furthermore, the dependence on system properties is very different for the two mechanisms, demonstrating that the fundamental principles leading to efficient charge separation depend strongly on the type of nanoscale material.« less

  7. Controlling photoinduced electron transfer from PbS@CdS core@shell quantum dots to metal oxide nanostructured thin films

    NASA Astrophysics Data System (ADS)

    Zhao, H.; Fan, Z.; Liang, H.; Selopal, G. S.; Gonfa, B. A.; Jin, L.; Soudi, A.; Cui, D.; Enrichi, F.; Natile, M. M.; Concina, I.; Ma, D.; Govorov, A. O.; Rosei, F.; Vomiero, A.

    2014-05-01

    N-type metal oxide solar cells sensitized by infrared absorbing PbS quantum dots (QDs) represent a promising alternative to traditional photovoltaic devices. However, colloidal PbS QDs capped with pure organic ligand shells suffer from surface oxidation that affects the long term stability of the cells. Application of a passivating CdS shell guarantees the increased long term stability of PbS QDs, but can negatively affect photoinduced charge transfer from the QD to the oxide and the resulting photoconversion efficiency (PCE). For this reason, the characterization of electron injection rates in these systems is very important, yet has never been reported. Here we investigate the photoelectron transfer rate from PbS@CdS core@shell QDs to wide bandgap semiconducting mesoporous films using photoluminescence (PL) lifetime spectroscopy. The different electron affinity of the oxides (SiO2, TiO2 and SnO2), the core size and the shell thickness allow us to fine tune the electron injection rate by determining the width and height of the energy barrier for tunneling from the core to the oxide. Theoretical modeling using the semi-classical approximation provides an estimate for the escape time of an electron from the QD 1S state, in good agreement with experiments. The results demonstrate the possibility of obtaining fast charge injection in near infrared (NIR) QDs stabilized by an external shell (injection rates in the range of 110-250 ns for TiO2 films and in the range of 100-170 ns for SnO2 films for PbS cores with diameters in the 3-4.2 nm range and shell thickness around 0.3 nm), with the aim of providing viable solutions to the stability issues typical of NIR QDs capped with pure organic ligand shells.N-type metal oxide solar cells sensitized by infrared absorbing PbS quantum dots (QDs) represent a promising alternative to traditional photovoltaic devices. However, colloidal PbS QDs capped with pure organic ligand shells suffer from surface oxidation that affects the

  8. On the participation of photoinduced N-H bond fission in aqueous adenine at 266 and 220 nm: a combined ultrafast transient electronic and vibrational absorption spectroscopy study.

    PubMed

    Roberts, Gareth M; Marroux, Hugo J B; Grubb, Michael P; Ashfold, Michael N R; Orr-Ewing, Andrew J

    2014-11-26

    A combination of ultrafast transient electronic absorption spectroscopy (TEAS) and transient vibrational absorption spectroscopy (TVAS) is used to investigate whether photoinduced N–H bond fission, mediated by a dissociative 1πσ(*) state, is active in aqueous adenine (Ade) at 266 and 220 nm. In order to isolate UV/visible and IR spectral signatures of the adeninyl radical (Ade[-H]), formed as a result of N–H bond fission, TEAS and TVAS are performed on Ade in D2O under basic conditions (pD = 12.5), which forms Ade[-H](-) anions via deprotonation at the N7 or N9 sites of Ade's 7H and 9H tautomers. At 220 nm we observe one-photon detachment of an electron from Ade[-H](-), which generates solvated electrons (eaq(-)) together with Ade[-H] radicals, with clear signatures in both TEAS and TVAS. Additional wavelength dependent TEAS measurements between 240–260 nm identify a threshold of 4.9 ± 0.1 eV (∼250 nm) for this photodetachment process in D2O. Analogous TEAS experiments on aqueous Ade at pD = 7.4 generate a similar photoproduct signal together with eaq(-) after excitation at 266 and 220 nm. These eaq(-) are born from ionization of Ade, together with Ade(+) cations, which are indistinguishable from Ade[-H] radicals in TEAS. Ade(+) and Ade[-H] are found to have different signatures in TVAS and we verify that the pD = 7.4 photoproduct signal observed in TEAS following 220 nm excitation is solely due to Ade(+) cations. Based on these observations, we conclude that: (i) N–H bond fission in aqueous Ade is inactive at wavelengths ≥220 nm; and (ii) if such a channel exists in aqueous solution, its threshold is strongly blue-shifted relative to the onset of the same process in gas phase 9H-Ade (≤233 nm). In addition, we extract excited state lifetimes and vibrational cooling dynamics for 9H-Ade and Ade[-H](-). In both cases, excited state lifetimes of <500 fs are identified, while vibrational cooling occurs within a time frame of 4–5 ps. In contrast, 7H

  9. Remarkable Dependence of the Final Charge Separation Efficiency on the Donor-Acceptor Interaction in Photoinduced Electron Transfer.

    PubMed

    Higashino, Tomohiro; Yamada, Tomoki; Yamamoto, Masanori; Furube, Akihiro; Tkachenko, Nikolai V; Miura, Taku; Kobori, Yasuhiro; Jono, Ryota; Yamashita, Koichi; Imahori, Hiroshi

    2016-01-11

    The unprecedented dependence of final charge separation efficiency as a function of donor-acceptor interaction in covalently-linked molecules with a rectilinear rigid oligo-p-xylene bridge has been observed. Optimization of the donor-acceptor electronic coupling remarkably inhibits the undesirable rapid decay of the singlet charge-separated state to the ground state, yielding the final long-lived, triplet charge-separated state with circa 100% efficiency. This finding is extremely useful for the rational design of artificial photosynthesis and organic photovoltaic cells toward efficient solar energy conversion.

  10. Photoinduced Single- and Multiple- Electron Dynamics Processes Enhanced by Quantum Confinement in Lead Halide Perovskite Quantum Dots.

    PubMed

    Vogel, Dayton Jon; Kryjevski, Andrei; Inerbaev, Talgat M; Kilin, Dmitri S

    2017-03-21

    Methyl-ammonium lead iodide perovskite (MAPbI3) is a promising material for photovoltaic devices. A modification of the MAPbI3 into confined nanostructures is expected to further increase efficiency of solar energy conversion. Photo-excited dynamic processes in a MAPbI3 quantum dot (QD) have been modeled by many-body perturbation theory and nonadiabatic dynamics. A photoexcitation is followed by either exciton cooling (EC), its radiative (RR) or non-radiative recombination (NRR), or multi-exciton generation (MEG) processes. Computed times of these processes fall in the order of MEG < EC < RR < NRR, where MEG is in the order of a few femtoseconds, EC at the picosecond range while RR and NRR are in the order of nanoseconds. Computed timescales indicate which electronic transition pathways can contribute to increase in charge collection efficiency. Simulated mechanism relaxation rates show that quantum confinement promotes MEG in MAPbI3 QDs.

  11. Modulation of ultrafast photoinduced electron transfer in H-bonding environment: PET from aniline to coumarin 153 in the presence of an inert co-solvent cyclohexane.

    PubMed

    Barman, Nabajeet; Hossen, Tousif; Mondal, Koushik; Sahu, Kalyanasis

    2015-12-28

    Despite intensive research, the role of the H-bonding environment on ultrafast PET remains illusive. For example, coumarin 153 (C153) undergoes ultrafast photoinduced electron transfer (PET) in electron-donating solvents, in both aniline (AN) and N,N-dimethylaniline (DMA), despite their very different H-bonding abilities. Thus, donor-acceptor (AN-C153) H-bonding may have only a minor role in PET (Yoshihara and co-workers, J. Phys. Chem. A, 1998, 102, 3089). However, donor-acceptor H-bonding may be somehow less effective in the neat H-bonding environment but could become dominant in the presence of an inert solvent (Phys. Chem. Chem. Phys., 2014, 16, 6159). We successfully applied and tested the proposal here. The nature of PET modulation of C153 in the presence of a passive component cyclohexane is found to be very different for aniline and DMA. Upon addition of cyclohexane to DMA, the PET process gradually becomes retarded but in the case of AN, the PET rate was indeed found to be accelerated at some intermediate composition (mole fraction of aniline, XAN∼ 0.74) compared to that of neat aniline. It is intuitive that cyclohexane may replace some of the donors (AN or DMA) from the vicinity of the acceptor and, thus, should disfavour PET. However, in the hydrogen bonding environment using molecular dynamics simulation, for the first time, we show that the average number of aniline molecules orienting their N-H group in the proximity of the C=O group of C153 is actually higher at the intermediate mole fraction (0.74) of aniline in a mixture rather than in neat aniline. This small but finite excess of C153-AN H-bonding already present in the ground state may possibly account for the anomalous effect. The TD-DFT calculations presented here showed that the intermolecular H-bonding between C153 and AN strengthens from 21.1 kJ mol(-1) in the ground state to 33.0 kJ mol(-1) in the excited state and, consequently, H-bonding may assist PET according to the Zhao and Han

  12. Non-equivalent conformations of D-amino acid oxidase dimer from porcine kidney between the two subunits. Molecular dynamics simulation and photoinduced electron transfer.

    PubMed

    Nueangaudom, Arthit; Lugsanangarm, Kiattisak; Pianwanit, Somsak; Kokpol, Sirirat; Nunthaboot, Nadtanet; Tanaka, Fumio

    2014-02-07

    The structural difference between two subunits of D-amino acid oxidase dimer from porcine kidney was studied by molecular dynamics simulation (MDS) and rate of photoinduced electron transfer (ET) from aromatic amino acids as tyrosines (Tyr) and tryptophanes (Trp) to the excited isoalloxazine (Iso*). The donor-acceptor distances (Rc) between isoalloxazine (Iso) and the donors were shortest in Tyr224 (0.74 nm) in Sub A at 10 °C (Sub A10), in Tyr224 (0.79 nm) in Sub B at 10 °C (Sub B10), in Tyr228 (0.85 nm) in Sub A at 30 °C (Sub A30), and in Tyr224 (0.72 nm) in Sub B at 30 °C (Sub B30). The Rcs were mostly shorter in the dimer than those in the monomer. Hydrogen bonding (H-bond) pairs between Iso and surrounding amino acids varied with the subunit and temperature. O2 of the Iso ring formed an H-bond exclusively with Thr317OG1 (side chain) in both Sub A10 and Sub A30, while it formed with Gly315N (peptide), Leu316N and Thr317N in Sub B10 and Sub B30. N3H of Iso formed an H-bond with Leu51O (peptide) in Sub A10 and Sub A30, but not in Sub B10 and Sub B30. Electron affinity of Iso* was appreciably lower in Sub A10 compared to Sub B10, while it was opposite at 30 °C. ET rate to Iso* was fastest from Tyr224 in Sub A10, while it was fastest from Tyr314 in Sub B10. The ET rate was fastest from Tyr314 in Sub A30, while it was fastest from Tyr224 in Sub B30. The greater ET rates in the dimer as compared to those in the monomer were elucidated with shorter Rc in the dimer as compared to the monomer. The static dielectric constants inside the subunits and the static dielectric constant between Iso and Tyr224 or Tyr228 were not different appreciably. A few water molecules and sometimes an amino acid were located between Iso and Tyr224, which may be the reason why the dielectric constant of the entire subunits did not differ from that between Iso and Tyr224.

  13. Photoinduced electron transfer through peptide-based self-assembled monolayers chemisorbed on gold electrodes: directing the flow-in and flow-out of electrons through peptide helices.

    PubMed

    Venanzi, Mariano; Gatto, Emanuela; Caruso, Mario; Porchetta, Alessandro; Formaggio, Fernando; Toniolo, Claudio

    2014-08-21

    Photoinduced electron transfer (PET) experiments have been carried out on peptide self-assembled monolayers (SAM) chemisorbed on a gold substrate. The oligopeptide building block was exclusively formed by C(α)-tetrasubstituted α-aminoisobutyric residues to attain a helical conformation despite the shortness of the peptide chain. Furthermore, it was functionalized at the C-terminus by a pyrene choromophore to enhance the UV photon capture cross-section of the compound and by a lipoic group at the N-terminus for linking to gold substrates. Electron transfer across the peptide SAM has been studied by photocurrent generation experiments in an electrochemical cell employing a gold substrate modified by chemisorption of a peptide SAM as a working electrode and by steady-state and time-resolved fluorescence experiments in solution and on a gold-coated glass. The results show that the electronic flow through the peptide bridge is strongly asymmetric; i.e., PET from the C-terminus to gold is highly favored with respect to PET in the opposite direction. This effect arises from the polarity of the Au-S linkage (Au(δ+)-S(δ-), junction effect) and from the electrostatic field generated by the peptide helix.

  14. Study of photoinduced energy and electron transfer in alpha-terthienyl-bovine serum albumin conjugates: a laser flash photolysis study.

    PubMed

    Boch, R; Mohtat, N; Lear, Y; Arnason, J T; Durst, T; Scaiano, J C

    1996-07-01

    The photochemistry of alpha-terthienyl (alpha-T) has been examined in bovine serum albumin (BSA). Freely associated and covalently conjugated alpha-T chromophores show similar behavior toward nonpolar quenchers such as oxygen and benzoquinone but show significant differences in the case of quenching by methyl viologen, a watersoluble cationic electron acceptor; in this case, triplet quenching reveals two distinct alpha-T populations, attributed to chromophores in sites showing very different accessibility from the aqueous phase. Rate constants for triplet quenching in BSA are generally slower than those observed in homogeneous solution for free alpha-T. For example, in the case of oxygen, the rate constant is about one order of magnitude smaller when alpha-T is associated or conjugated with the protein compared with alpha-T in solution. While triplet yields for alpha-T are essentially the same in solution and in the protein environment, the yield of detectable singlet oxygen is substantially reduced in the protein. This is attributed to a geminate reaction within the protein involving singlet oxygen trapping in the vicinity of the generation site.

  15. A novel photoinduced electron transfer (PET) primer technique for rapid real-time PCR detection of Cryptosporidium spp.

    PubMed

    Jothikumar, N; Hill, Vincent R

    2013-06-28

    We report the development of a fluorescently labeled oligonucleotide primer that can be used to monitor real-time PCR. The primer has two parts, the 3'-end of the primer is complimentary to the target and a universal 17-mer stem loop at the 5'-end forms a hairpin structure. A fluorescent dye is attached to 5'-end of either the forward or reverse primer. The presence of guanosine residues at the first and second position of the 3' dangling end effectively quenches the fluorescence due to the photo electron transfer (PET) mechanism. During the synthesis of nucleic acid, the hairpin structure is linearized and the fluorescence of the incorporated primer increases several-fold due to release of the fluorescently labeled tail and the absence of guanosine quenching. As amplicons are synthesized during nucleic acid amplification, the fluorescence increase in the reaction mixture can be measured with commercially available real-time PCR instruments. In addition, a melting procedure can be performed to denature the double-stranded amplicons, thereby generating fluorescence peaks that can differentiate primer dimers and other non-specific amplicons if formed during the reaction. We demonstrated the application of PET-PCR for the rapid detection and quantification of Cryptosporidium parvum DNA. Comparison with a previously published TaqMan® assay demonstrated that the two real-time PCR assays exhibited similar sensitivity for a dynamic range of detection of 6000-0.6 oocysts per reaction. PET PCR primers are simple to design and less-expensive than dual-labeled probe PCR methods, and should be of interest for use by laboratories operating in resource-limited environments.

  16. Photoinduced Multicomponent Reactions.

    PubMed

    Garbarino, Silvia; Ravelli, Davide; Protti, Stefano; Basso, Andrea

    2016-12-12

    The combination of multicomponent approaches with light-driven processes opens up new scenarios in the area of synthetic organic chemistry, where the need for sustainable, atom- and energy-efficient reactions is increasingly urgent. Photoinduced multicomponent reactions are still in their infancy, but significant developments in this area are expected in the near future.

  17. A novel photoinduced electron transfer (PET) primer technique for rapid real-time PCR detection of Cryptosporidium spp

    SciTech Connect

    Jothikumar, N. Hill, Vincent R.

    2013-06-28

    Highlights: •Uses a single-labeled fluorescent primer for real-time PCR. •The detection sensitivity of PET PCR was comparable to TaqMan PCR. •Melt curve analysis can be performed to confirm target amplicon production. •Conventional PCR primers can be converted to PET PCR primers. -- Abstract: We report the development of a fluorescently labeled oligonucleotide primer that can be used to monitor real-time PCR. The primer has two parts, the 3′-end of the primer is complimentary to the target and a universal 17-mer stem loop at the 5′-end forms a hairpin structure. A fluorescent dye is attached to 5′-end of either the forward or reverse primer. The presence of guanosine residues at the first and second position of the 3′ dangling end effectively quenches the fluorescence due to the photo electron transfer (PET) mechanism. During the synthesis of nucleic acid, the hairpin structure is linearized and the fluorescence of the incorporated primer increases several-fold due to release of the fluorescently labeled tail and the absence of guanosine quenching. As amplicons are synthesized during nucleic acid amplification, the fluorescence increase in the reaction mixture can be measured with commercially available real-time PCR instruments. In addition, a melting procedure can be performed to denature the double-stranded amplicons, thereby generating fluorescence peaks that can differentiate primer dimers and other non-specific amplicons if formed during the reaction. We demonstrated the application of PET-PCR for the rapid detection and quantification of Cryptosporidium parvum DNA. Comparison with a previously published TaqMan® assay demonstrated that the two real-time PCR assays exhibited similar sensitivity for a dynamic range of detection of 6000–0.6 oocysts per reaction. PET PCR primers are simple to design and less-expensive than dual-labeled probe PCR methods, and should be of interest for use by laboratories operating in resource

  18. Femtosecond studies of photoinduced electron dynamics in colloidal quantum-confined II-VI semiconductor nanoparticles: CdS, CdSe and CdZnS

    NASA Astrophysics Data System (ADS)

    Roberti, Trevor

    A variety of synthetic and spectroscopic techniques have been applied to elucidate photoinduced charge carrier processes in II-VI semiconductor quantum dots. These semiconductor nanoparticles exhibit both size-dependent optical tuning due to the quantum-confinement effect and power-dependent absorption, bleach and emission characteristics. Although the tunable-absorption has been well characterized, the subsequent trapping and recombination processes are still under much investigation and are the subject of this dissertation. Particles with vastly differing surfaces, sizes, energetics and solvents have been characterized using various spectroscopic techniques in unison. The primary technique was transient femtosecond near-IR absorption, which was used to characterize charge carrier processes on the subpicosecond and picosecond time scales. UV-visible spectroscopy was used to characterize the size of the particles. Static fluorescence measurements were used to characterize the surface of the particles and the relative amount of radiative recombination. Nanosecond fluorescence measurements were also used to assist in the assignment of the fast, power-dependent near-IR absorption decay. The research reported here makes two fundamental contributions to the photophysics of semiconductor nanoparticles. First, the power-dependent, few picosecond decay process has primarily been assigned to electron-hole recombination via exciton-exciton annihilation. As the power increases, higher order, Auger processes may also arise. The exciton-exciton annihilation mechanism was primarily deduced based on power-dependent fluorescence measurements which exhibited the formation of short-lived exciton fluorescence at high powers. Secondly, many nanoparticle properties and environments were varied in order to better understand the observed picosecond processes and the effect of variations on these processes. The systems studied ranged from aqueous acidic and basic quantum dots of differing

  19. Proton-Coupled Electron-Transfer Processes in Ultrafast Time Domain: Evidence for Effects of Hydrogen-Bond Stabilization on Photoinduced Electron Transfer.

    PubMed

    Dey, Ananta; Dana, Jayanta; Aute, Sunil; Maity, Partha; Das, Amitava; Ghosh, Hirendra N

    2017-03-08

    The proton-coupled electron-transfer (PCET) reaction is investigated for a newly synthesized imidazole-anthraquinone biomimetic model with a photoactive Ru(II) -polypyridyl moiety that is covalently coupled to the imidazole fragment. Intramolecular H-bonding interactions between imidazole and anthraquinone moieties favor the PCET process; this can be correlated to an appreciable positive shift in the one-electron reduction potential of the coordinated anthraquinone moiety functionalized with the imidazole fragment. This can also be attributed to the low luminescence quantum yield of the Ru(II) -polypyridyl complex used. The dynamics of the intramolecular electron-transfer (ET) and PCET processes are studied by using femtosecond transient absorption spectroscopy. The steady-state spectroscopic studies and the results of the time-resolved absorption studies confirm that H-bonded water molecules play a major role in both ET and PCET dynamics as a proton relay in the excited state. The electron-transfer process is followed by a change in the H-bonding equilibrium between AQ and imidazole in acetonitrile solvent, and protonation of AQ(.-) by water leads to PCET in the presence of water. A slower forward and backward electron-transfer rate is observed in the presence of D2 O compared with that in H2 O. These results provide further experimental support for a detailed understanding of the PCET process.

  20. Quantum pattern formation dynamics of photoinduced nucleation

    NASA Astrophysics Data System (ADS)

    Ishida, Kunio; Nasu, Keiichiro

    2008-06-01

    We study the dynamics of quantum pattern formation processes in molecular crystals which is concomitant with photoinduced nucleation. Since the nucleation process in coherent regime is driven by the nonadiabatic transition in each molecule followed by the propagation of phonons, it is necessary to take into account the quantum nature of both electrons and phonons in order to pursue the dynamics of the system. Therefore, we employ a model of localized electrons coupled with a quantized phonon mode and solve the time-dependent Schrödinger equation numerically. We found that there is a minimal size of clusters of excited molecules which triggers the photoinduced nucleation process; i.e., nucleation does not take place unless sufficient photoexcitation energy is concentrated within a narrow area of the system. We show that this result means that the spatial distribution of photoexcited molecules plays an important role in the nonlinearity of the dynamics and also in the optical properties observed in experiments. We calculate the conversion ratio, the rate of cluster formation, and correlation functions to reveal the dynamical properties of the pattern formation process; the initial dynamics of the photoinduced structural change is discussed from the viewpoint of pattern formation.

  1. Excited-state electronic coupling and photoinduced multiple electron transfer in two related ligand-bridged hexanuclear mixed-valence compounds.

    PubMed

    Pfennig, Brian W; Mordas, Carolyn J; McCloskey, Alex; Lockard, Jenny V; Salmon, Patty M; Cohen, Jamie L; Watson, David F; Bocarsly, Andrew B

    2002-08-26

    The synthesis, characterization, electrochemical, photophysical, and photochemical properties of two hexanuclear mixed-valence compounds are reported. Each supramolecular species consists of two cyano-bridged [(NC)(5)Fe(II)-CN-Pt(IV)(NH(3))(3)L-NC-Fe(II)(CN)(5)] triads that are linked to each other through a Pt(IV)-L-Pt(IV) bridge, where L = 4,4'-dipyridyl (bpy) or 3,3'-dimethyl-4,4'-dipyridyl (dmb). The major difference between the two compounds is the electronic nature of the bridging ligand between the two Pt atoms. Both species exhibit a broad Fe(II) --> Pt(IV) intervalent (IT) absorption band at 421 nm with an oscillator strength that is approximately four times that for [(NC)(5)Fe(II)-CN-Pt(IV)(NH(3))(5)] and twice that for [(NC)(5)Fe(II)-CN-Pt(IV)(NH(3))(4)-NC-Fe(II)(CN)(5)].(4-) When L = bpy, the resonance Raman spectrum obtained by irradiating the IT band at 488 nm exhibits several dipyridyl ring modes at 1604, 1291, and 1234 cm(-1) which are not present in the spectrum when L = dmb. In addition, femtosecond pump-probe spectroscopy performed at 400 nm yields a transient bleach of the IT absorption band with a single exponential decay of 3.5 ps for L = bpy, compared with only 1.8 ps for L = dmb and 2.1 ps for [(NC)(5)Fe(II)-CN-Pt(IV)(NH(3))(4)-NC-Fe(II)(CN)(5)].(4-) Last, prolonged irradiation of the complexes at 488 nm leads to the formation of 4 equiv of ferricyanide with a quantum efficiency of 0.0014 for L = bpy and 0.0011 for L = dmb. The transient absorption, resonance Raman, and photochemical data suggest that the degree of excited electronic coupling in these compounds is tunable by changing the electronic nature of the Pt-L-Pt bridging ligand.

  2. Characterization of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Emim][Tf2N])/TX-100/cyclohexane ternary microemulsion: Investigation of photoinduced electron transfer in this RTIL containing microemulsion

    NASA Astrophysics Data System (ADS)

    Sarkar, Souravi; Pramanik, Rajib; Ghatak, Chiranjib; Rao, Vishal Govind; Sarkar, Nilmoni

    2011-02-01

    In this study we have characterized a ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethyl- sulfonyl)imide containing ternary nonaqueous microemulsion ([Emim][Tf2N]//TX-100/cyclo- hexane). The phase behavior and dynamic light scattering study show that the [Emim][Tf2N]/TX-100/cyclohexane three component system can form microemulsion with [Emim][Tf2N] as polar core at suitable condition. We have investigated photoinduced electron transfer (PET) using dimethyl aniline as electron donor and several Coumarin dyes as electron acceptor molecules at two different R values (R = [ionic liquid]/[surfactant]) to observe how the dynamics of the PET rate is affected in this type of confined microenvironment compared to that of the PET dynamics in neat ionic liquid and other pure solvent media. The plot of observed kq values with the free energy change (ΔG0) for electron transfer reaction shows an apparent inversion in the observed rate as predicted by the Marcus theory.

  3. Photoinduced charge separation by polymer-bound chromophores

    SciTech Connect

    Rodgers, M.A.J.

    1991-09-01

    This project has examined the photodynamic behavior of water-soluble polymers that have covalently linked hydrophobic chromophores spaced along the chains. These polymeric systems have been examined for photoinduced charge separation with electron-accepting ions having different total charge. Focus has been on the excited singlet (S{sub 1}) state formed by laser flash absorption. The effects of pH and ionic strength -- factors that govern the conformational nature of the polymer in solution -- have been studied. A second major effort has been to study photoinduced redox processes involving excited states of water-soluble variants of anthracene and acridine. 27 refs., 16 figs., 2 tabs.

  4. Nanoscale chemical imaging by photoinduced force microscopy

    PubMed Central

    Nowak, Derek; Morrison, William; Wickramasinghe, H. Kumar; Jahng, Junghoon; Potma, Eric; Wan, Lei; Ruiz, Ricardo; Albrecht, Thomas R.; Schmidt, Kristin; Frommer, Jane; Sanders, Daniel P.; Park, Sung

    2016-01-01

    Correlating spatial chemical information with the morphology of closely packed nanostructures remains a challenge for the scientific community. For example, supramolecular self-assembly, which provides a powerful and low-cost way to create nanoscale patterns and engineered nanostructures, is not easily interrogated in real space via existing nondestructive techniques based on optics or electrons. A novel scanning probe technique called infrared photoinduced force microscopy (IR PiFM) directly measures the photoinduced polarizability of the sample in the near field by detecting the time-integrated force between the tip and the sample. By imaging at multiple IR wavelengths corresponding to absorption peaks of different chemical species, PiFM has demonstrated the ability to spatially map nm-scale patterns of the individual chemical components of two different types of self-assembled block copolymer films. With chemical-specific nanometer-scale imaging, PiFM provides a powerful new analytical method for deepening our understanding of nanomaterials. PMID:27051870

  5. Photoinduced (WO4)3--La3+ center in PbWO4: Electron spin resonance and thermally stimulated luminescence study

    NASA Astrophysics Data System (ADS)

    Laguta, V. V.; Martini, M.; Meinardi, F.; Vedda, A.; Hofstaetter, A.; Meyer, B. K.; Nikl, M.; Mihóková, E.; Rosa, J.; Usuki, Y.

    2000-10-01

    The localization of electrons at W6+ sites perturbed by lanthanum in PbWO4 is studied by electron spin resonance (ESR) and thermally stimulated luminescence (TSL) measurements. The (WO4)3--La3+ centers are created at the W6+ sites close to La3+ in two different ways: (i) direct trapping of electrons from the conduction band under ultraviolet or x-ray irradiation at T=60 K (ii) retrapping of electrons freed from unperturbed (WO4)3- centers after irradiation at T<40 K followed by heating up to T around 60 K. Electron transfer from La3+-perturbed to unperturbed W6+ sites stimulated by red light illumination is also observed. The proposed mechanism of electron localization at one of four equivalent tungstate ions close to La3+ is based on the pseudo-Jahn-Teller effect, which gives rise to a rhombic distortion of (WO4)3- complex. At T~95-98 K the (WO4)3--La3+ centers are thermally ionized giving rise to a TSL glow peak due to the recombination of detrapped electrons with localized holes. The emission spectrum of the TSL features one band peaking at 2.8 eV. The temperature dependence of both TSL and ESR intensity is analyzed in the frame of a general order recombination model. The thermal ionization energy of (WO4)3--La3+ centers has been calculated to be approximately 0.27 eV.

  6. Dynamical properties of nucleus boundaries in photoinduced structural change

    NASA Astrophysics Data System (ADS)

    Ishida, Kunio; Nasu, Keiichiro

    2014-01-01

    Dynamics of the boundaries of photoinduced nuclei in electron-phonon systems is theoretically studied. By regarding the spatial distribution of the excited electronic state population as a geometric pattern, we applied the multifractal analysis to it and calculated the temporal behavior of the fractal dimension f(α) as a function of the Lipschitz-Hölder exponent α, which is an appropriate method for understanding the cooperative relaxation process of photoexcited states. We found that the incubation period observed in various types of photoinduced cooperative phenomena corresponds to the formation of embryonic nuclei which is driven by nonadiabatic/adiabatic transition between electronic states during the relaxation of the Franck-Condon state.

  7. Photoinduced electron transfer involving eosin-tryptophan conjugates. Long-lived radical pair states for systems incorporating aromatic amino acid side chains

    SciTech Connect

    Jones, G. II; Farahat, C.W.; Oh, C. )

    1994-07-14

    The electron-transfer photochemistry of the covalent derivatives of the dye eosin, in which the xanthene dye is covalently attached to the amino acid L-tryptophan via the thiohydantoin derivative, the tryptophan dipeptide, and an ethyl ester derivative, has been investigated. The singlet excited state of the dye is significantly quenched on attachment of the aromatic amino acid residue. Dye triplet states are also intercepted through intramolecular interaction of excited dye and amino acid pendants. Flash photolysis experiments verify that this interaction involves electron transfer from the indole side chains of tryptophan. Rate constants for electron transfer are discussed in terms of the distance relationships for the eosin chromophore and aromatic redox sites on peptide derivatives, the pathway for [sigma]-[pi] through-bond interaction between redox sites, and the multiplicity and state of protonation for electron-transfer intermediates. Selected electron-transfer photoreactions were studied under conditions of binding of the peptide derivatives in a high molecular weight, water-soluble, globular polymer, poly(vinyl-2-pyrrolidinone). 28 refs., 4 figs., 1 tab.

  8. Photocatalytic activation of pyridine for addition reactions: an unconventional reaction feature between a photo-induced hole and electron on TiO2.

    PubMed

    Ma, Dongge; Yan, Yan; Ji, Hongwei; Chen, Chuncheng; Zhao, Jincai

    2015-12-21

    TiO2 photocatalysis can be performed for the addition of pyridines to vinylarenes in an anti-Markovnikov manner. Seven examples with considerable yields (56-91%) and selectivity were demonstrated. A comparative survey of the involved process through ESR revealed a novel concerted two electron transfer pathway for these photocatalytic bimolecular addition reactions.

  9. Role of the inner-sphere reorganization in the photoinduced electron transfer reaction of Ru(II) complexes containing imine C=N or Azo N=N double bonds in the ligands

    SciTech Connect

    Maruyama, Mutsuhiro; Kaizu, Youkoh

    1995-04-20

    Photoinduced oxidative and reductive electron transfer (ET) reactions of excited Ru(imin){sub 3}{sup 2+} (imin = 2-(N-methylformimidoyl)pyridine), Ru(imin){sub 2}(CN){sub 2}, and Ru(azpy){sub 3}{sup 2+} (azpy = 2-(phenylazo)pyridine), where imin and azpy contain imine C=N and azo N=N double bonds, respectively, with organic quenchers were investigated in acetonitrile solutions, and their {Delta}G dependencies of the quenching rate constants (k{sub q}) were compared with those of Ru(bpy){sub 3}{sup 2+} (bpy = 2,2`-bipyridine) and Ru(L){sub 2}(CN){sub 2} complexes where L = 4,4`- or 5,5`-dmbpy (dmbpy = dimethyl-2,2`-bipyridine) and phen (phen = 1,10-phenanthroline). The oxidative quenching rate constants of Ru(imin){sub 3}{sup 2+} and Ru(imin){sub 2}(CN){sub 2} are smaller than those of the corresponding bpy, dmbpy, and phen complexes at the same {Delta}G value in the normal region. However, the {Delta}G dependencies of the reductive quenching rate constants of Ru(imin){sub 3}{sup 2+} and Ru(azpy){sub 3}{sup 2+} coincide with that of the corresponding bpy complex. The inner-sphere reorganization ({lambda}{sub in}) caused by the deformation of the C=N bond of imin is considered to be the main reason for the disadvantage of ET in the normal region of the oxidative ET reactions of excited Ru(imin){sub 3}{sup 2+} and Ru(imin){sub 2}(CN){sub 2}. 44 refs., 6 figs., 6 tabs.

  10. Control over photoinduced energy and electron transfer in supramolecular polyads of covalently linked azaBODIPY-bisporphyrin 'molecular clip' hosting fullerene.

    PubMed

    D'Souza, Francis; Amin, Anu N; El-Khouly, Mohamed E; Subbaiyan, Navaneetha K; Zandler, Melvin E; Fukuzumi, Shunichi

    2012-01-11

    A 'molecular clip' featuring a near-IR emitting fluorophore, BF(2)-chelated tetraarylazadipyrromethane (aza-BODIPY) covalently linked to two porphyrins (MP, M = 2H or Zn) has been newly synthesized to host a three-dimensional electron acceptor fullerene via a 'two-point' metal-ligand axial coordination. Efficient singlet-singlet excitation transfer from (1)ZnP* to aza-BODIPY was witnessed in the dyad and triad in nonpolar and less polar solvents, such as toluene and o-dichlorobenzene, however, in polar solvents, additional electron transfer occurred along with energy transfer. A supramolecular tetrad was formed by assembling bis-pyridine functionalized fullerene via a 'two-point' metal-ligand axial coordination, and the resulted complex was characterized by optical absorption and emission, computational, and electrochemical methods. Electron transfer from photoexcited zinc porphyrin to C(60) is witnessed in the supramolecular tetrad from the femtosecond transient absorption spectral studies. Further, the supramolecular polyads (triad or tetrad) were utilized to build photoelectrochemical cells to check their ability to convert light into electricity by fabricating FTO/SnO(2)/polyad electrodes. The presence of azaBODIPY and fullerene entities of the tetrad improved the overall light energy conversion efficiency. An incident photon-to-current conversion efficiency of up to 17% has been achieved for the tetrad modified electrode.

  11. Theoretical characterization of photoinduced electron transfer in rigidly linked donor-acceptor molecules: the fragment charge difference and the generalized Mulliken-Hush schemes

    NASA Astrophysics Data System (ADS)

    Lee, Sheng-Jui; Chen, Hung-Cheng; You, Zhi-Qiang; Liu, Kuan-Lin; Chow, Tahsin J.; Chen, I.-Chia; Hsu, Chao-Ping

    2010-10-01

    We calculate the electron transfer (ET) rates for a series of heptacyclo[6.6.0.02,6.03,13.014,11.05,9.010,14]-tetradecane (HCTD) linked donor-acceptor molecules. The electronic coupling factor was calculated by the fragment charge difference (FCD) [19] and the generalized Mulliken-Hush (GMH) schemes [20]. We found that the FCD is less prone to problems commonly seen in the GMH scheme, especially when the coupling values are small. For a 3-state case where the charge transfer (CT) state is coupled with two different locally excited (LE) states, we tested with the 3-state approach for the GMH scheme [30], and found that it works well with the FCD scheme. A simplified direct diagonalization based on Rust's 3-state scheme was also proposed and tested. This simplified scheme does not require a manual assignment of the states, and it yields coupling values that are largely similar to those from the full Rust's approach. The overall electron transfer (ET) coupling rates were also calculated.

  12. Dimensionality of nanoscale TiO2 determines the mechanism of photoinduced electron injection from a CdSe nanoparticle

    SciTech Connect

    Tafen, De Nyago; Long, Run; Prezhdo, Oleg V.

    2014-03-10

    Assumptions about electron transfer (ET) mechanisms guide design of catalytic, photovoltaic, and electronic systems. We demonstrate that the mechanism of ET from a CdSe quantum dot (QD) into nanoscale TiO2 depends on TiO2 dimensionality. The injection into a TiO2 QD is adiabatic due to strong donor–acceptor coupling, arising from unsaturated chemical bonds on the QD surface, and low density of acceptor states. In contrast, the injection into a TiO2 nanobelt (NB) is nonadiabatic, because the state density is high, the donor–acceptor coupling is weak, and multiple phonons accommodate changes in the electronic energy. The CdSe adsorbant breaks symmetry of delocalized TiO2 NB states, relaxing coupling selection rules, and generating more ET channels. Both mechanisms can give efficient ultrafast injection. Furthermore, the dependence on system properties is very different for the two mechanisms, demonstrating that the fundamental principles leading to efficient charge separation depend strongly on the type of nanoscale material.

  13. Photoinduced electron and energy transfer and pH-induced modulation of the photophysical properties in homo- and heterobimetallic complexes of ruthenium(II) and rhodium(III) based on a heteroditopic phenanthroline-terpyridine bridge.

    PubMed

    Maity, Dinesh; Bhaumik, Chanchal; Karmakar, Srikanta; Baitalik, Sujoy

    2013-07-15

    Homo- and heterobimetallic complexes of compositions [(bpy)2Ru(II)(phen-Hbzim-tpy)Ru(II)(tpy/tpy-PhCH3/H2pbbzim)](4+) and [(bpy)2Ru(II)(phen-Hbzim-tpy)Rh(III)(tpy-PhCH3/H2pbbzim)](5+), where phen-Hbzim-tpy = 2-[4-(2,6-dipyridin-2-ylpyridin-4-yl)phenyl]-1H-imidazole[4,5-f][1,10]phenanthroline, bpy = 2,2'-bipyridine, tpy = 2,2':6',2"-terpyridine, tpy-PhCH3 = 4'-(4-methylphenyl)-2,2':6',2"-terpyridine, and H2pbbzim = 2,6-bis(benzimidazol-2-yl)pyridine, have been synthesized and characterized by elemental analyses, electrospray ionization mass spectrometry, and (1)H NMR spectroscopy. The absorption spectra, redox behavior, and luminescence properties of these bimetallic complexes have been thoroughly investigated and compared with those of monometallic [(bpy)2Ru(II)(phen-Hbzim-tpy)](2+) and [(tpy-PhCH3)Rh(III)(tpy-Hbzim-phen)](3+) model compounds. The electrochemistry of the complexes shows a reversible Ru(II/III) oxidation in the anodic region and an irreversible Rh(III/I) reduction and several ligand-based reductions in the cathodic region. Steady-state and time-resolved luminescence data at room temperature show that an efficient intramolecular electronic energy transfer from the metal-to-ligand charge-transfer (MLCT) excited state of the [(bpy)2Ru(II)(phen-Hbzim-tpy)] chromophore to the MLCT state of the tpy-containing chromophore [(phen-Hbzim-tpy)Ru(II)(tpy/tpy-PhCH3/H2pbbzim)] occurs in all three unsymmetrical homobimetallic complexes. On the other hand, for both heterometallic dyads, an efficient intramolecular photoinduced electron transfer from the excited ruthenium moiety to the rhodium-based unit takes place. The rate constants for the energy- and electron-transfer processes have been determined by time-resolved emission spectroscopy. The influence of the pH on the absorption, steady-state, and time-resolved emission properties of complexes has been thoroughly investigated. The absorption titration data were used to determine the ground-state pK values

  14. High-potential perfluorinated phthalocyanine-fullerene dyads for generation of high-energy charge-separated states: formation and photoinduced electron-transfer studies.

    PubMed

    Das, Sushanta K; Mahler, Andrew; Wilson, Angela K; D'Souza, Francis

    2014-08-25

    High oxidation potential perfluorinated zinc phthalocyanines (ZnF(n)Pcs) are synthesised and their spectroscopic, redox, and light-induced electron-transfer properties investigated systematically by forming donor-acceptor dyads through metal-ligand axial coordination of fullerene (C60) derivatives. Absorption and fluorescence spectral studies reveal efficient binding of the pyridine- (Py) and phenylimidazole-functionalised fullerene (C60Im) derivatives to the zinc centre of the F(n)Pcs. The determined binding constants, K, in o-dichlorobenzene for the 1:1 complexes are in the order of 10(4) to 10(5) M(-1); nearly an order of magnitude higher than that observed for the dyad formed from zinc phthalocyanine (ZnPc) lacking fluorine substituents. The geometry and electronic structure of the dyads are determined by using the B3LYP/6-31G* method. The HOMO and LUMO levels are located on the Pc and C60 entities, respectively; this suggests the formation of ZnF(n)Pc(.+)-C60Im(.-) and ZnF(n)Pc(.+)-C60Py(.-) (n=0, 8 or 16) intra-supramolecular charge-separated states during electron transfer. Electrochemical studies on the ZnPc-C60 dyads enable accurate determination of their oxidation and reduction potentials and the energy of the charge-separated states. The energy of the charge-separated state for dyads composed of ZnF(n)Pc is higher than that of normal ZnPc-C60 dyads and reveals their significance in harvesting higher amounts of light energy. Evidence for charge separation in the dyads is secured from femtosecond transient absorption studies in nonpolar toluene. Kinetic evaluation of the cation and anion radical ion peaks reveals ultrafast charge separation and charge recombination in dyads composed of perfluorinated phthalocyanine and fullerene; this implies their significance in solar-energy harvesting and optoelectronic device building applications.

  15. Photoinduced electron-transfer reactions of 2(3H)-furanones and bis(benzofuranones). Spectral and kinetic behavior of radicals and radical cations

    SciTech Connect

    Davis, H.F.; Lohray, B.B.; Gopidas, K.R.; Kumar, C.V.; Das, P.K.; George, M.V.

    1985-10-04

    The spectral and kinetic behaviors of radical cations produced under efficient electron-transfer quenching of 1,4-dicyanonaphthalene or 9,10-dicyanoanthracene singlet by a number of 2(3H)-furanones and bis(benzo-furanones) have been examined by nanosecond laser flash photolysis (337.1 and 425 nm). The efficiencies of net electron transfer in the course of quenching processes are moderately high (0.2-0.6) in acetonitrile. The radical cations from bis(benzofuranones) several 2(3H)-furanones containing a benzyl group at the 3-position undergo fragmentation to benzofuranoxy and furanoxy radicals (+ benzyl or benzofuranoyl carbocations) with rate constants of 0.3 x 10W s . The long-lived furanoxy radicals, independently generated via hydrogen abstraction by tert-butoxy radicals from 2(5H)-furanones and 3-phenyl-2(3H)-benzofuranone, as well as via direct photolysis of 3-benzoyl-3,5-diphenyl-2(3H)-furanone, are characterized by sharply structured absorption spectra and relatively slow second-order decay kinetics (6-8 x 10Y M s in 1:2 benzene-di-tert butyl peroxide, v/v). 28 references, 7 figures, 3 tables.

  16. Structural basis for the temperature-induced transition of D-amino acid oxidase from pig kidney revealed by molecular dynamic simulation and photo-induced electron transfer.

    PubMed

    Nueangaudom, Arthit; Lugsanangarm, Kiattisak; Pianwanit, Somsak; Kokpol, Sirirat; Nunthaboot, Nadtanet; Tanaka, Fumio

    2012-02-28

    The structural basis for the temperature-induced transition in the D-amino acid oxidase (DAAO) monomer from pig kidney was studied by means of molecular dynamic simulations (MDS). The center to center (Rc) distances between the isoalloxazine ring (Iso) and all aromatic amino acids (Trp and Tyr) were calculated at 10 °C and 30 °C. Rc was shortest in Tyr224 (0.82 and 0.88 nm at 10 and 30 °C, respectively), and then in Tyr228. Hydrogen bonding (H-bond) formed between the Iso N1 and Gly315 N (peptide), between the Iso N3H and Leu51 O (peptide) and between the Iso N5 and Ala49 N (peptide) at 10 °C, whilst no H-bond was formed at the Iso N1 and Iso N3H at 30 °C. The H-bond of Iso O4 with Leu51 N (peptide) at 10 °C switched to that with Ala49 N (peptide) at 30 °C. The reported fluorescence lifetimes (228 and 182 ps at 10 and 30 °C, respectively) of DAAO were analyzed with Kakitani and Mataga (KM) ET theory. The calculated fluorescence lifetimes displayed an excellent agreement with the observed lifetimes. The ET rate was fastest from Tyr224 to the excited Iso (Iso*) at 10 °C and from Tyr314 at 30 °C, despite the fact that the Rc was shortest between Iso and Tyr224 at both temperatures. This was explained by the electrostatic energy in the protein. The differences in the observed fluorescence lifetimes at 10 and 30 °C were ascribed to the differences in electron affinity of the Iso* at both temperatures, in which the free energies of the electron affinity of Iso* at 10 and 30 °C were -8.69 eV and -8.51 eV respectively. The other physical quantities related to ET did not differ appreciably at both temperatures. The electron affinities at both temperatures were calculated with a semi-empirical molecular orbital method (MO) of PM6. Mean calculated electron affinities over 100 snapshots with 0.1 ps intervals were -7.69 eV at 10 °C and -7.59 eV at 30 °C. The difference in the calculated electron affinities, -0.11 eV, was close to the observed difference in the

  17. A mixed quantum-classical Liouville study of the population dynamics in a model photo-induced condensed phase electron transfer reaction.

    PubMed

    Rekik, Najeh; Hsieh, Chang-Yu; Freedman, Holly; Hanna, Gabriel

    2013-04-14

    We apply two approximate solutions of the quantum-classical Liouville equation (QCLE) in the mapping representation to the simulation of the laser-induced response of a quantum subsystem coupled to a classical environment. These solutions, known as the Poisson Bracket Mapping Equation (PBME) and the Forward-Backward (FB) trajectory solutions, involve simple algorithms in which the dynamics of both the quantum and classical degrees of freedom are described in terms of continuous variables, as opposed to standard surface-hopping solutions in which the classical degrees of freedom hop between potential energy surfaces dictated by the discrete adiabatic state of the quantum subsystem. The validity of these QCLE-based solutions is tested on a non-trivial electron transfer model involving more than two quantum states, a time-dependent Hamiltonian, strong subsystem-bath coupling, and an initial energy shift between the donor and acceptor states that depends on the strength of the subsystem-bath coupling. In particular, we calculate the time-dependent population of the photoexcited donor state in response to an ultrafast, on-resonance pump pulse in a three-state model of an electron transfer complex that is coupled asymmetrically to a bath of harmonic oscillators through the optically dark acceptor state. Within this approach, the three-state electron transfer complex is treated quantum mechanically, while the bath oscillators are treated classically. When compared to the more accurate QCLE-based surface-hopping solution and to the numerically exact quantum results, we find that the PBME solution is not capable of qualitatively capturing the population dynamics, whereas the FB solution is. However, when the subsystem-bath coupling is decreased (which also decreases the initial energy shift between the donor and acceptor states) or the initial shift is removed altogether, both the PBME and FB results agree better with the QCLE-based surface-hopping results. These findings

  18. A mixed quantum-classical Liouville study of the population dynamics in a model photo-induced condensed phase electron transfer reaction

    SciTech Connect

    Rekik, Najeh; Freedman, Holly; Hanna, Gabriel; Hsieh, Chang-Yu

    2013-04-14

    We apply two approximate solutions of the quantum-classical Liouville equation (QCLE) in the mapping representation to the simulation of the laser-induced response of a quantum subsystem coupled to a classical environment. These solutions, known as the Poisson Bracket Mapping Equation (PBME) and the Forward-Backward (FB) trajectory solutions, involve simple algorithms in which the dynamics of both the quantum and classical degrees of freedom are described in terms of continuous variables, as opposed to standard surface-hopping solutions in which the classical degrees of freedom hop between potential energy surfaces dictated by the discrete adiabatic state of the quantum subsystem. The validity of these QCLE-based solutions is tested on a non-trivial electron transfer model involving more than two quantum states, a time-dependent Hamiltonian, strong subsystem-bath coupling, and an initial energy shift between the donor and acceptor states that depends on the strength of the subsystem-bath coupling. In particular, we calculate the time-dependent population of the photoexcited donor state in response to an ultrafast, on-resonance pump pulse in a three-state model of an electron transfer complex that is coupled asymmetrically to a bath of harmonic oscillators through the optically dark acceptor state. Within this approach, the three-state electron transfer complex is treated quantum mechanically, while the bath oscillators are treated classically. When compared to the more accurate QCLE-based surface-hopping solution and to the numerically exact quantum results, we find that the PBME solution is not capable of qualitatively capturing the population dynamics, whereas the FB solution is. However, when the subsystem-bath coupling is decreased (which also decreases the initial energy shift between the donor and acceptor states) or the initial shift is removed altogether, both the PBME and FB results agree better with the QCLE-based surface-hopping results. These findings

  19. Photoinduced electron detachment and proton transfer: the proposal for alternative path of formation of triplet states of guanine (G) and cytosine (C) pair.

    PubMed

    Gu, Jiande; Wang, Jing; Leszczynski, Jerzy

    2015-02-12

    A viable pathway is proposed for the formation of the triplet state of the GC Watson-Crick base pair. It includes the following steps: (a) a low-energy electron is captured by cytosine in the GC pair, forming the cytosine base-centered radical anion GC(-•); and (b) photoradiation with energy around 5 eV initiates the electron detachment from either cytosine (in the gas phase) or guanine (in aqueous solutions). This triggers interbase proton transfer from G to C, creating the triplet state of the GC pair. Double proton transfer involving the triplet state of GC pair leads to the formation of less stable tautomer G(N2-H)(•)C(O2H)(•). Tautomerization is accomplished through a double proton transfer process in which one proton at the N3 of C(H)(•) migrates to the N1 of G(-H)(•); meanwhile, the proton at the N2 of G transfers to the O2 of C. This process is energetically viable; the corresponding activation energy is around 12-13 kcal/mol. The base-pairing energy of the triplet is found to be ∼3-5 kcal/mol smaller than that of the singlet state. Thus, the formation of the triplet state GC pair in DNA double strand only slightly weakens its stability. The obtained highly reactive radicals are expected to cause serious damage in the DNA involved in biochemical processes, such as DNA replication where radicals are exposed in the single strands.

  20. Photo-induced water oxidation at the aqueous GaN (101¯0) interface: Deprotonation kinetics of the first proton-coupled electron-transfer step

    SciTech Connect

    Ertem, Mehmed Z.; Kharche, Neerav; Batista, Victor S.; Hybertsen, Mark S.; Tully, John C.; Muckerman, James T.

    2015-03-12

    Photoeclectrochemical water splitting plays a key role in a promising path to the carbon-neutral generation of solar fuels. Wurzite GaN and its alloys (e.g., GaN/ZnO and InGaN) are demonstrated photocatalysts for water oxidation, and they can drive the overall water splitting reaction when coupled with co-catalysts for proton reduction. In the present work, we investigate the water oxidation mechanism on the prototypical GaN (101¯0) surface using a combined ab initio molecular dynamics and molecular cluster model approach taking into account the role of water dissociation and hydrogen bonding within the first solvation shell of the hydroxylated surface. The investigation of free-energy changes for the four proton-coupled electron-transfer (PCET) steps of the water oxidation mechanism shows that the first PCET step for the conversion of –Ga-OH to –Ga-O˙⁻ requires the highest energy input. We further examine the sequential PCETs, with the proton transfer (PT) following the electron transfer (ET), and find that photo-generated holes localize on surface –NH sites is thermodynamically more favorable than –OH sites. However, proton transfer from –OH sites with subsequent localization of holes on oxygen atoms is kinetically favored owing to hydrogen bonding interactions at the GaN (101¯0)–water interface. We find that the deprotonation of surface –OH sites is the limiting factor for the generation of reactive oxyl radical ion intermediates and consequently for water oxidation.

  1. Photo-induced water oxidation at the aqueous GaN (101¯0) interface: Deprotonation kinetics of the first proton-coupled electron-transfer step

    DOE PAGES

    Ertem, Mehmed Z.; Kharche, Neerav; Batista, Victor S.; ...

    2015-03-12

    Photoeclectrochemical water splitting plays a key role in a promising path to the carbon-neutral generation of solar fuels. Wurzite GaN and its alloys (e.g., GaN/ZnO and InGaN) are demonstrated photocatalysts for water oxidation, and they can drive the overall water splitting reaction when coupled with co-catalysts for proton reduction. In the present work, we investigate the water oxidation mechanism on the prototypical GaN (101¯0) surface using a combined ab initio molecular dynamics and molecular cluster model approach taking into account the role of water dissociation and hydrogen bonding within the first solvation shell of the hydroxylated surface. The investigation ofmore » free-energy changes for the four proton-coupled electron-transfer (PCET) steps of the water oxidation mechanism shows that the first PCET step for the conversion of –Ga-OH to –Ga-O˙⁻ requires the highest energy input. We further examine the sequential PCETs, with the proton transfer (PT) following the electron transfer (ET), and find that photo-generated holes localize on surface –NH sites is thermodynamically more favorable than –OH sites. However, proton transfer from –OH sites with subsequent localization of holes on oxygen atoms is kinetically favored owing to hydrogen bonding interactions at the GaN (101¯0)–water interface. We find that the deprotonation of surface –OH sites is the limiting factor for the generation of reactive oxyl radical ion intermediates and consequently for water oxidation.« less

  2. Increase in the coordination number of a cobalt porphyrin after photo-induced interfacial electron transfer into nanocrystalline TiO2.

    PubMed

    Achey, Darren; Ardo, Shane; Meyer, Gerald J

    2012-09-17

    Spectroscopic, electrochemical, and kinetic data provide compelling evidence for a coordination number increase initiated by interfacial electron transfer. Light excitation of Co(I)(meso-5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin) anchored to a nanocrystalline TiO(2) thin film, abbreviated Co(I)P/TiO(2), immersed in an acetonitrile:pyridine electrolyte resulted in rapid excited state injection, k(inj) > 10(8) s(-1), to yield Co(II)P/TiO(2)(e(-)), followed by axial coordination of pyridine to the Co(II)P and hence an increase in coordination number from four to five. The formal oxidation state and coordination environment of the Co metalloporphyrin on TiO(2) were assigned through comparative studies in fluid solution as well as by comparisons to previously reported data. The kinetics for pyridine coordination were successfully modeled with a pseudo-first order kinetic model that yielded a second-order rate constant of k(+py) = 2 × 10(8) M(-1) s(-1). Spectro-electrochemical measurements showed that pyridine coordination resulted in a ∼200 mV negative shift in the Co(II/I) reduction potential, E°(Co(II/I)/TiO(2)) = -0.72 V and E°(Co(II/I)(py)/TiO(2)) = -0.85 V vs NHE. With some assumptions, this indicated an equilibrium formation constant K(f) = 400 M(-1) for the Co(II)P(py)/TiO(2) compound. The kinetics for charge recombination were non-exponential under all conditions studied, but were successfully modeled by the Kohlrausch-Williams-Watts (KWW) function with observed rate constants that decreased by about a factor of 100 when pyridine was present. The possible mechanisms for charge recombination are discussed.

  3. Photo-induced Defects in Semiconductors

    NASA Astrophysics Data System (ADS)

    Redfield, David; Bube, Richard H.

    2006-03-01

    1. Introduction: metastable defects; 2. III-V compounds: DX2 and EL2 centers; 3. Other crystalline materials; 4. Hydrogenated amorphous silicon: properties of defects; 5. Hydrogenated amorphous silicon: photo-induced defect kinetics and processes; 6. Other amorphous semiconductors; 7. Photo-induced defect effects in devices; References; Index.

  4. QSARs for photo-induced toxicity of polycyclic aromatic hydrocarbons (PAHs)

    SciTech Connect

    Mekenyan, O.; Call, D.; Ankley, G.; Veith, G.

    1994-12-31

    Photo-induced toxicity of polycyclic aromatic hydrocarbons (PAHs) was found to be a result of competing internal and external factors which interact to produce a complex, multilinear relationship between toxicity and chemical structure. The relationship between molecular electronic structure and photo-dynamic effects was studied in both ground and excited states. A measure of the energy required for an electron to be elevated from the highest occupied molecular orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO), or HOMO-LUMO gap, provided a useful ground state index to explain the persistence, light absorption, and eventual photo-induced toxicity of PAHs to Daphnia magna. The derived QSARs clearly distinguished photo-induced toxicity differences between pairs of structurally similar PAHs, such as phenanthrene and anthracene, benzo[a]anthracene and tetracene, etc. Those PAHs exhibiting photo-induced toxicity were consistently within a specific HOMO-LUMO gap range. The relationship between the excited state electronic parameters and toxicity was also studied. Significant correlations were found with the measured energies of singlet and triplet states from spectroscopic data. An investigation of the effect of substituent additions on photo-induced acute toxicity of parent PAHs revealed that alkyl and hydroxy moieties did not significantly reduce the HOMO-LUMO gap of the parent PAHs. Nitro, alkene and chloro substituents cause gap reductions, whereby certain derivatives of parent chemicals that were close to the ``toxic region`` of the electronic gap could become phototoxic with such additions.

  5. Inactivation of tyrosinase photoinduced by pterin

    SciTech Connect

    Laura Dantola, M.; Gojanovich, Aldana D.; Thomas, Andres H.

    2012-08-03

    Highlights: Black-Right-Pointing-Pointer Under UV-A radiation, tirosinase is photoinactivated by pterin. Black-Right-Pointing-Pointer The mechanism involves an electron transfer-initiated process. Black-Right-Pointing-Pointer The photochemical process affects both activities of tyrosinase. -- Abstract: Tyrosinase catalyzes in mammals the first and rate-limiting step in the biosynthesis of the melanin, the main pigment of the skin. Pterins, heterocyclic compounds able to photoinduce oxidation of DNA and its components, accumulate in the skin of patients suffering from vitiligo, a chronic depigmentation disorder in which the protection against UV radiation fails due to the lack of melanin. Aqueous solutions of tyrosinase were exposed to UV-A irradiation (350 nm) in the presence of pterin, the parent compound of oxidized pterins, under different experimental conditions. The enzyme activity in the irradiated solutions was determined by spectrophotometry and HPLC. In this work, we present data that demonstrate unequivocally that the enzyme is photoinactivated by pterin. The mechanism of the photosensitized process involves an electron transfer from tyrosinase to the triplet excited state of pterin, formed after UV-A excitation of pterin. The biological implications of the results are discussed.

  6. Photoinduced modulation and relaxation characteristics in LaAlO3/SrTiO3 heterointerface

    PubMed Central

    Jin, K. X.; Lin, W.; Luo, B. C.; Wu, T.

    2015-01-01

    We report the modulation and relaxation characteristics in the two-dimensional electron gas system at LaAlO3/SrTiO3 heterointerface induced by the ultraviolet light illumination (365 nm). The suppression of Kondo effect at the interface illuminated by the light originates from the light irradiation-induced decoherence effect of localized states. It is interesting to note that the persistent and transient photoinduced effects are simultaneously observed and the photoinduced maximum change values in resistance are 80.8% and 51.4% at T = 20 K, respectively. Moreover, the photoinduced relaxation processes after the irradiation are systematically analyzed using the double exponential model. These results provide the deeper understanding of the photoinduced effect and the experimental evidence of tunable Kondo effect in oxides-based two-dimensional electron gas systems. PMID:25739889

  7. Photoinduced formation of thiols in human hair.

    PubMed

    Fedorkova, M V; Brandt, N N; Chikishev, A Yu; Smolina, N V; Balabushevich, N G; Gusev, S A; Lipatova, V A; Botchey, V M; Dobretsov, G E; Mikhalchik, E V

    2016-11-01

    Raman, scanning electron, and optical microscopy of hair and spectrophotometry of soluble hair proteins are used to study the effect of UV-vis radiation on white hair. The samples of a healthy subject are irradiated using a mercury lamp and compared with non-irradiated (control) hair. The cuticle damage with partial exfoliation is revealed with the aid of SEM and optical microscopy of semifine sections. Gel filtration chromatography shows that the molecular weight of soluble proteins ranges from 5 to 7kDa. Absorption spectroscopy proves an increase in amount of thiols in a heavier fraction of the soluble proteins of irradiated samples under study. Raman data indicate a decrease in the amount of SS and CS bonds in cystines and an increase in the amount of SH bonds due to irradiation. Such changes are more pronounced in peripheral regions of hair. Conformational changes of hair keratins presumably related to the cleavage of disulfide bonds, follow from variations in amide I and low-frequency Raman bands. An increase in the content of thiols in proteins revealed by both photometric data on soluble proteins and Raman microspectroscopy of hair cuts can be used to develop a protocol of the analysis of photoinduced hair modification.

  8. Photoinduced color centers creation in superionic crystals RbAg 4 I 5

    NASA Astrophysics Data System (ADS)

    Kovaleva, N.; Boris, A.; Bredikhin, S.; Awano, T.

    1995-12-01

    A new phenomenon of a reversible photoinduced coloration caused by light irradiation is discovered and investigated in superionic RbAg 4 I 5 crystals. The reversible photoinduced absorption is found to be a result of irradiation by light with wavelengths in the region from 420 nm to 450 nm. The proposed mechanism of the discovered effect is associated with ambipolar diffusion of screened by mobile ions optically excited electronic carriers. The processes of color centers creation in superionic crystals RbAg 4 I 5 due to additive coloring in iodine vapours, ionic implantation and ?-ray irradiation are considered.

  9. Photo-induced and electrooptic properties of (Pb,La)(Zr,Ti)O{sub 3} films

    SciTech Connect

    Dimos, D.; Warren, W.L.; Tuttle, B.A.

    1993-07-01

    Photo-induced changes in the hysteresis behavior of sol-gel derived Pb(Zr,Ti)O{sub 3} (PZT) and (Pb,La)(Zr,Ti)O{sub 3} (PLZT) films have been characterized. Film photosensitivity has been evaluated with respect to magnitude of effects, time response and spectral dependence. Photo-induced hysteresis changes exhibit a stretched-exponential time dependence, which implies a dispersive mechanism. The spectral dependence is strongly peaked at the band edge ({approximately} 3.4 eV), which indicates that generation of electron-hole pairs in the material is critical. The photo-induced hysteresis changes are reproducible and stable, which indicates that the controlling charge traps are stable. However, improvements in film photosensitivity will be required to develop these materials for optical memory applications.

  10. Static and dynamic photoinduced magnetic effects in yttrium-iron garnet lightly doped with barium ions

    SciTech Connect

    Vorob'eva, N. V. Khalilov, R. Z.

    2012-04-15

    In yttrium-iron garnet lightly doped with barium, direct measurements of the photoinduced changes in magnetostrictive strains disagree with those in magnetostriction constants at 78-100 K. This is attributed to a considerable photoinduced modification of the initial state in this sample due to a redistribution of the charge (during illumination) between cations of the ferromagnetic octahedral sublattice. In the same sample, the temperature dependence of the photoinduced disaccomodation of magnetic permeability characterizing the initial demagnetized state is measured and calculated. A change in the electron mechanism of the phenomenon during the transition to room temperature is shown. The conclusion about the promising prospects for using such samples for remagnetization by light is advanced.

  11. Photoinduced Charge Transport in a BHJ Solar Cell Controlled by an External Electric Field

    PubMed Central

    Li, Yongqing; Feng, Yanting; Sun, Mengtao

    2015-01-01

    This study investigated theoretical photoinduced charge transport in a bulk heterojunction (BHJ) solar cell controlled by an external electric field. Our method for visualizing charge difference density identified the excited state properties of photoinduced charge transfer, and the charge transfer excited states were distinguished from local excited states during electronic transitions. Furthermore, the calculated rates for the charge transfer revealed that the charge transfer was strongly influenced by the external electric field. The external electric field accelerated the rate of charge transfer by up to one order when charge recombination was significantly restrained. Our research demonstrated that photoinduced charge transport controlled by an external electric field in a BHJ solar cell is efficient, and the exciton dissociation is not the limiting factor in organic solar cells.Our research should aid in the rational design of a novel conjugated system of organic solar cells. PMID:26353997

  12. Photoinduced magnetic force between nanostructures

    NASA Astrophysics Data System (ADS)

    Guclu, Caner; Tamma, Venkata Ananth; Wickramasinghe, Hemantha Kumar; Capolino, Filippo

    2015-12-01

    Photoinduced magnetic force between nanostructures, at optical frequencies, is investigated theoretically. Till now optical magnetic effects were not used in scanning probe microscopy because of the vanishing natural magnetism with increasing frequency. On the other hand, artificial magnetism in engineered nanostructures led to the development of measurable optical magnetism. Here two examples of nanoprobes that are able to generate strong magnetic dipolar fields at optical frequency are investigated: first, an ideal magnetically polarizable nanosphere and then a circular cluster of silver nanospheres that has a looplike collective plasmonic resonance equivalent to a magnetic dipole. Magnetic forces are evaluated based on nanostructure polarizabilities, i.e., induced magnetic dipoles, and magnetic-near field evaluations. As an initial assessment on the possibility of a magnetic nanoprobe to detect magnetic forces, we consider two identical magnetically polarizable nanoprobes and observe magnetic forces on the order of piconewtons, thereby bringing it within detection limits of conventional atomic force microscopes at ambient pressure and temperature. The detection of magnetic force is a promising method in studying optical magnetic transitions that can be the basis of innovative spectroscopy applications.

  13. Photoinduced toxicity of engineered nanomaterials

    NASA Astrophysics Data System (ADS)

    Jones, Philip Scott

    Engineered nanomaterials including metal, metal oxide and carbon based nanomaterials are extensively used in a wide variety of applications to the extent that their presence in the environment is expected to increase dramatically over the next century. These nanomaterials may be photodegraded by solar radiation and thereby release metal ions into the environment that can produce cytotoxic and genotoxic effects. Photoinduced toxicity experiments are performed exposing human lung epithelial carcinoma cells [H1650] to engineered semiconductor nanoparticles such as CdSe quantum dots and ZnO nanoparticles after exposure to 3, 6, and 9 hours of solar simulated radiation. Cytotoxicity and genotoxicity of the metal ions are evaluated using ZnSO4 and CdCl2 solutions for the MTT assay and Comet assay respectively. The objective of the dissertation is to obtain quantitative information about the environmental transformation of engineered nanomaterials and their mechanism of toxicity. This information is critical for addressing the environmental health and safety risks of engineered nanomaterials to workers, consumers and the environment.

  14. Photoinduced development of antibacterial materials derived from isosorbide moiety.

    PubMed

    Lorenzini, Cedric; Haider, Adnan; Kang, Inn-Kyu; Sangermano, Marco; Abbad-Andalloussi, Samir; Mazeran, Pierre-Emmanuel; Lalevée, Jacques; Renard, Estelle; Langlois, Valérie; Versace, Davy-Louis

    2015-03-09

    A straightforward method for immobilizing in situ generated silver nanoparticles on the surface of a photoactivable isosorbide-derived monomer is developed with the objective to design a functional material having antibacterial properties. The photoinduced thiol-ene mechanism involved in these syntheses is described by the electron spin resonance/spin trapping technique. The resulting materials with or without silver nanoparticles (Ag NPs) were used as films or as coatings on glass substrate. The surface of the synthesized materials was characterized by X-ray photoelectron spectroscopy and scanning electron microscopy, and their thermal and mechanical properties were evaluated by dynamic-mechanical thermal tests, differential scanning calorimetry, thermogravimetric analyses, along with pencil hardness, nanoindentation, and scratch resistance tests. The photoinduced formation of Ag NPs is also confirmed by UV spectrophotometry. Finally, a primary investigation demonstrates the antibacterial properties of the isosorbide-derived material against Staphylococcus aureus and Escherichia coli, as well as its cytocompatibility toward NIH 3T3 fibroblastic cells.

  15. Millisecond Photoinduced Absorption Studies of Pyridine-Based Copolymer Films

    NASA Astrophysics Data System (ADS)

    Coplin, K. A.; Clark, D. T.; Jessen, S. W.; Epstein, A. J.; Fu, D.-K.; Swager, T. M.

    1997-03-01

    We present a study of the photoexcited states in copolymers of poly(p-pyridyl vinylene) and poly(p-phenylene vinylene) (PPyVPR_iV) with sidegroups R_1=C_12H_25 or R_2=COOC_12H_25 attached at the 2 and 5 positions of the phenyl ring. Previous studies discussed the millisecond photoinduced absorption (ms PA) characteristics of PPyVPR_iV powders(S.W. Jessen et al.), Synth. Met., in press.. In particular, triplet-triplet (T-T) transitions were observed at 1.6 eV for both materials. Additional polaron signatures were also observed in both the electronic ( ~ 0.85 eV) and infrared (1100 - 1600 cm-1) regions of the photoinduced spectrum. We compare these powder results with ms PA features for film morphologies of both the copolymers. We observe a weaker ( ~ 10X) T-T^* transition for copolymer films cast from xylene solution indicating a reduction in triplet exciton production as compared to powder samples. These results are contrasted with the behavior we reported(S.W. Jessen et al.), to be published. earlier for film and powder samples of the parent polymer poly(p-pyridyl vinylene).

  16. Photoinduced Oxidative DNA Damage Revealed by an Agarose Gel Nicking Assay: A Biophysical Chemistry Laboratory Experiment

    NASA Astrophysics Data System (ADS)

    Shafirovich, Vladimir; Singh, Carolyn; Geacintov, Nicholas E.

    2003-11-01

    Oxidative damage of DNA molecules associated with electron-transfer reactions is an important phenomenon in living cells, which can lead to mutations and contribute to carcinogenesis and the aging processes. This article describes the design of several simple experiments to explore DNA damage initiated by photoinduced electron-transfer reactions sensitized by the acridine derivative, proflavine (PF). A supercoiled DNA agarose gel nicking assay is employed as a sensitive probe of DNA strand cleavage. A low-cost experimental and computer-interfaced imaging apparatus is described allowing for the digital recording and analysis of the gel electrophoresis results. The first experiment describes the formation of direct strand breaks in double-stranded DNA induced by photoexcitation of the intercalated PF molecules. The second experiment demonstrates that the addition of the well-known electron acceptor, methylviologen, gives rise to a significant enhancement of the photochemical DNA strand cleavage effect. This occurs by an electron transfer step to methylviologen that renders the inital photoinduced charge separation between photoexcited PF and DNA irreversible. The third experiment demonstrates that the action spectrum of the DNA photocleavage matches the absorption spectrum of DNA-bound, intercalated PF molecules, which differs from that of free PF molecules. This result demonstrates that the photoinduced DNA strand cleavage is initiated by intercalated rather than free PF molecules.

  17. Photoinduced mass transport in azo compounds

    NASA Astrophysics Data System (ADS)

    Klismeta, K.; Teteris, J.; Aleksejeva, J.

    2013-12-01

    The photoinduced changes of optical properties in azobenzene containing compound thin films were studied under influence of polarized and non-polarized 532 nm laser light. Under influence of light azo compounds experience trans-cis isomerisation process, that can be observed in the absorbance spectrum of the sample. If the light is linearly polarized, molecules align perpendicularly to the electric field vector and as a result photoinduced dichroism and birefringence is obtained. If a known lateral polarization modulation of the light beam is present, mass transport of the azobenzene containing compound occurs. By measuring the surface relief with a profilometer the direction of mass transport can be determined. The studies of this work show that direct holographic recording of surface relief gratings can be used in optoelectronics, telecommunications and data storage.

  18. Photoinduced charge transfer phase transition in cesium manganese hexacyanoferrate

    SciTech Connect

    Matsuda, Tomoyuki; Tokoro, Hiroko; Hashimoto, Kazuhito; Ohkoshi, Shin-ichi

    2007-05-01

    Cesium manganese hexacyanoferrate, Cs{sub 1.51}Mn[Fe(CN){sub 6}], shows a thermal phase transition between Mn{sup II}-NC-Fe{sup III} [high-temperature (HT) phase] and Mn{sup III}-NC-Fe{sup II} [low-temperature (LT) phase] with phase transition temperatures of 170 K (HT{yields}LT) and 230 K (LT{yields}HT). The LT phase shows ferromagnetism with Curie temperature of 7 K and coercive field of 60 Oe. Irradiating with 532 nm laser light converts the LT phase into the photoinduced (PI) phase, which does not have spontaneous magnetization. The electronic state of the PI phase corresponds to that of the HT phase and the relaxation temperature from the PI to the LT phase is observed at 90 K.

  19. Time-resolved x-ray absorption spectroscopy of photoinduced insulator-metal transition in a colossal magnetoresistive manganite

    SciTech Connect

    Rini, M.; Tobey, R.; Wall, S.; Zhu, Y.; Tomioka, Y.; Tokura, Y.; Cavalleri, A.; Schoenlein, R.W.

    2008-08-01

    We studied the ultrafast insulator-metal transition in a manganite by means of picosecond X-ray absorption at the O K- and Mn L-edges, probing photoinduced changes in O-2p and Mn-3d electronic states near the Fermi level.

  20. The nature of photoinduced phase transition and metastable states in vanadium dioxide

    PubMed Central

    Tao, Zhensheng; Zhou, Faran; Han, Tzong-Ru T.; Torres, David; Wang, Tongyu; Sepulveda, Nelson; Chang, Kiseok; Young, Margaret; Lunt, Richard R.; Ruan, Chong-Yu

    2016-01-01

    Photoinduced threshold switching processes that lead to bistability and the formation of metastable phases in photoinduced phase transition of VO2 are elucidated through ultrafast electron diffraction and diffusive scattering techniques with varying excitation wavelengths. We uncover two distinct regimes of the dynamical phase change: a nearly instantaneous crossover into an intermediate state and its decay led by lattice instabilities over 10 ps timescales. The structure of this intermediate state is identified to be monoclinic, but more akin to M2 rather than M1 based on structure refinements. The extinction of all major monoclinic features within just a few picoseconds at the above-threshold-level (~20%) photoexcitations and the distinct dynamics in diffusive scattering that represents medium-range atomic fluctuations at two photon wavelengths strongly suggest a density-driven and nonthermal pathway for the initial process of the photoinduced phase transition. These results highlight the critical roles of electron correlations and lattice instabilities in driving and controlling phase transformations far from equilibrium. PMID:27982066

  1. The nature of photoinduced phase transition and metastable states in vanadium dioxide

    NASA Astrophysics Data System (ADS)

    Tao, Zhensheng; Zhou, Faran; Han, Tzong-Ru T.; Torres, David; Wang, Tongyu; Sepulveda, Nelson; Chang, Kiseok; Young, Margaret; Lunt, Richard R.; Ruan, Chong-Yu

    2016-12-01

    Photoinduced threshold switching processes that lead to bistability and the formation of metastable phases in photoinduced phase transition of VO2 are elucidated through ultrafast electron diffraction and diffusive scattering techniques with varying excitation wavelengths. We uncover two distinct regimes of the dynamical phase change: a nearly instantaneous crossover into an intermediate state and its decay led by lattice instabilities over 10 ps timescales. The structure of this intermediate state is identified to be monoclinic, but more akin to M2 rather than M1 based on structure refinements. The extinction of all major monoclinic features within just a few picoseconds at the above-threshold-level (~20%) photoexcitations and the distinct dynamics in diffusive scattering that represents medium-range atomic fluctuations at two photon wavelengths strongly suggest a density-driven and nonthermal pathway for the initial process of the photoinduced phase transition. These results highlight the critical roles of electron correlations and lattice instabilities in driving and controlling phase transformations far from equilibrium.

  2. The photoinduced dynamics of X[M(dmit)2]2 salts

    NASA Astrophysics Data System (ADS)

    Ishikawa, Tadahiko; Hayes, Stuart A.; Miller, R. J. Dwayne; Hada, Masaki; Koshihara, Shinya

    2017-03-01

    We review our work on the photoinduced dynamics of X[M(dmit)2]2 salts in the charge-separated (CS) phase from the viewpoints of both electronic structural change and lattice or molecular structural change. The driving force for the CS phase formation is a strong correlation among the charge distribution, orbital energies, and the molecular structure; this is in contrast to frequently studied charge-ordered systems such as EDOTTF2PF6, whose formation is mainly driven by the intersite Coulomb repulsion. Despite the localized nature of the structural component, the cooperativity inherent to the crystal is likely to play an important role in photoinduced phenomena. In this review, we summarize the results obtained by a series of optical pump-probe experiments on this class of materials. We have also recently extended these studies using ultrafast electron diffraction to follow the nuclear motion in one of these systems. Such information is crucial for a full understanding of the photoinduced phenomena and it is anticipated that combining the results of the optical and diffraction studies will lead to more fruitful insight than either technique can offer in isolation.

  3. Supramolecular photomagnetic materials: photoinduced dimerization of ferrocene-based polychlorotriphenylmethyl radicals.

    PubMed

    Ratera, Imma; Ruiz-Molina, Daniel; Vidal-Gancedo, José; Novoa, Juan J; Wurst, Klaus; Letard, Jean-François; Rovira, Concepció; Veciana, Jaume

    2004-02-06

    New ferrocenyl Schiff-base polychlorotriphenylmethyl radicals have been synthesized and characterized. The imino group of one such radical undergoes an irreversible trans to cis structural isomerization induced by light. Such photoinduced isomerization has been monitored by UV/Vis and ESR spectroscopy and also monitored by HPLC. ESR frozen solution experiments at low temperature revealed that the cis isomer dimerizes, showing a strong antiferromagnetic interaction. Although numerous photochromic supramolecular systems have been described, such a photoinduced self-assembly process represents the first example of a one-way photoswitchable magnetic system in which a conversion between a doublet and a singlet ground state species is promoted by a photoinduced dimerization process driven by the formation of hydrogen bonds. DFT calculations on the minimized structure and on the rotational barriers have been performed to establish the origin of such behavior. The effect of the substituents and the media polarity on the photoisomerization of this imine chromophore have also been studied. It has been observed that the efficiency of the process is markedly dependent on the presence and characteristics of electron-donor and electron-acceptor substituents of the ferrocenyl Schiff-base polychlorotriphenylmethyl radicals as well as on the polarity of the solvent.

  4. Photoinduced heterostructure in a vanadium dioxide film

    NASA Astrophysics Data System (ADS)

    Semenov, A. L.

    2017-02-01

    A photoinduced semiconductor-metal phase transition that occurs in a surface layer of vanadium dioxide film on an aluminum substrate within the time Δ t < 1 ps has been studied theoretically. A nonthermal mechanism of the development of instability has been considered. It has been shown that a heterophase structure containing metallic and semiconductor layers is formed in the VO2 film. The phase transition time τ has been calculated as a function of the distance z from the film surface. Comparison with the experiment has been carried out.

  5. Photoinduced Force Mapping of Plasmonic Nanostructures.

    PubMed

    Tumkur, Thejaswi U; Yang, Xiao; Cerjan, Benjamin; Halas, Naomi J; Nordlander, Peter; Thomann, Isabell

    2016-12-14

    The ability to image the optical near-fields of nanoscale structures, map their morphology, and concurrently obtain spectroscopic information, all with high spatiotemporal resolution, is a highly sought-after technique in nanophotonics. As a step toward this goal, we demonstrate the mapping of electromagnetic forces between a nanoscale tip and an optically excited sample consisting of plasmonic nanostructures with an imaging platform based on atomic force microscopy. We present the first detailed joint experimental-theoretical study of this type of photoinduced force microscopy. We show that the enhancement of near-field optical forces in gold disk dimers and nanorods follows the expected plasmonic field enhancements with strong polarization sensitivity. We then introduce a new way to evaluate optically induced tip-sample forces by simulating realistic geometries of the tip and sample. We decompose the calculated forces into in-plane and out-of-plane components and compare the calculated and measured force enhancements in the fabricated plasmonic structures. Finally, we show the usefulness of photoinduced force mapping for characterizing the heterogeneity of near-field enhancements in precisely e-beam fabricated nominally alike nanostructures - a capability of widespread interest for precise nanomanufacturing, SERS, and photocatalysis applications.

  6. Towards efficient photoinduced charge separation in carbon nanodots and TiO2 composites in the visible region.

    PubMed

    Sun, Mingye; Qu, Songnan; Ji, Wenyu; Jing, Pengtao; Li, Di; Qin, Li; Cao, Junsheng; Zhang, Hong; Zhao, Jialong; Shen, Dezhen

    2015-03-28

    In this work, photoinduced charge separation behaviors in non-long-chain-molecule-functionalized carbon nanodots (CDs) with visible intrinsic absorption (CDs-V) and TiO2 composites were investigated. Efficient photoinduced electron injection from CDs-V to TiO2 with a rate of 8.8 × 10(8) s(-1) and efficiency of 91% was achieved in the CDs-V/TiO2 composites. The CDs-V/TiO2 composites exhibited excellent photocatalytic activity under visible light irradiation, superior to pure TiO2 and the CDs with the main absorption band in the ultraviolet region and TiO2 composites, which indicated that visible photoinduced electrons and holes in such CDs-V/TiO2 composites could be effectively separated. The incident photon-to-current conversion efficiency (IPCE) results for the CD-sensitized TiO2 solar cells also agreed with efficient photoinduced charge separation between CDs-V and the TiO2 electrode in the visible range. These results demonstrate that non-long-chain-molecule-functionlized CDs with a visible intrinsic absorption band could be appropriate candidates for photosensitizers and offer a new possibility for the development of a well performing CD-based photovoltaic system.

  7. Fourth-order perturbative model for photoinduced internal conversion processes.

    PubMed

    Molesky, Brian P; Moran, Andrew M

    2013-12-27

    Essential to the functionality of numerous biological and synthetic molecular systems is the ability to rapidly convert electronic excitation energy into heat. Such internal conversion (IC) transitions often cannot be described by traditional second-order kinetic theories because of time-coincident electronic and nuclear relaxation processes. Here, we present a perturbative fourth-order phenomenological model for photoinduced IC that incorporates effects associated with finite laser bandwidths and nonequilibrium nuclear motions. Specialized knowledge of first-principles computational methods is not required, and many parameters can be obtained with standard spectroscopic measurements. The model is applied to the IC processes that precede electrocyclic ring-opening in α-terpinene. It is shown that the primary factor governing the shape of the population decay profile (Gaussian versus exponential) is the rate at which the wavepacket approaches the geometry corresponding to degeneracy between the excited states. Other parameters such as the displacement in the promoting mode and the thermal fluctuation amplitudes affect the sensitivity of the IC dynamics to motion of the wavepacket but do not alter the basic physical picture. Finally, we suggest a wavepacket representation of the IC process to visualize correlations between population-transfer dynamics and the amount of energy transferred from the system to the bath.

  8. Phase diagram of the ultrafast photoinduced insulator-metal transition in vanadium dioxide

    NASA Astrophysics Data System (ADS)

    Cocker, T. L.; Titova, L. V.; Fourmaux, S.; Holloway, G.; Bandulet, H.-C.; Brassard, D.; Kieffer, J.-C.; El Khakani, M. A.; Hegmann, F. A.

    2012-04-01

    We use time-resolved terahertz spectroscopy to probe the ultrafast dynamics of the insulator-metal phase transition induced by femtosecond laser pulses in a nanogranular vanadium dioxide (VO2) film. Based on the observed thresholds for characteristic transient terahertz dynamics, a phase diagram of critical pump fluence versus temperature for the insulator-metal phase transition in VO2 is established for the first time over a broad range of temperatures down to 17 K. We find that both Mott and Peierls mechanisms are present in the insulating state and that the photoinduced transition is nonthermal. We propose a critical-threshold model for the ultrafast photoinduced transition based on a critical density of electrons and a critical density of coherently excited phonons necessary for the structural transition to the metallic state. As a result, evidence is found at low temperatures for an intermediate metallic state wherein the Mott state is melted but the Peierls distortion remains intact, consistent with recent theoretical predictions. Finally, the observed terahertz conductivity dynamics above the photoinduced transition threshold reveal nucleation and growth of metallic nanodomains over picosecond time scales.

  9. Convergent synthesis and photoinduced processes in multi-chromophoric rotaxanes.

    PubMed

    Megiatto, Jackson D; Li, Ke; Schuster, David I; Palkar, Amit; Herranz, M Ángeles; Echegoyen, Luis; Abwandner, Silke; de Miguel, Gustavo; Guldi, Dirk M

    2010-11-18

    A series of [2]rotaxane materials, in which [60]fullerene is linked to a macrocycle and ferrocene (Fc) moieties are placed at the termini of a thread, both of which possess a central Cu(I)-1,10-phenanthroline [Cu(phen)(2)](+) complex, were synthesized by self-assembly using Sauvage metal template methodology. Two types of threads were constructed, one with terminal ester linkages, and a second with terminal 1,2,3-triazole linkages derived from Cu(I)-catalyzed "click" 1,3-cycloaddition reactions. Model compounds lacking the fullerene moiety were prepared in an analogous manner. The ability of the interlocked Fc-[Cu(phen)(2)](+)-C(60) hybrids to undergo electron transfer upon photoexcitation in benzonitrile, dichloromethane, and ortho-dichlorobenzene was investigated by means of time-resolved fluorescence and transient absorption spectroscopy, using excitation wavelengths directed at the fullerene and [Cu(phen)(2)](+) subunits. The energies of the electronic excited states and charge separated (CS) states that might be formed upon photoexcitation were determined from spectroscopic and electrochemical data. These studies showed that MLCT excited states of the copper complex in the fullerenerotaxanes were quenched by electron transfer to the fullerene in benzonitrile, resulting in charge separated states with oxidized copper and reduced fullerene moieties, (Fc)(2)-[Cu(phen)(2)](2+)-C(60)(•-). Even though electron transfer from Fc to the oxidized copper complex is predicted to be exergonic by 0.16 to 0.20 eV, no unequivocal evidence in support of such a process was obtained. The conclusion that Fc plays no role in the photoinduced processes in our systems rests on the lack of enhancement of the lifetime of the charge separated state, as measured by decay of C(60)(•-) at ∼1000 nm, since one-electron oxidized Fc is very difficult to detect spectroscopically in the 500-800 nm spectral region.

  10. Cobalt(III) tetraaza-macrocyclic complexes as efficient catalyst for photoinduced hydrogen production in water: Theoretical investigation of the electronic structure of the reduced species and mechanistic insight.

    PubMed

    Gueret, Robin; Castillo, Carmen E; Rebarz, Mateusz; Thomas, Fabrice; Hargrove, Aaron-Albert; Pécaut, Jacques; Sliwa, Michel; Fortage, Jérôme; Collomb, Marie-Noëlle

    2015-11-01

    We recently reported a very efficient homogeneous system for visible-light driven hydrogen production in water based on the cobalt(III) tetraaza-macrocyclic complex [Co(CR)Cl2](+) (1) (CR=2,12-dimethyl-3,7,11,17-tetra-azabicyclo(11.3.1)-heptadeca-1(17),2,11,13,15-pentaene) as a noble metal-free catalyst, with [Ru(II)(bpy)3](2+) (Ru) as photosensitizer and ascorbate/ascorbic acid (HA(-)/H2A) as a sacrificial electron donor and buffer (PhysChemChemPhys 2013, 15, 17544). This catalyst presents the particularity to achieve very high turnover numbers (TONs) (up to 1000) at pH 4.0 at a relative high concentration (0.1mM) generating a large amount of hydrogen and having a long term stability. A similar activity was observed for the aquo derivative [Co(III)(CR)(H2O)2](3+) (2) due to substitution of chloro ligands by water molecule in water. In this work, the geometry and electronic structures of 2 and its analog [Zn(II)(CR)Cl](+) (3) derivative containing the redox innocent Zn(II) metal ion have been investigated by DFT calculations under various oxidation states. We also further studied the photocatalytic activity of this system and evaluated the influence of varying the relative concentration of the different components on the H2-evolving activity. Turnover numbers versus catalyst (TONCat) were found to be dependent on the catalyst concentration with the highest value of 1130 obtained at 0.05 mM. Interestingly, the analogous nickel derivative, [Ni(II)(CR)Cl2] (4), when tested under the same experimental conditions was found to be fully inactive for H2 production. Nanosecond transient absorption spectroscopy measurements have revealed that the first electron-transfer steps of the photocatalytic H2-evolution mechanism with the Ru/cobalt tetraaza/HA(-)/H2A system involve a reductive quenching of the excited state of the photosensitizer by ascorbate (kq=2.5×10(7) M(-1) s(-1)) followed by an electron transfer from the reduced photosensitizer to the catalyst (ket=1.4×10(9) M

  11. Photoinduced Fusion of Lipid Bilayer Membranes.

    PubMed

    Suzuki, Yui; Nagai, Ken H; Zinchenko, Anatoly; Hamada, Tsutomu

    2017-03-14

    We have developed a novel system for photocontrol of the fusion of lipid vesicles through the use of a photosensitive surfactant containing an azobenzene moiety (AzoTAB). Real-time microscopic observations clarified a change in both the surface area and internal volume of vesicles during fusion. We also determined the optimal cholesterol concentrations and temperature for inducing fusion. The mechanism of fusion can be attributed to a change in membrane tension, which is caused by the solubilization of lipids through the isomerization of AzoTAB. We used a micropipet technique to estimate membrane tension and discuss the mechanism of fusion in terms of membrane elastic energy. The obtained results regarding this novel photoinduced fusion could lead to a better understanding of the mechanism of membrane fusion in living cells and may also see wider applications, such as in drug delivery and biomimetic material design.

  12. Photoinduced decomposition of trichloroethylene in soil components

    SciTech Connect

    Tao, T.; Yang, J.J.; Maciel, G.E.

    1999-01-01

    The photoinduced decomposition of trichloroethylene adsorbed on Ca-montmorillonite by long-wavelength UV irradiation has been studied in a quartz tube open to air or through which air or oxygen is passed. Solid-sample and liquid-solution NMR techniques were used to identify apparent products or intermediates of the photodecomposition. Dichloroacetic acid was identified as a major organic product/intermediate; substantial amounts of pentachloroethane and trichloroacetic acid were also identified. The formation of CO{sub 2} was characterized quantitatively by wet chemical analysis. About 40% and 57%, respectively, of the total carbon of trichloroethylene was converted to carbon dioxide in air and O{sub 2} environments over a period of 16 days. Phosgene and HCl were also detected. The photodecomposition of trichloroethylene adsorbed on whole soil, on Zn{sup 2+}-exchanged and Cu{sup 2+}-exchanged montmorillonites, on kaolinite, and on silica gel was also examined in less detail; qualitatively, the conversion of trichloroethylene to dichloroacetic acid in a 48-h period occurred with the following order of decreasing efficiencies: Zn{sup 2+}-montmorillonite > silica gel > kaolinite > Ca{sup 2+}-montmorillonite > whole soil > Cu{sup 2+}-montmorillonite. These results show that the photoinduced decomposition of adsorbed trichloroethylene occurs on a variety of adsorbents, generating products and intermediates that are similar to what have been reported previously for TiO{sub 2}-based photodecomposition but with much longer time scales. These conversions can, therefore, be expected to occur in sunlight at the air-soil interface.

  13. Review of the photo-induced toxicity of environmental contaminants.

    PubMed

    Roberts, Aaron P; Alloy, Matthew M; Oris, James T

    2017-01-01

    Solar radiation is a vital component of ecosystem function. However, sunlight can also interact with certain xenobiotic compounds in a phenomenon known as photo-induced, photo-enhanced, photo-activated, or photo-toxicity. This phenomenon broadly refers to an interaction between a chemical and sunlight resulting in increased toxicity. Because most aquatic ecosystems receive some amount of sunlight, co-exposure to xenobiotic chemicals and solar radiation is likely to occur in the environment, and photo-induced toxicity may be an important factor impacting aquatic ecosystems. However, photo-induced toxicity is not likely to be relevant in all aquatic systems or exposure scenarios due to variation in important ecological factors as well as physiological adaptations of the species that reside there. Here, we provide an updated review of the state of the science of photo-induced toxicity in aquatic ecosystems.

  14. Photoinduced nanocomposites—creation, modification, linear and nonlinear optical properties

    NASA Astrophysics Data System (ADS)

    Bityurin, N.; Alexandrov, A.; Afanasiev, A.; Agareva, N.; Pikulin, A.; Sapogova, N.; Soustov, L.; Salomatina, E.; Gorshkova, E.; Tsverova, N.; Smirnova, L.

    2013-07-01

    UV irradiation of materials consisting of a polymer matrix that possesses precursors of noble metals followed by annealing results in creation of metal nanoparticles within the irradiated domains. Such photoinduced nanocomposites are promising for photonics applications due to the strong alteration of their optical properties compared to initial nonirradiated materials. We report our results on the synthesis and investigation of two kinds of these materials: (a) Photoinduced Au nanocomposites based on PMMA matrices, including bulk materials prepared by means of the polymerization technique;

  15. Photoinduced electro-optics measurements of biosilica transformation to cristobalite

    SciTech Connect

    Fuchs, Ido; Aluma, Yaniv; Ilan, Micha; Kityk, Iwan; Mastai, Yitzhak

    2015-03-15

    In this paper we studied the photoinduced electro optics effects in the thermal transformation process of biosilica to cristobalite, at a relatively low temperature and ambient pressure. This process was characterized by a variety of standards techniques with emphasis on linear electro optic effect measurements. Overall we demonstrated that photoinduced electro optics measurements are very sensitive to the transformation from amorphous structure of silica in the natural sponge samples to laminar string morphology of cristobalite. With this technique we could probe the change in the samples chirality from achiral bio silica to chiral cristobalite structure. Furthermore it is shown that natural biosilica have photoinduced linear electro optics respond indicating the chiral natural of biosilica. - Graphical abstract: The phase transformation of biosilica from marine sponges to Cristobalite under thermal treatment was investigated using photoinduced electro optics measurements. The figure shows the changes of the electro-optic coefficient of cristobalite and biosilica. - Highlights: • We examine phase transformation of biosilica. • We report transition from amorphous biosilica to crystalline Cristobalite. • Biosilica transformation to Cristobalite at temperature of 850 °C. • Biosilica transformation is studied with photoinduced measurements. • We examine changes in the photoinduced linear electro optics properties.

  16. Electric Field Dependence of Photo-Induced Field Emission Current.

    NASA Astrophysics Data System (ADS)

    Egert, Charles Michael

    We have measured the photo-induced field emission current from a tungsten field emitter as a function of electric field. These experiments were performed with a retardation energy analyzer to measure total current and a 127(DEGREES) cylindrical differential energy analyzer to measure the energy resolved PFE current. The results of these experiments are compared with a simple theory of PFE, developed by Schwartz and Schaich, which is an extension of field emission theory including the surface photoeffect, but assuming constant photoexcitation matrix elements. Our experimental results disagree with this theory in two ways: First, for high fields and photon energy (electrons emitted above the field emission barrier maximum) theory predicts a larger increase in PFE current than is observed experimentally. Second, we have also confirmed the existence of a field dependent oscillatory component of the PFE current emitted from the W(110) surface with photon energies of 2.7 eV and 3.5 eV. The simple theory described here, as well as more sophisticated calculations, have been unable to explain this oscillatory feature. We have also reported, for the first time, the field dependence of the energy resolved PFE current measured with a 127(DEGREES) cylindrical energy analyzer. These preliminary results show evidence of the oscillatory component previously only observed in the total PFE current.

  17. Highly Twisted Triarylamines for Photoinduced Intramoleculer ChargeTransfer

    SciTech Connect

    Chudomel, J. M.; Yang, B. Q.; Barnes, M. D.; Achermann, M.; Mague, J. T.; Lahti, P. M.

    2011-08-04

    9-(N,N-Dianisylamino)anthracene (9DAAA), 9-(N,N-dianisylamino)dinaphth([1,2-a:2'-1'-j]-anthracene (9DAAH), and 9,10-bis(N,N-dianisylamino)anthracene (910BAA) were synthesized as highly twisted triarylamines with potential for photoexcited internal charge transfer. Crystallography of 9DAAA shows its dianisylamino group to be twisted nearly perpendicular to its anthracene unit, similar to a report for 910BAA. The solution fluorescence spectra show strong bathochromic shifts for each of the three molecular systems with strongly decreased quantum efficiency in higher polarity solvents. Solution-phase (ensemble) time-resolved photoluminescence measurements show up to 4-fold decreases in fluorescence lifetime in acetonitrile compared to hexane. The combined results are consistent with photoinduced, transient intramolecular charge-transfer from the bis-anisylamine unit to the polycyclic aromatic unit. Computational modeling is in accord with intramolecular transfer of electron density from the bis-anisylamino unit to the anthracene, based on in comparisons of HOMO and LUMO.

  18. Tuning of photoinduced energy transfer in a bichromophoric coumarin supermolecule by cation binding

    SciTech Connect

    Valeur, B.; Pouget, J.; Bourson, J.; Kaschke, M.; Ernsting, N.P.

    1992-08-06

    This paper discussed tuning of photoinduced electronic energy transfer in two coumarins linked by a pentakis (ethylene oxide) spacer by Pb{sup 2+} binding in acetonitrile and propylene carbonate. The ligand:metal ratio is observed to be 1:1 in acetonitrile with a significant increase in efficiency and rate of energy transfer as compared to propylene carbonate, which has a ratio of 1:3. This may be due to a different complex structure in the two solvents. 12 refs., 10 figs., 1 tab.

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

    PubMed

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

    2013-04-21

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

  20. Primary ultrafast events preceding the photoinduced proton transfer from pyranine to water

    NASA Astrophysics Data System (ADS)

    Tran-Thi, T.-H.; Gustavsson, T.; Prayer, C.; Pommeret, S.; Hynes, James T.

    2000-10-01

    Femtosecond fluorescence and absorption spectroscopies are used to probe the early events of the photoinduced proton transfer (PT) from pyranine to water. The process is found to involve two ultrafast steps (300 fs and 2.5 ps) which precede the relatively slow (87 ps) PT step. From the comparative study of the properties of the excited acid and its conjugate anion in various aqueous and alcoholic media, these ultrafast steps are identified as the solvation dynamics of the locally excited (LE) state of the acid and its subsequent relaxation to an intermediate electronic state, whose nature is discussed.

  1. Photoinduced Reconfiguration Cycle in a Molecular Adsorbate Layer Studied by Femtosecond Inner-Shell Photoelectron Spectroscopy

    SciTech Connect

    Dachraoui, H.; Michelswirth, M.; Bartz, P.; Pfeiffer, W.; Heinzmann, U.; Siffalovic, P.; Schaefer, C.; Schnatwinkel, B.; Mattay, J.; Drescher, M.

    2011-03-11

    A time-resolved study of core-level chemical shifts in a monolayer of aromatic molecules reveals complex photoinduced reaction dynamics. The combination of electron spectroscopy for chemical analysis and ultrashort pulse excitation in the extreme ultraviolet allows performing time-correlated 4d-core-level spectroscopy of iodine atoms that probe the local chemical environment in the adsorbate molecule. The selectivity of the method unveils metastable molecular configurations that appear about 50 ps after the excitation and are efficiently quenched back to the ground state.

  2. Fourier transform infrared spectrum of the radical cation of beta-carotene photoinduced in photosystem II.

    PubMed

    Noguchi, T; Mitsuka, T; Inoue, Y

    1994-12-19

    A Fourier-transform infrared (FTIR) spectrum of the radical cation of beta-carotene photoinduced in photosystem II (PSII) membranes was obtained at 80K under oxidizing conditions, by utilizing the light-induced FTIR difference technique. Formation of the beta-carotene cation was monitored with the electronic absorption band at 993 nm. An FTIR spectrum of a chemically-generated beta-carotene cation in chloroform was also measured and compared with the spectrum of PSII. Since the FTIR bands of carotenoid cation have characteristic features with strong intensities, they can be useful markers in studying the reaction of carotenoid in PSII.

  3. Model of photo-induced neutral-ionic phase transition in organic charge-transfer salts

    NASA Astrophysics Data System (ADS)

    Yartsev, V. M.

    1998-01-01

    One-dimensional donor-acceptor mixed chains are modeled by a periodic DADA tetramer. Electron coupling to intramolecular vibrations are taken into account explicitly. Generalized adiabatic potentials are calculated for the cases of regular and dimerized stacks which are characteristic, respectively, of quasi-neutral (N) and quasi-ionic (I) phases of a tetrathiafulvalene-chloranil compound. A sharp difference in life-times of photo-induced I-states in the N-phase and N-states in the I-phase is discussed within the periodic DADA tetramer model.

  4. Photoinduced cytotoxicity by a platinum diimine complex employing magnetite-silica nanocomposites as delivery vehicles.

    PubMed

    Zhang, Zhigang; Li, Haisha; Dai, Ruihui; Chai, Aiyun

    2015-10-01

    Tartaric acid-modified core-shell magnetite-silica nanocomposites were prepared by a sol-gel method, and characterized by X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy and dynamic light scattering. Then the nanocomposites were employed as carriers of a photoactive platinum diimine complex. Photoinduced cytotoxicity by the photosensitizer-loaded nanocomposites in different human carcinoma cells has been studied by cell viability assay. The results suggest that the as-synthesized nanocomposites have good stability in water, and the cytotoxicity induced by the platinum diimine complex in red light can be significantly enhanced when the photosensitizer is loaded with the magnetic nanocomposites.

  5. POLARON DYNAMICS. Long-lived photoinduced polaron formation in conjugated polyelectrolyte-fullerene assemblies.

    PubMed

    Huber, Rachel C; Ferreira, Amy S; Thompson, Robert; Kilbride, Daniel; Knutson, Nicholas S; Devi, Lekshmi Sudha; Toso, Daniel B; Challa, J Reddy; Zhou, Z Hong; Rubin, Yves; Schwartz, Benjamin J; Tolbert, Sarah H

    2015-06-19

    The efficiency of biological photosynthesis results from the exquisite organization of photoactive elements that promote rapid movement of charge carriers out of a critical recombination range. If synthetic organic photovoltaic materials could mimic this assembly, charge separation and collection could be markedly enhanced. We show that micelle-forming cationic semiconducting polymers can coassemble in water with cationic fullerene derivatives to create photoinduced electron-transfer cascades that lead to exceptionally long-lived polarons. The stability of the polarons depends on the organization of the polymer-fullerene assembly. Properly designed assemblies can produce separated polaronic charges that are stable for days or weeks in aqueous solution.

  6. Photoinduced intramolecular charge transfer process of betaine pyridinium: A theoretical spectroscopic study

    NASA Astrophysics Data System (ADS)

    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.

  7. Photo-induced conductance fluctuations in mesoscopic Ge/Si systems with quantum dots

    SciTech Connect

    Stepina, N. P.; Dvurechenskii, A. V.; Nikiforov, A. I.; Moers, J.; Gruetzmacher, D.

    2014-08-20

    We study the evolution of electron transport in strongly localized mesoscopic system with quantum dots under small photon flux. Exploring devices with narrow transport channels lead to the observation of giant fluctuations of the photoconductance, which is attributed to the strong dependence of hopping current on the filling of dots by holes. In our experiments, single-photon mode operation is indicated by the linear dependence of the frequency of photo-induced fluctuations on the light intensity and the step-like response of conductance on the pulse excitation. The effect of the light wavelength, measurement temperature, size of the conductive channel on the device efficiency are considered.

  8. Photoinduced adsorption of hydrogen and methane on gamma-alumina. the photoinduced chesorluminescence (PhICL) effect.

    PubMed

    Andreev, N S; Emeline, A V; Polikhova, S V; Ryabchuk, V K; Serpone, N

    2004-01-06

    Adsorption of hydrogen and methane on a preirradiated surface of gamma-Al2O3 produces an afterglow, which has been described as a photoinduced chesorluminescence (PhICL), whose spectral features identify with the intrinsic photoluminescence of alumina. The emission spectrum consists of at least four overlapping single emission bands. For methane adsorption, the PhICL phenomenon is seen only if the solid is preirradiated in the presence of oxygen. Emission decay kinetics of the PhICL effect for gamma-Al2O3 reveal two wavelength regimes: a short wavelength regime at lambda = 300-370 nm (decay time tau = 1.1 +/- 0.2 s; signal width = 2.8 s), and a longer wavelength regime at lambda = 380-700 nm (decay time tau = 2.1 +/- 0.1 s; signal width = 4.3 s). A model is proposed in which there exist two different emission centers and, thus, two different pathways for emission decay. In the first, emission originates with electron trapping by such deep energy traps as anion vacancies {e- + Va --> F+ + hv1} to yield electron F-type color centers, whereas in the second, emission originates from electron/trapped hole recombination {e- + Os*- --> Os2- + hv2}. The first common step of the pathways is homolytic dissociative chemisorption of hydrogen and methane upon interaction with surface-active hole centers Os*-, produced upon preirradiation of alumina, to give atomic hydrogen H* and methyl radicals CH3*. Thermoprogrammed desorption spectra of photoadsorbed or postsorbed oxygen show that adsorbed oxygen interacts with atomic hydrogen and methyl radicals. The products of thermodesorption were H2O for hydrogen and H2O, CO2, and CH3CH3 for methane. The Solonitsyn memory effect coefficient was also evaluated for oxygen photoadsorption.

  9. Tailored heterojunctions for efficient thin-film organic solar cells: a photoinduced absorption study

    NASA Astrophysics Data System (ADS)

    Schueppel, R.; Schmidt, K.; Uhrich, C.; Schulze, K.; Wynands, D.; Brédas, J. L.; Maennig, B.; Pfeiffer, M.; Leo, K.; Brier, E.; Reinold, E.; Bu, H.-B.; Baeuerle, P.

    2007-09-01

    Recently, we have demonstrated an open circuit voltage of 1.0V and a power conversion efficiency of 3.4% in thin film solar cells, utilizing a new acceptor-substituted oligothiophene with an optical gap of 1.77 eV as donor and C 60 as acceptor. Stimulated by this result, we systematically study the energy and electron transfer processes taking place at the oligothiophene:fullerene heterojunction along a homologous series of these oligothiophenes. The heterojunction is modified by tuning the HOMO level using different oligothiophene chain lengths, while the LUMO level is essentially fixed by the choice of the acceptor-type end-groups (dicyanovinyl) attached to the oligothiophene. We study electron transfer at the heterojunction to C 60 using photoinduced absorption. The observed transitions are unambiguously identified by TD-DFT calculations. With increasing the effective energy gap of the donor-acceptor pair, charge carrier dissociation following the photoinduced electron transfer is eventually replaced by recombination into the triplet state, which alters the photovoltaic operation conditions. Therefore, the optimum open-circuit voltage of a solar cell is a trade-off between an efficient charge separation at the interface and a maximized effective gap. We conclude that values between 1.0 and 1.1 V for the open-circuit voltage in our solar cell devices present an optimum, as higher voltages were only achieved with concomitant losses in charge separation efficiency.

  10. Ultrafast dynamics during the photoinduced phase transition in VO2

    NASA Astrophysics Data System (ADS)

    Wegkamp, Daniel; Stähler, Julia

    2015-12-01

    The phase transition of VO2 from a monoclinic insulator to a rutile metal, which occurs thermally at TC = 340 K, can also be driven by strong photoexcitation. The ultrafast dynamics during this photoinduced phase transition (PIPT) have attracted great scientific attention for decades, as this approach promises to answer the question of whether the insulator-to-metal (IMT) transition is caused by electronic or crystallographic processes through disentanglement of the different contributions in the time domain. We review our recent results achieved by femtosecond time-resolved photoelectron, optical, and coherent phonon spectroscopy and discuss them within the framework of a selection of latest, complementary studies of the ultrafast PIPT in VO2. We show that the population change of electrons and holes caused by photoexcitation launches a highly non-equilibrium plasma phase characterized by enhanced screening due to quasi-free carriers and followed by two branches of non-equilibrium dynamics: (i) an instantaneous (within the time resolution) collapse of the insulating gap that precedes charge carrier relaxation and significant ionic motion and (ii) an instantaneous lattice potential symmetry change that represents the onset of the crystallographic phase transition through ionic motion on longer timescales. We discuss the interconnection between these two non-thermal pathways with particular focus on the meaning of the critical fluence of the PIPT in different types of experiments. Based on this, we conclude that the PIPT threshold identified in optical experiments is most probably determined by the excitation density required to drive the lattice potential change rather than the IMT. These considerations suggest that the IMT can be driven by weaker excitation, predicting a transiently metallic, monoclinic state of VO2 that is not stabilized by the non-thermal structural transition and, thus, decays on ultrafast timescales.

  11. Native vs photoinduced chemiluminescence in dimethoate determination.

    PubMed

    Catalá-Icardo, M; López-Paz, J L; Choves-Barón, C; Peña-Bádena, A

    2012-01-13

    The determination of dimethoate using either its native chemiluminescent (CL) properties or its photoinduced chemiluminescence obtained by irradiation with a 15 W low-pressure mercury lamp was studied. Thereby, two flow injection systems (FIA) with and without irradiation were exhaustively optimized and their analytical characteristics studied. Better sensitivity and selectivity was found in absence of irradiation, due to the enhancing effect of hexadecylpyridinium chloride (HPC), which acted as a sensitizer. In the developed FIA-CL system, the alkaline hydrolysis of dimethoate with NaOH was performed on-line in presence of HPC. The oxidation of the product of hydrolysis with Ce(IV) in hydrochloric medium induced chemiluminescence. The method provided a limit of detection of only 0.05 ng mL(-1) without any pre-treatment. However, the combination with solid phase extraction allowed the removal of some potential interferents as well as the preconcentration of the pesticide. Finally, the developed method was successfully applied to natural waters with recoveries between 95 and 108%.

  12. Photoinduced chemiluminescence determination of carbamate pesticides.

    PubMed

    Catalá-Icardo, M; Meseguer-Lloret, S; Torres-Cartas, S

    2016-05-11

    A liquid chromatography method with post-column photoinduced chemiluminescence (PICL) detection is proposed for the simultaneous determination of eight carbamate pesticides, namely aldicarb, butocarboxim, ethiofencarb, methomyl, methiocarb, thiodicarb, thiofanox and thiophanate-methyl. After chromatographic separation, quinine (sensitizer) was incorporated and the flow passed through an UV lamp (67 s of irradiation time) to obtain the photoproducts, which reacted with acidic Ce(iv) and provided a CL emission. The PICL method showed great selectivity for carbamate pesticides containing sulphur in their chemical structure. A solid-phase extraction process increased sensitivity (LODs ranging from 0.06 to 0.27 ng mL(-1)) and allowed the carbamate pesticides in surface and ground water samples to be determined, with recoveries in the range 87-110% (except for thiophanate-methyl, whose recoveries were between 60 and 75%). The intra- and inter-day precision was evaluated, with RSD ranging from 1.1 to 7.5% and from 2.6 to 12.3%, respectively. A discussion about the PICL mechanism is also included.

  13. Linear and Nonlinear Optical Spectroscopy at the Nanoscale with Photoinduced Force Microscopy.

    PubMed

    Jahng, Junghoon; Fishman, Dmitry A; Park, Sung; Nowak, Derek B; Morrison, Will A; Wickramasinghe, H Kumar; Potma, Eric O

    2015-10-20

    The enormous advances made in nanotechnology have also intensified the need for tools that can characterize newly synthesized nanoaterials with high sensitivity and with high spatial resolution. Many existing tools with nanoscopic resolution or better, including scanning electron microscopy (SEM), atomic force microscopy (AFM), and scanning tunneling microscopy (STM) methods, can generate highly detailed maps of nanoscopic structures. However, while these approaches provide great views of the morphological properties of nanomaterials, it has proven more challenging to derive chemical information from the corresponding images. To address this issue, attempts have been made to dress existing nanoscopy methods with spectroscopic sensitivity. A powerful approach in this direction is the combination of scan probe techniques with optical illumination, which aims to marry the nanoscopic resolution provided by a sharp tip with the chemical selectivity provided by optical spectroscopy. Examples of this approach include existing techniques such as scattering-type scanning near-field optical microscopy and tip-enhanced Raman spectroscopy. A new and emerging technique in this direction is photoinduced force microscopy (PiFM), which enables spectroscopic probing of materials with a spatial resolution well under 10 nm. In PiFM, the sample is optically excited and the response of the material is probed directly in the near-field by reading out the time-integrated force between the tip and the sample. Because the magnitude of the force is dependent on the photoinduced polarization in the sample, PiFM exhibits spectroscopic sensitivity. The photoinduced forces measured in PiFM are spatially confined on the nanometer scale, which translates into a very high spatial resolution even under ambient conditions. The PiFM approach is compatible with a wide range optical excitation frequencies, from the visible to the mid-infrared, enabling nanoscale imaging contrast based on either

  14. Perovskites for Photovoltaics in the Spotlight: Photoinduced Physical Changes and Their Implications.

    PubMed

    Gottesman, Ronen; Zaban, Arie

    2016-02-16

    Organic-inorganic halide perovskites are in consensus to revolutionize the field of photovoltaics and optoelectronic devices due to their superior optical and electronic properties which are unprecedented in comparison to those of other solution processed semiconductors. These hybrid materials are used as light absorbers and also as charge carriers which makes them very versatile to be implemented and studied in a multitude of fields. Traditionally, the working paradigm in solar cells and optoelectronic devices' characterization has been that the properties of photovoltaic materials remain stable following illumination of varying times and intensities. However, recently there has been a growing number of reports on prolonged illumination-dependent physical changes in perovskite films and perovskite based devices. The changes are reversible and range from structural transformations and differences in optical characteristics, to an increase in optoelectronic properties and physical parameters. In this Account, we review the physical changes in three reported model systems which display changes under prolonged illumination of light intensities of ∼0.01-1 sun. The three systems are (i) a free-standing perovskite film on a glass substrate, (ii) a symmetrical system with nonselective electrical contacts, and (iii) a working perovskite solar cell (either a planar or a porous structure). We examine each model system and discuss its photoinduced physical changes and conclude with the implications on future experimentation design, data analysis, and characterization that involve organic-inorganic halide perovskites illumination. Since hybrid perovskites are considered to be mixed ionic-electronic conductors in nature, ions that migrate in the perovskite under electrical fields can influence its properties. Therefore, an important distinction is made between photoinduced effects and photo and electric field induced effects. Thus, photoinduced effects are designated as

  15. Photoinduced electro-optics measurements of biosilica transformation to cristobalite

    NASA Astrophysics Data System (ADS)

    Fuchs, Ido; Aluma, Yaniv; Ilan, Micha; Kityk, Iwan; Mastai, Yitzhak

    2015-03-01

    In this paper we studied the photoinduced electro optics effects in the thermal transformation process of biosilica to cristobalite, at a relatively low temperature and ambient pressure. This process was characterized by a variety of standards techniques with emphasis on linear electro optic effect measurements. Overall we demonstrated that photoinduced electro optics measurements are very sensitive to the transformation from amorphous structure of silica in the natural sponge samples to laminar string morphology of cristobalite. With this technique we could probe the change in the samples chirality from achiral bio silica to chiral cristobalite structure. Furthermore it is shown that natural biosilica have photoinduced linear electro optics respond indicating the chiral natural of biosilica.

  16. Photoinduced structural changes to protein kinase A

    NASA Astrophysics Data System (ADS)

    Rozinek, Sarah C.; Thomas, Robert J.; Brancaleon, Lorenzo

    2014-03-01

    The importance of porphyrins in organisms is underscored by the ubiquitous biological and biochemical functions that are mediated by these compounds and by their potential biomedical and biotechnological applications. Protoporphyrin IX (PPIX) is the precursor to heme and has biomedical applications such as its use as a photosensitizer in phototherapy and photodetection of cancer. Among other applications, our group has demonstrated that low-irradiance exposure to laser irradiation of PPIX, Fe-PPIX, or meso-tetrakis (4-sulfonatophenyl) porphyrin (TSPP) non-covalently docked to a protein causes conformational changes in the polypeptide. Such approach can have remarkable consequences in the study of protein structure/function relationship and can be used to prompt non-native protein properties. Therefore we have investigated protein kinase A (PKA), a more relevant protein model towards the photo-treatment of cancer. PKA's enzymatic functions are regulated by the presence of cyclic adenosine monophosphate for intracellular signal transduction involved in, among other things, stimulation of transcription, tumorigenesis in Carney complex and migration of breast carcinoma cells. Since phosphorylation is a necessary step in some cancers and inflammatory diseases, inhibiting the protein kinase, and therefore phosphorylation, may serve to treat these diseases. Changes in absorption, steady-state fluorescence, and fluorescence lifetime indicate: 1) both TSPP and PPIX non-covalently bind to PKA where they maintain photoreactivity; 2) absorptive photoproduct formation occurs only when PKA is bound to TSPP and irradiated; and 3) PKA undergoes secondary structural changes after irradiation with either porphyrin bound. These photoinduced changes could affect the protein's enzymatic and signaling capabilities.

  17. Enhanced emission and photoconductivity due to photo-induced charge transfer from Au nanoislands to ZnO

    SciTech Connect

    Wu, Shang-Hsuan; Chan, Ching-Hsiang; Liang, Ching-Tarng; Chien, Ching-Hang; Yaseen, Mohammad Tariq; Chang, Yia-Chung

    2016-01-25

    We report systematic studies based on photoluminescence, Hall, and photoconductivity measurements together with theoretical modeling in order to identify mechanisms for the photo-induced charge transfer effects in ZnO thin film incorporated with the Au nano-islands (AuNIs). Significant enhancement of near band edge emission and improvement in conductivity of ZnO/AuNIs samples after illumination are observed, which are attributed to the photo-induced hot electrons in Au which are then transferred into the conduction band of ZnO as long as the excitation energy is higher than the offset between the ZnO conduction-band minimum and Au Fermi level. Our experimental results are consistent with the general features predicted by first principles calculations.

  18. Photo-induced chaos in the Briggs-Rauscher reaction

    NASA Astrophysics Data System (ADS)

    Okazaki, Noriaki; Hanazaki, Ichiro

    1998-07-01

    Discovery of the photo-induced chaos in the Briggs-Rauscher system is reported. The chaotic oscillations were observed between the large- and the small-amplitude simple oscillatory states existent in low and high light intensity regions, respectively. Period-doubling sequence from the large-amplitude oscillations to the chaos was observed. Deterministic nature of the chaos was confirmed by the next-amplitude return map. The stretching and folding mechanism of the trajectories was revealed through the three-dimensional attractor reconstructed via the singular value decomposition method. The chemical origin of the photoinduced chaos is discussed based on the photoautocatalysis of HIO2.

  19. Quantitative analysis of sideband coupling in photoinduced force microscopy

    NASA Astrophysics Data System (ADS)

    Jahng, Junghoon; Kim, Bongsu; Lee, Eun Seong; Potma, Eric Olaf

    2016-11-01

    We present a theoretical and experimental analysis of the cantilever motions detected in photoinduced force microscopy (PiFM) using the sideband coupling detection scheme. In sideband coupling, the cantilever dynamics are probed at a combination frequency of a fundamental mechanical eigenmode and the modulation frequency of the laser beam. Using this detection mode, we develop a method for reconstructing the modulated photoinduced force gradient from experimental parameters in a quantitative manner. We show evidence, both theoretically and experimentally, that the sideband coupling detection mode provides PiFM images with superior contrast compared to images obtained when detecting the cantilever motions directly at the laser modulation frequency.

  20. Photoinduced axial ligation and deligation dynamics of nonplanar nickel dodecaarylporphyrins.

    PubMed

    Retsek, Jennifer L; Drain, Charles Michael; Kirmaier, Christine; Nurco, Daniel J; Medforth, Craig J; Smith, Kevin M; Sazanovich, Igor V; Chirvony, Vladimir S; Fajer, Jack; Holten, Dewey

    2003-08-13

    The ground- and excited-state metal-ligand dynamics of nonplanar nickel(II) 2,3,5,7,8,10,12,13,15,17,18,20-dodecaphenylporphyrin (NiDPP) and two fluorinated analogues (NiF(20)DPP and NiF(28)DPP) have been investigated using static and time-resolved absorption spectroscopy in toluene and in ligating media that differ in basicity, aromaticity, and steric encumbrance. Because of the electronic and steric consequences of nonplanarity, NiDPP does not bind axial ligands in the ground state, but metal coordination does occur after photoexcitation with multistep dynamics that depend on the properties of the ligand. Following the structural relaxations that occur in all nickel porphyrins within approximately 10 ps, ligand binding to photoexcited NiDPP is progressively longer in pyridine, piperidine, and 3,5-lutidine (25-100 ps) but does not occur at all in 2,6-lutidine in which the ligating nitrogen is sterically encumbered. The transient intermediate that is formed, which nominally could be either a five- or six-coordinate species, also has a ligand-dependent lifetime (200-550 ps). Decay of this intermediate occurs partially via ligand release to re-form the uncoordinated species, in competition with binding of the second axial ligand and/or conformational/electronic relaxations (of a six-coordinate intermediate) to give the ground state of the bis-ligated photoproduct. The finding that the photoproduct channel principally depends on ligand characteristics along with the time-evolving spectra suggests that the transient intermediate may involve a five-coordinate species. In contrast to NiDPP, the fluorinated analogues NiF(20)DPP and NiF(28)DPP do coordinate axial ligands in the ground state but eject them after photoexcitation. Collectively, these results demonstrate the sensitivity with which the electronic and structural characteristics of the macrocycle, substituents, and solvent (ligands) can govern the photophysical and photochemical properties of nonplanar porphyrins

  1. Measurements of Photo-induced Changes in Conjugated Polymers

    DOE R&D Accomplishments Database

    Seager, C. H.; Sinclair, M. B.; Mc Branch, D.; Heeger, A. J.; Baker, G. L.

    1991-01-01

    We have used the highly sensitive technique of Photothermal Deflection Spectroscopy (PDS) to measure changes in the infrared absorption spectra of MEHPPV, P3HT and Polydiacetylene-4BCMU induced by pumping these polymers with light above the {pi} - {pi}* transition energy. In contrast to previous chopped light transmission measurements of these effects, the PDS technique can directly measure the buildup or decay of the absorption coefficient, {alpha}, on the time scale of second to days. In the case of MEHPPV we observe that the time scale of seconds to days. In the case of MEHPPV we observe that above-gap light causes the appearance of a broad infrared peak in {alpha}, which continues to grow-in hours after the pump light is first applied. For this polymer the general shape of the absorption spectra in the unpumped state mimics the photo-induced changes, suggesting that remnant photo-induced states determine the maximum transparency observed under normal experimental conditions. For P3HT and to a lesser extent, MEHPPV, we also observe irreversible photo-induced absorption components which we tentatively identify with photo-induced oxidation of the polymer matrix.

  2. Photoinduced fluorescence enhancement in CdSe /ZnS quantum dot monolayers: Influence of substrate

    NASA Astrophysics Data System (ADS)

    Uematsu, Takafumi; Maenosono, Shinya; Yamaguchi, Yukio

    2006-07-01

    Photoinduced fluorescence enhancement (PFE) of CdSe /ZnS core/shell quantum dot (QD) films on SiOx substrates was investigated. The fluorescence intensity of the QD film on SiO1.9 was greatly enhanced by continuous irradiation in vacuum, while the same QD film on SiO0.6 showed a small enhancement of the fluorescence intensity. After irradiation, the rate of fluorescence decay of the QD film on SiO0.6 was smaller than that of the QD film on SiO1.9. Our results suggest that the origin of PFE derives from the photoejection of electrons into the substrate, and that the oxygen-excess-related defects work as trap sites for the electrons.

  3. Photo-induced halide redistribution in organic–inorganic perovskite films

    DOE PAGES

    deQuilettes, Dane W.; Zhang, Wei; Burlakov, Victor M.; ...

    2016-05-24

    Organic-inorganic perovskites such as CH3NH3PbI3 are promising materials for a variety of optoelectronic applications, with certified power conversion efficiencies in solar cells already exceeding 21%. Nevertheless, state-of-the-art films still contain performance-limiting non-radiative recombination sites and exhibit a range of complex dynamic phenomena under illumination that remain poorly understood. Here we use a unique combination of confocal photoluminescence (PL) microscopy and chemical imaging to correlate the local changes in photophysics with composition in CH3NH3PbI3 films under illumination. We demonstrate that the photo-induced 'brightening' of the perovskite PL can be attributed to an order-of-magnitude reduction in trap state density. By imaging themore » same regions with time-of-flight secondary-ion-mass spectrometry, we correlate this photobrightening with a net migration of iodine. In conclusion, our work provides visual evidence for photo-induced halide migration in triiodide perovskites and reveals the complex interplay between charge carrier populations, electronic traps and mobile halides that collectively impact optoelectronic performance.« less

  4. Photo-induced halide redistribution in organic-inorganic perovskite films

    NASA Astrophysics Data System (ADS)

    Dequilettes, Dane W.; Zhang, Wei; Burlakov, Victor M.; Graham, Daniel J.; Leijtens, Tomas; Osherov, Anna; Bulović, Vladimir; Snaith, Henry J.; Ginger, David S.; Stranks, Samuel D.

    2016-05-01

    Organic-inorganic perovskites such as CH3NH3PbI3 are promising materials for a variety of optoelectronic applications, with certified power conversion efficiencies in solar cells already exceeding 21%. Nevertheless, state-of-the-art films still contain performance-limiting non-radiative recombination sites and exhibit a range of complex dynamic phenomena under illumination that remain poorly understood. Here we use a unique combination of confocal photoluminescence (PL) microscopy and chemical imaging to correlate the local changes in photophysics with composition in CH3NH3PbI3 films under illumination. We demonstrate that the photo-induced `brightening' of the perovskite PL can be attributed to an order-of-magnitude reduction in trap state density. By imaging the same regions with time-of-flight secondary-ion-mass spectrometry, we correlate this photobrightening with a net migration of iodine. Our work provides visual evidence for photo-induced halide migration in triiodide perovskites and reveals the complex interplay between charge carrier populations, electronic traps and mobile halides that collectively impact optoelectronic performance.

  5. Photo-induced halide redistribution in organic–inorganic perovskite films

    SciTech Connect

    deQuilettes, Dane W.; Zhang, Wei; Burlakov, Victor M.; Graham, Daniel J.; Leijtens, Tomas; Osherov, Anna; Bulovic, Vladimir; Snaith, Henry J.; Ginger, David S.; Stranks, Samuel D.

    2016-05-24

    Organic-inorganic perovskites such as CH3NH3PbI3 are promising materials for a variety of optoelectronic applications, with certified power conversion efficiencies in solar cells already exceeding 21%. Nevertheless, state-of-the-art films still contain performance-limiting non-radiative recombination sites and exhibit a range of complex dynamic phenomena under illumination that remain poorly understood. Here we use a unique combination of confocal photoluminescence (PL) microscopy and chemical imaging to correlate the local changes in photophysics with composition in CH3NH3PbI3 films under illumination. We demonstrate that the photo-induced 'brightening' of the perovskite PL can be attributed to an order-of-magnitude reduction in trap state density. By imaging the same regions with time-of-flight secondary-ion-mass spectrometry, we correlate this photobrightening with a net migration of iodine. In conclusion, our work provides visual evidence for photo-induced halide migration in triiodide perovskites and reveals the complex interplay between charge carrier populations, electronic traps and mobile halides that collectively impact optoelectronic performance.

  6. Photo-induced halide redistribution in organic–inorganic perovskite films

    PubMed Central

    deQuilettes, Dane W.; Zhang, Wei; Burlakov, Victor M.; Graham, Daniel J.; Leijtens, Tomas; Osherov, Anna; Bulović, Vladimir; Snaith, Henry J.; Ginger, David S.; Stranks, Samuel D.

    2016-01-01

    Organic–inorganic perovskites such as CH3NH3PbI3 are promising materials for a variety of optoelectronic applications, with certified power conversion efficiencies in solar cells already exceeding 21%. Nevertheless, state-of-the-art films still contain performance-limiting non-radiative recombination sites and exhibit a range of complex dynamic phenomena under illumination that remain poorly understood. Here we use a unique combination of confocal photoluminescence (PL) microscopy and chemical imaging to correlate the local changes in photophysics with composition in CH3NH3PbI3 films under illumination. We demonstrate that the photo-induced ‘brightening' of the perovskite PL can be attributed to an order-of-magnitude reduction in trap state density. By imaging the same regions with time-of-flight secondary-ion-mass spectrometry, we correlate this photobrightening with a net migration of iodine. Our work provides visual evidence for photo-induced halide migration in triiodide perovskites and reveals the complex interplay between charge carrier populations, electronic traps and mobile halides that collectively impact optoelectronic performance. PMID:27216703

  7. Optimizing organic photovoltaics using tailored heterojunctions: A photoinduced absorption study of oligothiophenes with low band gaps

    NASA Astrophysics Data System (ADS)

    Schueppel, R.; Schmidt, K.; Uhrich, C.; Schulze, K.; Wynands, D.; Brédas, J. L.; Brier, E.; Reinold, E.; Bu, H.-B.; Baeuerle, P.; Maennig, B.; Pfeiffer, M.; Leo, K.

    2008-02-01

    A power conversion efficiency of 3.4% with an open-circuit voltage of 1V was recently demonstrated in a thin film solar cell utilizing fullerene C60 as acceptor and a new acceptor-substituted oligothiophene with an optical gap of 1.77eV as donor [K. Schulze , Adv. Mater. (Weinheim, Ger.) 18, 2872 (2006)]. This prompted us to systematically study the energy- and electron transfer processes at the oligothiophene:fullerene heterojunction for a homologous series of these oligothiophenes. Cyclic voltammetry and ultraviolet photoelectron spectroscopy data show that the heterojunction is modified due to tuning of the highest occupied molecular orbital energy for different oligothiophene chain lengths, while the lowest unoccupied molecular orbital energy remains essentially fixed due to the presence of electron-withdrawing end groups (dicyanovinyl) attached to the oligothiophene. Use of photoinduced absorption (PA) allows the study of the electron transfer process at the heterojunction to C60 . Quantum-chemical calculations performed at the density functional theory and/or time-dependent density functional theory level and cation absorption spectra of diluted DCVnT provide an unambiguous identification of the transitions observed in the PA spectra. Upon increasing the effective energy gap of the donor-acceptor pair by increasing the ionization energy of the donor, photoinduced electron transfer is eventually replaced with energy transfer, which alters the photovoltaic operation conditions. The optimum open-circuit voltage of a solar cell is thus a trade-off between efficient charge separation at the interface and maximized effective gap. It appears that the open-circuit voltages of 1.0-1.1V in our solar cell devices have reached an optimum since higher voltages result in a loss in charge separation efficiency.

  8. Photoinduced "stick-slip" on superhydrophilic semiconductor surfaces.

    PubMed

    Denison, Kieth R; Boxall, Colin

    2007-04-10

    Transparent mesoporous TiO2 (M-TiO2) thin films were prepared on quartz via a reverse micelle, sol-gel, spin-coating technique. Films were characterized by atomic force microscopy (AFM) and Raman and UV-vis spectroscopies and were found to be mostly anatase with low surface roughness (Rt approximately 5 nm). The time dependence of film photoinduced superhydrophilicity (PISH) was measured by observation of the spreading of a sessile water drop using a new, continuous measurement technique wherein the drop was first applied to the semiconductor surface and then was filmed while it and the underlying substrate were illuminated by 315 nm ultraband gap light. Results obtained at 100% relative humidity (RH) at 293 K showed that drops on M-TiO2 surfaces exhibited a photoinduced "stick-slip" behavior, the first time such an effect has been observed. The thermodynamic driving force for this photoinduced stick-slip was the departure of the system from capillary equilibrium as, with increasing illumination time, the concentration of surface Ti-OH groups increased and the equilibrium contact angle of the drop, theta0, decreased. A simple theoretical description of photoinduced stick-slip is derived and is used to calculate a value of the potential energy barrier associated with surface inhomogeneities that oppose onset of movement of the triple line, U = 6.63 x 10(-6) J m(-1). This is the first time that U has been quantified for a surface with photoinduced superhydrophilicity. Triple line retreat measurements on an evaporating drop on M-TiO2 in the dark, RH = 60%, T = 293 K, gave a value of U = 9.4 x 10(-6) J m(-1), indicating that U decreases upon UV illumination and that U in the light is primarily associated with inhomogeneities that are unaffected by an increase in the surface Ti-OH population, such as the physical roughness of the surface. In the dark evaporation experiment, the drop was found to retreat with an areal velocity of 1.48 x 10(-8) m2 s(-1). However, under UV

  9. The time of a photoinduced spin-Peierls phase transition

    SciTech Connect

    Semenov, A. L.

    2015-02-15

    The time τ of the spin-Peierls phase transition is analyzed theoretically as a function of the duration τ{sub p} of the exciting light pulse and the average number x{sub 0} of absorbed photons per magnetic ion after the transmission of the pulse. It is shown that the phase transition occurs at x{sub 0} > x{sub c}. The critical value x{sub c} is determined as a function of the duration τ{sub p} of the light pulse. A photoinduced variation in the optical reflection coefficient R is calculated as a function of time t. The results of calculation are compared with experimental data on ultrafast photoinduced melting of the low-temperature spin-Peierls phase into potassium tetracyanoquinodimethan (K-TCNQ)

  10. Heterodyne technique in photoinduced force microscopy with photothermal effect

    NASA Astrophysics Data System (ADS)

    Yamanishi, J.; Naitoh, Y.; Li, Y. J.; Sugawara, Y.

    2017-03-01

    The heterodyne technique is used to detect short-range forces. Using the heterodyne technique, we demonstrate photoinduced force microscopy (PiFM) imaging and z-spectroscopy without the artifact of photothermal vibration. The rejection ratio was at least 99.975% under a high-scattering condition. In addition, the heterodyne technique employs the optimal amplitude at the first resonance frequency of the cantilever to detect the photoinduced force sensitively. According to our calculation, the optimal ratio of the amplitude to the distance between the dipole of the tip and that of the sample is 0.4448. The heterodyne technique can be employed to perform PiFM without the artifact by using the optimal amplitude.

  11. Photoinduced translational molecular mobility in solid nanostructured azo dye films

    SciTech Connect

    Ezhov, A A; Kozenkov, V M; Magnitskii, Sergey A; Nagorskii, Nikolay M; Panov, Vladimir I

    2011-11-30

    A new mechanism controlling the molecular motion in thin azo-containing films during a photoinduced change in the surface nanorelief is found. It is shown experimentally that exposure of a solid AD-1 azo dye, deposited on a glass substrate, to incoherent linearly polarised light leads to formation of nanostructures with a characteristic size of 200 nm, which are similar to droplets of melt of this dye on the same substrate. It is shown that photoinduced mass transport in a solid AD-1 azo dye film can be explained by the mobility of molecules related to their trans-cis-photoisomerisation, which leads to film softening with subsequent formation of spherical protrusions under surface tension forces.

  12. TDDFT-MD Study on Dynamics in Photoinduced Ring Opening of Benzene

    NASA Astrophysics Data System (ADS)

    Tateyama, Yoshitaka; Miyamoto, Yoshiyuki; Oyama, Norihisa; Ohno, Takahisa

    2004-03-01

    Coupled dynamics of ions and electrons in the excited states of molecular and solid benzene is investigated on the femtosecond scale by the efficient simulation scheme recently developed for the time-dependent density functional theory. Within the π arrow π excitations, any out-of-plane motion of ions is not induced in the molecular system basically. In the solid, however, we found that large swing of the C-H bonds and subsequent twist of the carbon ring takes place, leading to sp^3-like bonding of carbon ions. This swing-to-twist motion presents a plausible mechanism underlying the photoinduced ring opening in solid benzene experimentally observed under pressure. This research is partially supported by ACT-JST, and also by FSIS and Special Coordination Funds of Ministry of Education, Culture, Sports, Science and Technology of Japanese Government.

  13. Direct and real time probe of photoinduced structure transition in colossal magnetoresistive material

    DOE PAGES

    Li, Junjie; Wang, Xuan; Zhou, Haidong; ...

    2016-07-29

    Here, we report a direct and real time measurement of photoinduced structure phase transition in single crystal La0.84Sr0.16MnO3 using femtosecond electron diffraction. The melting of orthorhombic lattice ordering under femtosecond optical excitation is found involving two distinct processes with different time scales, an initial fast melting of orthorhombic phase in about 4 ps and a subsequent slower transformation in 90 ps and longer timescales. Furthermore, the fast process is designated as the initial melting of orthorhombic phase induced by the Mn-O bond change that is most likely driven by the quenching of the dynamic Jahn-Teller distortion following the photo-excitation. Wemore » attribute the slow process to the growing of newly formed structure domain from the photo-excited sites to the neighboring non-excited orthorhombic sites.« less

  14. Surface modification of ultra high molecular weight polyethylene fibers via the sequential photoinduced graft polymerization

    NASA Astrophysics Data System (ADS)

    Li, Zhi; Zhang, Wei; Wang, Xinwei; Mai, Yongyi; Zhang, Yumei

    2011-06-01

    In this study, a sequential photoinduced graft polymerization process was proposed to improve the poor interfacial bonding property of ultra high molecular weight polyethylene (UHMWPE) fibers. The polymerization was initiated by dormant semipinacol (SP) groups and carried out in a thin liquid layer. Methacrylic acid (MAA) and acryl amide (AM) were grafted stepwise onto the surface of UHMWPE fibers. Attenuated total reflectance infrared spectroscopy (ATR-IR) and thermo gravimetric analysis (TGA) confirmed the grafting. The analysis result of pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) indicated the structure of grafted chains. Scanning electron microscopy (SEM) images and atomic force microscopy (AFM) images revealed the apparent morphology changing, and the grafted layers were observed. Interfacial shear stress (IFSS) test of the modified fibers showed an extensively improved interfacial bonding property. The active groups grafted onto the fibers would supply enough anchor points for the chemical bonding with various resins or further reactions.

  15. Direct and real time probe of photoinduced structure transition in colossal magnetoresistive material

    NASA Astrophysics Data System (ADS)

    Li, Junjie; Wang, Xuan; Zhou, Haidong; Zhou, Jun; Cheng, J. G.; Cao, Jianming

    2016-07-01

    We report a direct and real time measurement of photoinduced structure phase transition in single crystal La0.84Sr0.16MnO3 using femtosecond electron diffraction. The melting of orthorhombic lattice ordering under femtosecond optical excitation is found involving two distinct processes with different time scales, an initial fast melting of orthorhombic phase in about 4 ps and a subsequent slower transformation in 90 ps and longer timescales. The fast process is designated as the initial melting of orthorhombic phase induced by the Mn-O bond change that is most likely driven by the quenching of the dynamic Jahn-Teller distortion following the photo-excitation. The slow process is attributed to the growing of newly formed structure domain from the photo-excited sites to the neighboring non-excited orthorhombic sites.

  16. Photo-induced persistent inversion of germanium in a 200-nm-deep surface region.

    PubMed

    Prokscha, T; Chow, K H; Stilp, E; Suter, A; Luetkens, H; Morenzoni, E; Nieuwenhuys, G J; Salman, Z; Scheuermann, R

    2013-01-01

    The controlled manipulation of the charge carrier concentration in nanometer thin layers is the basis of current semiconductor technology and of fundamental importance for device applications. Here we show that it is possible to induce a persistent inversion from n- to p-type in a 200-nm-thick surface layer of a germanium wafer by illumination with white and blue light. We induce the inversion with a half-life of ~12 hours at a temperature of 220 K which disappears above 280 K. The photo-induced inversion is absent for a sample with a 20-nm-thick gold capping layer providing a Schottky barrier at the interface. This indicates that charge accumulation at the surface is essential to explain the observed inversion. The contactless change of carrier concentration is potentially interesting for device applications in opto-electronics where the gate electrode and gate oxide could be replaced by the semiconductor surface.

  17. Evidence for Photoinduced Insulator-to-Metal transition in B-phase vanadium dioxide

    PubMed Central

    Lourembam, James; Srivastava, Amar; La-o-vorakiat, Chan; Cheng, Liang; Venkatesan, T.; Chia, Elbert E. M.

    2016-01-01

    Ultrafast optical studies have been performed on epitaxial films of the novel B-phase of vanadium dioxide using temperature-dependent optical pump-probe technique. Signature of temperature-driven metal-to-insulator transition was distinctly observed in the ultrafast dynamics — the insulating phase showed two characteristic electronic relaxation times while the metallic phase showed only one. Beyond a threshold value of the pump fluence, the insulating state collapses into a ‘metallic-like’ phase which can be further subdivided into two regimes according to the lengths of the fast characteristic time. The first regime can be explained by lattice heating due to the optical pump; the other cannot be accounted by simple lattice heating effects alone, and thus offers evidence for a true photoinduced phase transition. PMID:27157532

  18. Direct and real time probe of photoinduced structure transition in colossal magnetoresistive material

    SciTech Connect

    Li, Junjie; Wang, Xuan; Zhou, Haidong; Zhou, Jun; Cheng, J. G.; Cao, Jianming

    2016-07-29

    Here, we report a direct and real time measurement of photoinduced structure phase transition in single crystal La0.84Sr0.16MnO3 using femtosecond electron diffraction. The melting of orthorhombic lattice ordering under femtosecond optical excitation is found involving two distinct processes with different time scales, an initial fast melting of orthorhombic phase in about 4 ps and a subsequent slower transformation in 90 ps and longer timescales. Furthermore, the fast process is designated as the initial melting of orthorhombic phase induced by the Mn-O bond change that is most likely driven by the quenching of the dynamic Jahn-Teller distortion following the photo-excitation. We attribute the slow process to the growing of newly formed structure domain from the photo-excited sites to the neighboring non-excited orthorhombic sites.

  19. Direct visualization of photoinduced glassy dynamics on the amorphous silicon carbide surface by STM movies

    NASA Astrophysics Data System (ADS)

    Nguyen, Duc; Nienhaus, Lea; Haasch, Richard T.; Lyding, Joseph; Gruebele, Martin

    2015-03-01

    Glassy dynamics can be controlled by light irradiation. Sub- and above-bandgap irradiation cause numerous phenomena in glasses including photorelaxation, photoexpansion, photodarkening and pohtoinduced fluidity. We used scanning tunneling microscopy to study surface glassy dynamics of amorphous silicon carbide irradiated with above- bandgap 532 nm light. Surface clusters of ~ 4-5 glass forming unit in diameter hop mostly in a two-state fashion, both without and with irradiation. Upon irradiation, the average surface hopping activity increases by a factor of 3. A very long (~1 day) movie of individual clusters with varying laser power density provides direct evidence for photoinduced enhanced hopping on the glass surfaces. We propose two mechanisms: heating and electronic for the photoenhanced surface dynamics.

  20. Modeling photoinduced fluorescence enhancement in semiconductor nanocrystal arrays

    NASA Astrophysics Data System (ADS)

    Maenosono, Shinya

    2003-07-01

    Photoinduced fluorescence enhancement (PFE) in semiconductor nanocrystal (NC) arrays is modeled based on the rate equations for ground-state, excited-state and photoionized NCs in the array. The photoionization process is broken down into fast and slow ionization processes, which are expected to relate to blinking and darkening phenomena, respectively. Consequently, PFE behavior is found to change drastically, as it depends on both the intrinsic properties of NCs, and on external conditions, such as surface-capping molecules and atmosphere.

  1. Vicinal Difluoroalkylation and Aminosulfonylation of Alkynes under Photoinduced Conditions.

    PubMed

    Xiang, Yuanchao; Li, Yuewen; Kuang, Yunyan; Wu, Jie

    2017-01-23

    A photoinduced vicinal difluoroalkylation and aminosulfonylation of alkynes under photocatalysis was realized. The combination of ethyl 2-bromo-2,2-difluoroacetate, alkynes, and DABCO⋅(SO2 )2 with hydrazines, catalyzed by 9-mes-10-methyl acridinium perchlorate in the presence of visible light, afforded (E)-ethyl 2,2-difluoro-4-aryl-4-sulfamoylbut-3-enoates in good yields with high stereoselectivity. This four-component reaction proceeds through radical addition with the insertion of sulfur dioxide.

  2. Photoinduced Dynamics and Toxicity of a Cancer Drug in Proximity of Inorganic Nanoparticles under Visible Light.

    PubMed

    Chaudhuri, Siddhi; Sardar, Samim; Bagchi, Damayanti; Dutta, Shreyasi; Debnath, Sushanta; Saha, Partha; Lemmens, Peter; Pal, Samir Kumar

    2016-01-18

    Drug sensitization with various inorganic nanoparticles (NPs) has proved to be a promising and an emergent concept in the field of nanomedicine. Rose bengal (RB), a notable photosensitizer, triggers the formation of reactive oxygen species under green-light irradiation, and consequently, it induces cytotoxicity and cell death. In the present study, the effect of photoinduced dynamics of RB upon complexation with semiconductor zinc oxide NPs is explored. To accomplish this, we successfully synthesized nanohybrids of RB with ZnO NPs with a particle size of 24 nm and optically characterized them. The uniform size and integrity of the particles were confirmed by high-resolution transmission electron microscopy. UV/Vis absorption and steady-state fluorescence studies reveal the formation of the nanohybrids. ultrafast picosecond-resolved fluorescence studies of RB-ZnO nanohybrids demonstrate an efficient electron transfer from the photoexcited drug to the semiconductor NPs. Picosecond-resolved Förster resonance energy transfer from ZnO NPs to RB unravel the proximity of the drug to the semiconductor at the molecular level. The photoinduced ROS formation was monitored using a dichlorofluorescin oxidation assay, which is a conventional oxidative stress indicator. It is observed that the ROS generation under green light illumination is greater at low concentrations of RB-ZnO nanohybrids compared with free RB. Substantial photodynamic activity of the nanohybrids in bacterial and fungal cell lines validated the in vitro toxicity results. Furthermore, the cytotoxic effect of the nanohybrids in HeLa cells, which was monitored by MTT assay, is also noteworthy.

  3. Photoinduced reduction and pattern preservation of giant surface potential on tris(8-hydroxyquinolinato) aluminum(III) thin films

    NASA Astrophysics Data System (ADS)

    Ozasa, Kazunari; Nemoto, Shigeyuki; Isoshima, Takashi; Ito, Eisuke; Maeda, Mizuo; Hara, Masahiko

    2008-12-01

    The characteristics and mechanisms of photoinduced reduction in giant surface potential (gSP) on tris(8-hydroxyquinolinato) aluminum(III) (Alq3) thin films were investigated and discussed from the results of the reduction dependences on exposure time/intensity and the preservation of photopatterned gSP. The reduction dependences are explained well with numerical-model calculation of surface potential reduction due to the drift of photoexcited carriers assuming the Poole-Frenkel formula for electron mobility. The preservation of patterned gSPs suggests the existence of deep traps involved in the carrier-drift mechanism.

  4. On the mechanism of photoinduced refractive index changes in phosphosilicate glass

    SciTech Connect

    Larionov, Yu V; Sokolov, V O; Plotnichenko, V G

    2010-05-26

    The photoinduced growth of the refractive index of phosphosilicate glass during Bragg grating inscription and the thermal decay of the grating have a number of unusual features. The observed index variations are interpreted in terms of a new model for photoinduced glass network rearrangement. The model assumes the formation of photoinduced voids (nanopores) in the glass network near point defects. The nanopores may migrate through the network via bond switching when the network is in a 'soft' state. The photoinduced variations in network density lead to index variations. (fibres)

  5. Direct characterization of photoinduced lattice dynamics in BaFe2As2.

    PubMed

    Gerber, S; Kim, K W; Zhang, Y; Zhu, D; Plonka, N; Yi, M; Dakovski, G L; Leuenberger, D; Kirchmann, P S; Moore, R G; Chollet, M; Glownia, J M; Feng, Y; Lee, J-S; Mehta, A; Kemper, A F; Wolf, T; Chuang, Y-D; Hussain, Z; Kao, C-C; Moritz, B; Shen, Z-X; Devereaux, T P; Lee, W-S

    2015-06-08

    Ultrafast light pulses can modify electronic properties of quantum materials by perturbing the underlying, intertwined degrees of freedom. In particular, iron-based superconductors exhibit a strong coupling among electronic nematic fluctuations, spins and the lattice, serving as a playground for ultrafast manipulation. Here we use time-resolved X-ray scattering to measure the lattice dynamics of photoexcited BaFe2As2. On optical excitation, no signature of an ultrafast change of the crystal symmetry is observed, but the lattice oscillates rapidly in time due to the coherent excitation of an A1g mode that modulates the Fe-As-Fe bond angle. We directly quantify the coherent lattice dynamics and show that even a small photoinduced lattice distortion can induce notable changes in the electronic and magnetic properties. Our analysis implies that transient structural modification can be an effective tool for manipulating the electronic properties of multi-orbital systems, where electronic instabilities are sensitive to the orbital character of bands.

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

    PubMed

    Dereka, Bogdan; Koch, Marius; Vauthey, Eric

    2017-02-21

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

  7. Photo-Induced Effect on Bacterial Cells

    NASA Astrophysics Data System (ADS)

    El Batanouny, M. H.; Amin, Rehab M.; Naga, M. I.; Ibrahim, M. K.

    2010-04-01

    Bacterial resistance against antibiotics is an increasing problem in medicine. This stimulates study of other bactericidal regimens, one of which is photodynamic therapy (PDT), which involves the killing of bacterial species by low power laser light (LLL) in the presence of photosensitizing agent. It has already been shown that, various gram- negative and gram-positive bacteria can be killed by photodynamic therapy in vitro, using exogenous sensitizers. The mechanisms of laser action on bacteria are not adequately understood. Here, PDT on H. pylori, as an example of gram negative bacteria was studied. The ultra structure changes of the organism after PDT were examined under electron microscope. Neither Irradiation with laser without sensitizer nor sensitizing without laser has any lethal effect on bacterial cells. However, the successful lethal photosensitization was achieved by applying certain laser dose with the corresponding concentration of the photosensitizer. On the other hand, PDT has no significant effect on the genomic DNA of the cells.

  8. Photoinduced surface reactions on TiO{sub 2} and SrTiO{sub 3} films: Photocatalytic oxidation and photoinduced hydrophilicity

    SciTech Connect

    Miyauchi, Masahiro; Nakajima, Akira; Fujishima, Akira; Hashimoto, Kazuhito; Watanabe, Toshiya

    2000-01-01

    In the present study, the authors have evaluated photocatalytic activities and photoinduced wettabilities for TiO{sub 2} and SrTiO{sub 3} films. Although both types of films had almost the same photocatalytic oxidation activity, photoinduced wettabilities of these films showed different phenomena. The photoinduced hydrophilicity peculiar to TiO{sub 2} is not caused by the photocatalytic oxidation of organic compounds adsorbed on the surface. The highly hydrophilic surface of TiO{sub 2} is ascribed to photogenerated Ti{sup 3+} defect sites that are favorable for dissociative water absorption. The yield of this photoinduced hydrophilic reaction is not clear at the present time. It is noted that this reaction involves a surface structural change, which should not require a high quantum efficiency as compared to conventional photocatalytic oxidation.

  9. Photoswitchable stable charge-distributed states in a new cobalt complex exhibiting photo-induced valence tautomerism.

    PubMed

    Slota, Michael; Blankenhorn, Marian; Heintze, Eric; Vu, Minh; Hübner, Ralph; Bogani, Lapo

    2015-01-01

    We report the synthesis and magnetic and photomagnetic behaviour of a novel valence tautomeric cobalt complex, [Co(3,5-dbbq)2(μ-bpym)] (1) (3,5-dbbq = 3,5-di-tert-butyl-1,2-benzoquinone and μ-bpym = 2,2'-bipyrimidine). The synthesis is performed by reacting Co2(CO)8 and μ-bpym in the presence of the ligand 3,5-dbbq in a mixed solvent under inert atmosphere. The magnetic behavior clearly shows the presence of electron transfer from the catecholate ligand to the cobalt center, producing valence tautomers of [Co(II)(SQ)2] with a transition temperature (T1/2) of 215 K. Photomagnetic studies, performed via both SQUID magnetometry and X-band electron paramagnetic resonance, show the clear presence of photoinduced valence tautomerism, at temperatures considerably higher than previous systems. A metastable charge distribution is observed, strengthening previous investigations on the character of mixed valence ligands. Entropy-driven valence tautomeric interconversion is observed, and drives the transition to the most stable charge distribution. The complex has the ability to coordinate and can be used as a photoswitchable building block, with the photomagnetic characterisation evidencing a metastable state lifetime of the photo-induced valence tautomeric process of ca. 2.9 × 10(4) s below 20 K. The observed yields are higher than ones in similar systems, showing that tiny changes in the molecular structures may have a huge impact.

  10. Photo-induced oxidative damage to dissolved free amino acids by the photosensitizer polycyclic musk tonalide: Transformation kinetics and mechanisms.

    PubMed

    Fang, Hansun; Gao, Yanpeng; Wang, Honghong; Yin, Hongliang; Li, Guiying; An, Taicheng

    2017-05-15

    Residue from the polycyclic musks (PCMs) in household and personal care products may harm human beings through skin exposure. To understand the health effects of PCMs when exposed to sunlight at molecular level, both experimental and computational methods were employed to investigate the photosensitized oxidation performance of 19 natural amino acids, the most basic unit of life. Results showed that a typical PCM, tonalide, acts as a photosensitizer to significantly increase photo-induced oxidative damage to amino acids. Both common and exceptional transformation pathways occurred during the photosensitization damage of amino acids. Experimental tests further identified the different mechanisms involved. The common transformation pathway occurred through the electron transfer from α amino-group of amino acids, accompanying with the formation of O2(•-). This pathway was controlled by the electronic density of N atom in α amino-group. The exceptional transformation pathway was identified only for five amino acids, mainly due to the reactions with reactive oxygen species, e.g. (1)O2 and excited triplet state molecules. Additionally, tonalide photo-induced transformation products could further accelerate the photosensitization of all amino acids with the common pathway. This study may support the protection of human health, and suggests the possible need to further restrict polycyclic musks use.

  11. Photoinduced ordering and anchoring properties of azo-dye films.

    PubMed

    Kiselev, Alexei D; Chigrinov, Vladimir; Huang, Dan Ding

    2005-12-01

    We study both theoretically and experimentally the anchoring properties of photoaligning azo-dye films in contact with a nematic liquid crystal depending on the photoinduced ordering of azo-dye molecules. In the mean field approximation, we found that the bare surface anchoring energy depends linearly on the azo-dye order parameter and the azimuthal anchoring strength decays to zero in the limit of vanishing photoinduced ordering. From the absorption dichroism spectra measured in azo-dye films that are prepared from an azo-dye derivative with polymerizable terminal groups we obtain the dependence of the dichroic ratio on the irradiation dose. We also measure the polar and azimuthal anchoring strengths in nematic liquid crystal (NLC) cells aligned by the azo-dye films and derive the anchoring strengths as functions of the dichroic ratio, which is proportional to the photoinduced order parameter. Although linear fitting of the experimental data for both anchoring strengths gives reasonable results, it, predicts vanishing of the azimuthal anchoring strength at some nonzero value of the azo-dye order parameter, in contradiction with theory. By using a simple phenomenological model we show that this discrepancy can be attributed to the difference between the surface and bulk order parameters in the films. The measured polar anchoring energy is found to be an order of magnitude higher than the azimuthal strength. Our theory suggests that the quadrupole term of the spherical harmonics expansion for the azo-dye-NLC intermolecular potential might be of importance for the understanding of this difference.

  12. Persistent photoinduced modifications in the phase-separated states of L a2 -2 xS r1 +2 xM n2O7

    NASA Astrophysics Data System (ADS)

    Sun, Kai; Sun, Shuaishuai; Li, Xingyuan; Li, Zhongwen; Zhang, Ruixin; Wei, Linlin; Guo, Cong; Zheng, Dingguo; Tian, Huanfang; Yang, Huaixin; Li, Jianqi

    2016-11-01

    Reentrant charge-ordering transition (RCOT) in the bilayered perovskite manganite L a2 -2 xS r1 +2 xM n2O7 can yield observable changes in both the structural and physical properties associated with phase separation. Our recent measurements show that laser illumination can result in persistent modifications of both the resistance and microstructure in the phase-separated (PS) states. Measurements of photoinduced effects on an x =0.6 sample reveal a persistent increase of the resistance by as much as 40%. Low-temperature laser in situ transmission electron microscope observations clearly show that in situ laser irradiation can modify the PS nature and strengthen the charge-ordered state. We attribute these photoinduced phenomena to the optical modulation of the hole concentration in the Mn O2 layers and the alteration of the local Mn orbital configurations in the PS states.

  13. Photoinduced underwater superoleophobicity of TiO2 thin films.

    PubMed

    Sawai, Yusuke; Nishimoto, Shunsuke; Kameshima, Yoshikazu; Fujii, Eiji; Miyake, Michihiro

    2013-06-11

    The photoinduced wettabilities of water, n-hexadecane, dodecane, and n-heptane on a flat TiO2 surface prepared by a sol-gel method-based coating were investigated. An amphiphilic surface produced by UV irradiation exhibited underwater superoleophobicity with an extremely high static oil contact angle (CA) of over 160°. The TiO2 surface almost completely repelled the oil droplet in water. A robust TiO2 surface with no fragile nanomicrostructure was fabricated on a Ti mesh with a pore size of approximately 150 μm. The fabricated mesh was found to be applicable as an oil/water separation filter.

  14. Photo-induced transmittance in copper selenide nanowires

    NASA Astrophysics Data System (ADS)

    Statkutė, G.; Mikulskas, I.; Jagminas, A.; Tomašiūnas, R.

    2008-01-01

    Photo-induced transmission was investigated in Cu 1.7Se nanowires electrochemically deposited in alumina matrix pores with a central channel of the diameters of 12, 15 and 60 nm by means of the degenerate picosecond pump-probe technique at 1.064 μm wavelength. Resonant excitation intensity dependencies were interpreted. Absorption saturation was ascertained as a result of the drain of acceptor shallow centers. The estimated absorption cross-section was 10 -12 cm 2, saturation intensity - was 1-10 mJ cm -2.

  15. Photoinduced switching to metallic states in the two-dimensional organic Mott insulator dimethylphenazine-tetrafluorotetracyanoquinodimethane with anisotropic molecular stacks

    NASA Astrophysics Data System (ADS)

    Matsuzaki, Hiroyuki; Ohkura, Masa-aki; Ishige, Yu; Nogami, Yoshio; Okamoto, Hiroshi

    2015-06-01

    A photoinduced phase transition was investigated in an organic charge-transfer (CT) complex M2P -TCNQ F4 , [M2P : 5,10-dihydro-5,10-dimethylphenazine, donor (D) molecule; TCNQ F4 : 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane, acceptor (A) molecule] by means of femtosecond pump-probe reflection spectroscopy. This is an ionic compound and has a peculiar two-dimensional (2D) molecular arrangement; the same A (or D) molecules arrange along the [100] direction, and A and D molecules alternately arrange along the [111] direction. It results in a strongly anisotropic two-dimensional electronic structure. This compound shows a structural and magnetic phase transition at 122 K below which the two neighboring molecules are dimerized along both the [100] and [111] directions. We demonstrate that two kinds of photoinduced phase transitions occur by irradiation of a femtosecond laser pulse; in the high-temperature lattice-uniform phase, a quasi-one-dimensional (1D) metallic state along the AA(DD) stack is generated, and in the low-temperature lattice-dimerized phase, a quasi-2D metallic state is initially produced and molecular dimerizations are subsequently released. Mixed-stack CT compounds consisting of DA stacks are generally insulators or semiconductors in the ground state. Here, such a dynamical metallization in the DA stack is demonstrated. The release of the dimerizations drives several kinds of coherent oscillations which play an important role in the stabilization of the lattice-dimerized phase. The mechanisms of those photoinduced phase transitions are discussed in terms of the magnitudes of the anisotropic bandwidths and molecular dimerizations along two different directions of the molecular stacks.

  16. Time-domain ab initio modeling of photoinduced dynamics at nanoscale interfaces.

    PubMed

    Wang, Linjun; Long, Run; Prezhdo, Oleg V

    2015-04-01

    Nonequilibrium processes involving electronic and vibrational degrees of freedom in nanoscale materials are under active experimental investigation. Corresponding theoretical studies are much scarcer. The review starts with the basics of time-dependent density functional theory, recent developments in nonadiabatic molecular dynamics, and the fusion of the two techniques. Ab initio simulations of this kind allow us to directly mimic a great variety of time-resolved experiments performed with pump-probe laser spectroscopies. The focus is on the ultrafast photoinduced charge and exciton dynamics at interfaces formed by two complementary materials. We consider purely inorganic materials, inorganic-organic hybrids, and all organic interfaces, involving bulk semiconductors, metallic and semiconducting nanoclusters, graphene, carbon nanotubes, fullerenes, polymers, molecular crystals, molecules, and solvent. The detailed atomistic insights available from time-domain ab initio studies provide a unique description and a comprehensive understanding of the competition between electron transfer, thermal relaxation, energy transfer, and charge recombination processes. These advances now make it possible to directly guide the development of organic and hybrid solar cells, as well as photocatalytic, electronic, spintronic, and other devices relying on complex interfacial dynamics.

  17. Time-Domain Ab Initio Modeling of Photoinduced Dynamics at Nanoscale Interfaces

    NASA Astrophysics Data System (ADS)

    Wang, Linjun; Long, Run; Prezhdo, Oleg V.

    2015-04-01

    Nonequilibrium processes involving electronic and vibrational degrees of freedom in nanoscale materials are under active experimental investigation. Corresponding theoretical studies are much scarcer. The review starts with the basics of time-dependent density functional theory, recent developments in nonadiabatic molecular dynamics, and the fusion of the two techniques. Ab initio simulations of this kind allow us to directly mimic a great variety of time-resolved experiments performed with pump-probe laser spectroscopies. The focus is on the ultrafast photoinduced charge and exciton dynamics at interfaces formed by two complementary materials. We consider purely inorganic materials, inorganic-organic hybrids, and all organic interfaces, involving bulk semiconductors, metallic and semiconducting nanoclusters, graphene, carbon nanotubes, fullerenes, polymers, molecular crystals, molecules, and solvent. The detailed atomistic insights available from time-domain ab initio studies provide a unique description and a comprehensive understanding of the competition between electron transfer, thermal relaxation, energy transfer, and charge recombination processes. These advances now make it possible to directly guide the development of organic and hybrid solar cells, as well as photocatalytic, electronic, spintronic, and other devices relying on complex interfacial dynamics.

  18. Photoinduced dipoles and charge pairs in condensed phase. Progress report, November 14, 1993--November 15, 1994

    SciTech Connect

    Not Available

    1994-12-31

    Efforts during the past year centered on expanding the understanding of the photocurrent transients produced by photoinduced dipoles in solution. In addition to exploring intramolecular charge transfer in a molecule which exhibits a giant dipole, the authors began an intensive look at intermolecular electron transfer between photoexcited electron donors and acceptors. The three projects which are farthest along are described in abstract form in the paragraphs which follow. The first makes use of the generous gift from Dr. Michael Wasielewski (Argonne National Laboratory) of a carefully constructed molecular triad which exemplifies artificial photosynthesis. Measurements reveal that the triad possesses a substantial ground state dipole moment as well as the long-lived charge separation which was expected for the excited state. The second and third abstracts describe the quantification of fractional charge transfer in excited state complexes (exciplexes). All exciplexes are not the same and the authors found that the fractional electron transfer increases with reaction exoergicity. The first and second abstracts describe work which is nearly ready to be submitted. The third outlines the mechanistically fascinating story of how one donor replaces another in an excited state complex. Their tentative conclusion is that the mechanism depends on reaction exoergicity.

  19. Effects of molecular symmetry on quantum reaction dynamics: novel aspects of photoinduced nonadiabatic dynamics.

    PubMed

    Al-Jabour, Salih; Leibscher, Monika

    2015-01-15

    Nonadiabatic coupling terms (NACTs) between different electronic states lead to fast radiationless decay in photoexcited molecules. Using molecular symmetry, i.e., symmetry with respect to permutation of identical nuclei and inversion of the molecule in space, the irreducible representations of the NACTs can be determined with a combination of molecular symmetry arguments and quantization rules. Here, we extend these symmetry rules for electronic states and coupling elements and demonstrate the importance of molecular symmetry for nonadiabatic nuclear dynamics. As an example, we consider the NACTs related to the torsion around the CN bond in C5H4NH. We present the results of quantum dynamical simulations of the photoinduced large amplitude torsion on three coupled electronic states and show how the interference between wavepackets leads to radiationless decay, which depends on the symmetry of the NACTs. Moreover, we show that the nuclear spin of the system determines the symmetry of the initial nuclear wave function and thus influences the torsional dynamics. This may open new possibilities for nuclear spin selective laser control of nuclear dynamics.

  20. Nonadiabatic quantum molecular dynamics with hopping. III. Photoinduced excitation and relaxation of organic molecules

    NASA Astrophysics Data System (ADS)

    Fischer, M.; Handt, J.; Schmidt, R.

    2014-07-01

    Photoinduced excitation and relaxation of organic molecules (C2H4 and CH2NH2+) are investigated by means of nonadiabatic quantum molecular dynamics with hopping (NA-QMD-H), developed recently [Fischer, Handt, and Schmidt, paper I of this series, Phys. Rev. A 90, 012525 (2014), 10.1103/PhysRevA.90.012525]. This method is first applied to molecules assumed to be initially ad hoc excited to an electronic surface. Special attention is drawn to elaborate the role of electron-nuclear correlations, i.e., of quantum effects in the nuclear dynamics. It is found that they are essential for a realistic description of the long-time behavior of the electronic relaxation process, but only of minor importance to portray the short-time scenario of the nuclear dynamics. Migration of a hydrogen atom, however, is identified as a quantum effect in the nuclear motion. Results obtained with explicit inclusion of an fs-laser field are presented as well. It is shown that the laser-induced excitation process generally leads to qualitatively different gross features of the relaxation dynamics, as compared to the field-free case. Nevertheless, the nuclear wave packet contains all subtleties of the cis-trans isomerization mechanism as observed without a laser field.

  1. Dynamics of photoinduced reactions at oxide surfaces

    NASA Astrophysics Data System (ADS)

    Al-Shamery, K.

    1996-11-01

    This report summarizes our work on UV-laser induced desorption of small molecules and atoms from transition metal oxides. The systems presented serve as examples for a simple photochemical reaction, the fission of the molecule surface bond. State resolved detection methods were used to record the final state distributions of the desorbing neutral molecules. Detailed results on the systems NO/NiO(1 1 1) and CO/Cr2O3(0 0 0 1) are presented. The experiments include investigations on stereodynamic aspects like the angular distributions of the desorbing molecules and, in the case of CO desorption, the rotational alignment with respect to the surface normal. Large desorption cross sections of (6±1) ṡ 10-17 cm2 for NO and (3.5±1) ṡ 10-17 cm2 for CO have been found for the desorption at 6.4 eV. The wavelength dependence indicates that the primary excitation step is substrate induced. The final state distributions show a high degree of translational, rotational and vibrational excitation and are clearly nonthermal of origin. The results are consistent with the formation of a negative ion intermediate state of the adsorbate. This observation is supported from a comparison to former results on NO/NiO(1 0 0) for which extensive ab initio calculations including electronically excited states exist. A spin state dependence of the vibrational excitation of NO could only be observed for NO/NiO(1 1 1) and is absent for NO/NiO(1 0 0). We attribute this observation to a spin state dependent coupling of the desorbing molecule to the surface in case the spin lattice orientation of the surface shows a preferential orientation. In the (1 1 1) plane the spin orientation is parallel within neighbour nickel ions while it is alternating in the (1 0 0) plane. For both systems studied the velocity component parallel to the surface is constant leading to a strong peaking along the surface normal for the fast molecules. The change from a preferred helicopter rotation (angular momentum

  2. Design of a Molecular Memory Device: The Electron Transfer Shift Register Memory

    NASA Technical Reports Server (NTRS)

    Beratan, D.

    1993-01-01

    A molecular shift register memory at the molecular level is described. The memory elements consist of molecules can exit in either an oxidized or reduced state and the bits are shifted between the cells with photoinduced electron transfer reactions.

  3. Photoinduced Birefringence in Azo-Dye Doped Polyurethane

    NASA Astrophysics Data System (ADS)

    Aleksejeva, J.; Gerbreders, A.; Reinfelde, M.; Teteris, J.

    2011-01-01

    In this report we describe a photoinduced birefringence in disperse red (DR1) azo-dye doped polyurethane films. DR1 dye molecules in these films are chemically bound with the polyurethane polymer's main chain. Under laser radiation the DR1 molecules experience the isomerization process; as a result, the dipole moment of such a molecule changes and they align in the presence of electric field. Photo-birefringence was induced by linearly polarized laser radiation (532 nm, 448 nm, 375 nm and 632.8 nm) in the films with various concentrations of DR1 dye. The photo-induced birefringence (PIBR) Δn was measured at 634 nm wavelength, and its dependences on the pumping beam wavelength and intensity were evaluated. The Δn relaxation was studied both in the dark and under light illumi-nation. In DR1-doped polyurethane films the holographic recording was performed using laser light radiation (532 nm). The profile of surface relief grating (SRG) was studied using AFM. The relationship between SRG formation and PIBR is discussed.

  4. Photo-induced Mass Transport through Polymer Networks

    NASA Astrophysics Data System (ADS)

    Meng, Yuan; Anthamatten, Mitchell

    2014-03-01

    Among adaptable materials, photo-responsive polymers are especially attractive as they allow for spatiotemporal stimuli and response. We have recently developed a macromolecular network capable of photo-induced mass transport of covalently bound species. The system comprises of crosslinked chains that form an elastic network and photosensitive fluorescent arms that become mobile upon irradiation. We form loosely crosslinked polymer networks by Michael-Addition between multifunctional thiols and small molecule containing acrylate end-groups. The arms are connected to the network by allyl sulfide, that undergoes addition-fragmentation chain transfer (AFCT) in the presence of free radicals, releasing diffusible fluorophore. The networks are loaded with photoinitiator to allow for spatial modulation of the AFCT reactions. FRAP experiments within bulk elastomers are conducted to establish correlations between the fluorophore's diffusion coefficient and experimental variables such as network architecture, temperature and UV intensity. Photo-induced mass transport between two contacted films is demonstrated, and release of fluorophore into a solvent is investigated. Spatial and temporal control of mass transport could benefit drug release, printing, and sensing applications.

  5. Model for photoinduced bending of slender molecular crystals.

    PubMed

    Nath, Naba K; Pejov, Ljupčo; Nichols, Shane M; Hu, Chunhua; Saleh, Na'il; Kahr, Bart; Naumov, Panče

    2014-02-19

    The growing realization that photoinduced bending of slender photoreactive single crystals is surprisingly common has inspired researchers to control crystal motility for actuation. However, new mechanically responsive crystals are reported at a greater rate than their quantitative photophysical characterization; a quantitative identification of measurable parameters and molecular-scale factors that determine the mechanical response has yet to be established. Herein, a simple mathematical description of the quasi-static and time-dependent photoinduced bending of macroscopic single crystals is provided. This kinetic model goes beyond the approximate treatment of a bending crystal as a simple composite bilayer. It includes alternative pathways for excited-state decay and provides a more accurate description of the bending by accounting for the spatial gradient in the product/reactant ratio. A new crystal form (space group P21/n) of the photoresponsive azo-dye Disperse Red 1 (DR1) is analyzed within the constraints of the aforementioned model. The crystal bending kinetics depends on intrinsic factors (crystal size) and external factors (excitation time, direction, and intensity).

  6. Photo-induced reduction of flavin mononucleotide in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Song, S.-H.; Dick, B.; Penzkofer, A.

    2007-01-01

    The photo-induced reduction of flavin mononucleotide (FMN) in aqueous solutions is studied by absorption spectra measurement under aerobic and anaerobic conditions. Samples without exogenous reducing agent and with the exogenous reducing agents ethylene-diamine-tetraacetic acid (EDTA) and dithiothreitol (DTT) are investigated. Under anaerobic conditions the photo-induced reduction with and without reducing agents is irreversible. Under aerobic conditions the photo-reduction without added reducing agent is small compared to the photo-degradation, and the photo-reduction of FMN by the reducing agents is reversible (re-oxidation in the dark). During photo-excitation of FMN the dissolved oxygen is consumed by singlet oxygen formation and subsequent chemical reaction. After light switch-off slow re-oxidation (slow absorption recovery) occurs due to air in-diffusion from surface. EDTA degradation by FMN excitation leads to oxygen scavenging. The quantum efficiencies of photo-reduction under aerobic and anaerobic conditions are determined. The re-oxidation of reduced FMN under aerobic conditions and due to air injection is investigated.

  7. Photoinduced giant magnetic polarons in EuTe

    NASA Astrophysics Data System (ADS)

    Henriques, A. B.; Naupa, A. R.; Usachev, P. A.; Pavlov, V. V.; Rappl, P. H. O.; Abramof, E.

    2017-01-01

    Photoinduced magnetic polarons in EuTe, with a magnetic moment of several hundred Bohr magnetons, were investigated as a function of pump intensity and temperature by pump-probe Faraday rotation. The quantum efficiency for optical generation of magnetic polarons is found to be 0.09. The pump-intensity dependence of the photoinduced Faraday rotation shows a sublinear increase, from which we deduce that the population of photoexcited polarons is limited by a maximum value of 4.5 ×1015cm-3 . This is four orders of magnitude less than the concentration of polarons that would completely fill the crystal, which suggests that the photoexcited polarons are anchored by defects. In addition to the generation of polarons, at high pump densities the modulated pump light also causes a small alternating heating of the illuminated region. The temperature dependence of the polaron magnetic moment is well described by the Curie-Weiss law. Above 100 K, polarons are thermally quenched with an activation energy of 11 meV.

  8. Photoinduced Kondo effect in CeZn3P3

    NASA Astrophysics Data System (ADS)

    Kitagawa, J.; Kitajima, D.; Shimokawa, K.; Takaki, H.

    2016-01-01

    The Kondo effect, which originates from the screening of a localized magnetic moment by a spin-spin interaction, is widely observed in nonartificial magnetic materials, artificial quantum dots, and carbon nanotubes. In devices based on quantum dots or carbon nanotubes that target quantum information applications, the Kondo effect can be tuned by a gate voltage, a magnetic field, or light. However, the manipulation of the Kondo effect in nonartificial materials has not been thoroughly studied; in particular, the artificial creation of the Kondo effect remains unexplored. Per this subject study, however, a route for the optical creation of the Kondo effect in the nonartificial material p -type semiconductor CeZn3P3 is presented. The Kondo effect emerges under visible-light illumination of the material by a continuous-wave laser diode and is ultimately revealed by photoinduced electrical resistivity, which clearly exhibits a logarithmic temperature dependency. By contrast, a La-based compound (LaZn3P3 ) displays only normal metallic behavior under similar illumination. The photoinduced Kondo effect, which occurs at higher temperatures when compared with the Kondo effect in artificial systems, provides a potential range of operation for not only quantum information/computation devices but also for operation of magneto-optic devices, thereby expanding the range of device applications based on the Kondo effect.

  9. Imaging of photoinduced tautomerism in single porphyrin molecules

    NASA Astrophysics Data System (ADS)

    Jäger, Regina; Chizhik, Anna M.; Chizhik, Alexey I.; Mack, Hans-Georg; Lyubimtsev, Alexey; Hanack, Michael; Meixner, Alfred J.

    2011-10-01

    In this work we present our new experimental and theoretical results upon investigations of the photoinduced tautomerism processes of single metal-free porphyrin-type molecules. During tautomerization a molecule changes its structure, therefore the excitation transition dipole moment (TDM) of the molecule changes its orientation. Using confocal microscopy in combination with azimuthally and radially polarized laser beams we are able to determine the orientation of the TDM as well as the orientation of a single molecule itself. In the case of tautomerism we are able to visualize this process and even the involved isomers separately. The study first focuses on two symmetrical compounds: a phthalocyanine and a porphyrin. Additionally, differences of the single molecules embedded in a polymer matrix or just spin-coated on a glass cover slide and under nitrogen flow are investigated. In the latter case we observe a higher frequency of the change of the TDM orientation. The experimental studies are supplemented by quantum chemical calculations. Variations of the molecular substituents, the environment and excitation wavelength can give new insights into the excited-state tautomerism process of a single molecule. We also introduce some suggestions for future experiments to support the understanding of the photoinduced tautomerism.

  10. Kinetics of photoinduced anisotropy in bacteriorhodopsin film under two pumping beams.

    PubMed

    Han, Junhe; Yao, Baoli; Gao, Peng; Chen, Liju; Wang, Yingli; Lei, Ming

    2008-07-20

    Photoinduced anisotropy in bacteriorhodopsin (BR) film arises from the selective bleaching of BR molecules to linearly polarized light. The kinetics of photoinduced anisotropy excited by single and two pumping beams are investigated theoretically and experimentally. Compared with a single pumping beam (650 nm), which produces comparatively small photoinduced anisotropy, dual-wavelength linearly polarized pumping beams (650 and 405 nm) can obviously change the photoinduced anisotropy. When the polarization orientation of the 405 nm pumping beam is perpendicular to that of the 650 nm pumping beam, the peak and steady values of the photoinduced anisotropy kinetic curves are remarkably enhanced. But when the two pumping beams have parallel polarization orientation, the peak and steady values are restrained. At a fixed intensity of the 650 nm pumping beam, there exists an optimal intensity for the 405 nm pumping beam to maximize the value of the photoinduced anisotropy. The photoinduced transmittance of the polarizer-BR-analyzer system is modulated by the polarization angle of the 405 nm pumping beam in an approximate-cosine form.

  11. Type II guanine oxidation photoinduced by the antibacterial fluoroquinolone Rufloxacin in isolated DNA and in 2'-deoxyguanosine.

    PubMed

    Belvedere, Alessandra; Boscá, Francisco; Catalfo, Alfio; Cuquerella, Maria C; de Guidi, Guido; Miranda, Miguel A

    2002-09-01

    The role played by type I (radical) and type II (singlet oxygen) mechanisms in the Rufloxacin (RFX)-photoinduced production of 8-hydroxy-2'-deoxyguanosine in DNA has been evaluated. This fluoroquinolone drug has been shown to be able to photoinduce increased levels of some DNA base oxidation products, such as 8-OH-dGuo, that are indicative of mutagenic and carcinogenic events, with probable implications in aging processes. The relative weight of the two photosensitization mechanisms was obtained via determination of two different photoproducts of 2'-deoxyguanosine (dGuo), which are diagnostic of the two different pathways, namely, (4R)- and (4S)-4,8-dihydro-4-hydroxy-8-oxo-2'-deoxyguanosine and 2,2-diamino-4-[(2-deoxy-beta-D-erythro-pentofuranosyl)amino]-2,5-dihydrooxazol-5-one. The observed predominance of type II reaction is in agreement with the fact that the triplet state of RFX is able to transfer with high efficiency its energy to molecular oxygen, giving rise to singlet oxygen. Photophysical measurements suggest that hydrated electrons produced by Rufloxacin photoionization react with dGuo, Thd, and DNA, whereas these biomolecules quench the RFX triplet state with low efficiency. Static quenching of Rufloxacin fluorescence indicates an interaction of this drug both with DNA and with dGuo. On the basis of these experimental data, Rufloxacin photosensitization of DNA is proposed to occur by a type II mechanism.

  12. Probing of local structures of thermal and photoinduced phases in rubidium manganese hexacyanoferrate by resonant Raman spectroscopy.

    PubMed

    Fukaya, Ryo; Asahara, Akifumi; Ishige, Shun; Nakajima, Makoto; Tokoro, Hiroko; Ohkoshi, Shin-ichi; Suemoto, Tohru

    2013-08-28

    Resonant couplings of the electronic states and the stretching vibrations of CN(-) ligands, which bridges metal ions, is investigated by resonance Raman spectroscopy for Rb(0.94)Mn[Fe(CN)6](0.98)·0.2H2O. Large excitation wavelength dependences over one order of magnitude were found for Raman peaks corresponding to different valence pairs of metal ions in the excitation wavelength range between 350 and 632 nm. In the thermal low-temperature phase, the CN(-) stretching modes due to the low-temperature-phase configuration (Fe(2+)-Mn(3+)) and the phase-boundary configuration (Fe(3+)-Mn(3+)) are coupled to the Fe(2+)-to-Mn(3+) intervalence transfer band and Jahn-Teller distorted Mn(3+) d-d transition band, respectively. In the photoinduced low-temperature phase, the Fe(3+)-Mn(3+) mode shows strong resonant enhancement with the CN(-)-to-Fe(3+) charge-transfer band, which exists in the high-temperature phase with a cubic structure. From these resonance behaviors, we conclude that the local lattice symmetry of the photoinduced phase is cubic in contrast with the tetragonal symmetry in the thermal low-temperature phase.

  13. Photo-induced anisotropy in ZnO/PVA nanocomposites prepared by modified electrochemical method in PMA matrix

    NASA Astrophysics Data System (ADS)

    Yanchuk, O. M.; Ebothé, J.; El-Naggar, A. M.; Albassam, A.; Tsurkova, L. V.; Marchuk, O. V.; Lakshminarayana, G.; Tkaczyk, S.; Kityk, I. V.; Fedorchuk, A. O.; Vykhryst, O. M.; Urubkov, I. V.

    2017-02-01

    Substantial photo-induced optical anisotropy was discovered in ZnO/PVA nanocomposites under the influence of external bicolor laser illumination. Zinc oxide nanoparticles were synthesized by electrolysis of a sodium chloride aqueous medium including poly-methacrylic acid (PMA) in a cell system having a soluble zinc anode. The structural analysis of the ZnO powder samples has been carried out by X-Ray Diffractometry (XRD) and Scanning Electron Microscopy (SEM). The polyvinyl alcohol (PVA) embedded ZnO films obtained from the powder samples possess larger grain sizes than those in powder form. The films were prepared from the same polymer matrix but elaborated with two different PVA contents which are respectively 15% and 30%. The photoinduced anisotropy was identified by using two bicolor Er: glass laser beams incident at different angles. Substantial influence of the technological processes on the embedded nanoparticle sizes and related birefringence was explored. The process of laser induced anisotropy shows an occurrence of birefringence saturation.

  14. Role of Conical Intersections in Molecular Spectroscopy and Photoinduced Chemical Dynamics

    NASA Astrophysics Data System (ADS)

    Domcke, Wolfgang; Yarkony, David R.

    2012-05-01

    This review describes how conical intersections affect measured molecular spectra and simple photofragmentation processes. We consider excitations that result in electron ejection, that is, photoionization or photodetachment, as well as photoinduced H-atom elimination. Section 1 presents a brief overview of the history of conical intersections and their rise from an arcane theoretical concept to a major paradigm in nonadiabatic chemistry. In Section 2, the generic properties of conical intersections are discussed, as well as their characterization with modern electronic-structure methods. Section 3 briefly discusses computational tools used to compute the nuclear motion involving conical intersections. Section 4 describes how the ideas of Sections 2 and 3 are combined to simulate molecular spectra impacted by conical intersections. Section 5 describes selected recent experimental and computational studies of photoelectron, photodetachment, and photofragment spectra. Rather than providing an encyclopedic bibliography of the previous and current literature, we illustrate significant problems currently being addressed and describe what can be accomplished with current computational techniques and how these results are achieved. Section 6 suggests future directions in this field.

  15. Effect of initial solution pH on photo-induced reductive decomposition of perfluorooctanoic acid.

    PubMed

    Qu, Yan; Zhang, Chao-Jie; Chen, Pei; Zhou, Qi; Zhang, Wei-Xian

    2014-07-01

    The effects of initial solution pH on the decomposition of perfluorooctanoic acid (PFOA) with hydrated electrons as reductant were investigated. The reductive decomposition of PFOA depends strongly on the solution pH. In the pH range of 5.0-10.0, the decomposition and defluorination rates of PFOA increased with the increase of the initial solution pH. The rate constant was 0.0295 min(-1) at pH 10.0, which was more than 49.0 times higher than that at pH 5.0. Higher pH also inhibits the generation of toxic intermediates during the PFOA decomposition. For example, the short-chain PFCAs reached a lower maximum concentration in shorter reaction time as pH increasing. The peak areas of accumulated fluorinated and iodinated hydrocarbons detected by GC/MS under acidic conditions were nearly 10-100 times more than those under alkaline conditions. In short, alkaline conditions were more favorable for photo-induced reduction of PFOA as high pH promoted the decomposition of PFOA and inhibited the accumulation of intermediate products. The concentration of hydrated electron, detected by laser flash photolysis, increased with the increase of the initial pH. This was the main reason why the decomposition of PFOA in the UV-KI system depended strongly on the initial pH.

  16. Nitroxides as redox probes of melanins: dark-induced and photoinduced changes in redox equilibria

    SciTech Connect

    Sarna, T.; Korytowski, W.; Sealy, R.C.

    1985-05-15

    The interaction of nitroxide free radicals and their reduced products (hydroxylamines) with synthetic and natural melanins has been studied. Electron spin resonance spectroscopy was used to measure changes in radical concentration in the dark and during irradiation with visible or uv light. Some reduction of nitroxide occurs in the dark, and is reversible: the nitroxide can be completely regenerated by the one-electron oxidant ferricyanide. The kinetics of the process depend strongly on radical charge and pH. For positively charged nitroxides the rate is much faster than for either neutral or anionic radicals. At pH 10 the rate is about 20 times faster than at pH 5. Oxidation of hydroxylamine also can occur so that a redox equilibrium is established. The equilibrium constant has been estimated for the reaction between a nitroxide and melanin from autoxidation of 3,4-dihydroxyphenylalanine. Results are also dependent upon the type of melanin used and chemical modification (oxidation or reduction) of the melanin. Redox equilibria are altered during irradiation with either visible or uv light. Rapid oxidation of hydroxylamine to nitroxide is apparent, together with a slower reduction of nitroxide. Action spectra for these processes are related to those for melanin radical production and oxygen consumption in nitroxide-free melanin systems. Reduction of nitroxide is inhibited by oxygen, suggesting a competition between nitroxide and oxygen for photoinduced reducing equivalents.

  17. Role of conical intersections in molecular spectroscopy and photoinduced chemical dynamics.

    PubMed

    Domcke, Wolfgang; Yarkony, David R

    2012-01-01

    This review describes how conical intersections affect measured molecular spectra and simple photofragmentation processes. We consider excitations that result in electron ejection, that is, photoionization or photodetachment, as well as photoinduced H-atom elimination. Section 1 presents a brief overview of the history of conical intersections and their rise from an arcane theoretical concept to a major paradigm in nonadiabatic chemistry. In Section 2, the generic properties of conical intersections are discussed, as well as their characterization with modern electronic-structure methods. Section 3 briefly discusses computational tools used to compute the nuclear motion involving conical intersections. Section 4 describes how the ideas of Sections 2 and 3 are combined to simulate molecular spectra impacted by conical intersections. Section 5 describes selected recent experimental and computational studies of photoelectron, photodetachment, and photofragment spectra. Rather than providing an encyclopedic bibliography of the previous and current literature, we illustrate significant problems currently being addressed and describe what can be accomplished with current computational techniques and how these results are achieved. Section 6 suggests future directions in this field.

  18. Side chain variations on a series of dicyanovinyl-terthiophenes: a photoinduced absorption study.

    PubMed

    Ziehlke, Hannah; Fitzner, Roland; Koerner, Christian; Gresser, Roland; Reinold, Egon; Bäuerle, Peter; Leo, Karl; Riede, Moritz K

    2011-08-04

    We characterize a series of dicyanovinyl-terthiophenes with different alkyl side chains. Variations of side chain substitution patterns and length mainly affect the morphology of the evaporated thin films, which in turn sensitively influences properties like absorption, energy levels, and thin film roughness. To investigate changes in transfer processes between electron donor (D) and acceptor (A) molecules due to side chain variations, we use photoinduced absorption spectroscopy (PIA). PIA probes the long-living photoexcited species at the D-A interface: triplet excitons, cations, and anions. For a blend layer of dicyanovinyl-terthiophene and the electron acceptor fullerene C(60), an energy transfer via the singlet and triplet manifold of C(60) occurs. The recombination dynamics of the triplet excitons reveal two components that differ in their lifetime and generation rate by 1 order of magnitude. By comparing the dynamics of triplet excitons in neat and blend layers, we estimate the energy transfer efficiency in dependence of the type of side chain. The compound with methyl side chains shows remarkable properties regarding thin film absorption, surface roughness, and energy transfer efficiency, which we attribute to the specific nanomorphology of the thin film.

  19. Enhanced Rates of Photoinduced Molecular Orientation in a Series of Molecular Glassy Thin Films.

    PubMed

    Snell, Kristen E; Hou, Renjie; Ishow, Eléna; Lagugné-Labarthet, François

    2015-07-07

    Photoinduced orientation in a series of molecular glasses made of small push-pull azo derivatives is dynamically investigated for the first time. Birefringence measurements at 632.8 nm are conducted with a temporal resolution of 100 ms to probe the fast rate of the azo orientation induced under polarized light and its temporal stability over several consecutive cycles. To better evaluate the influence of the azo chemical substituents and their electronic properties on the orientation of the whole molecule, a series of push-pull azo derivatives involving a triphenylaminoazo core substituted with distinct electron-withdrawing moieties is studied. All resulting thin films are probed using polarization modulation infrared spectroscopy that yields dynamical linear dichroism measurements during a cycle of orientation followed by relaxation. We show here in particular that the orientation rates of small molecule-based azo materials are systematically increased up to 7-fold compared to those of a reference polymer counterpart. For specific compounds, the percentage of remnant orientation is also higher, which makes these materials of great interest and promising alternatives to azobenzene-containing polymers for a variety of applications requiring a fast response and absolute control over the molecular weight.

  20. Photoinduced currents in pristine and ion irradiated kapton-H polyimide

    SciTech Connect

    Sharma, Anu Sridharbabu, Y. Quamara, J. K.

    2014-10-15

    The photoinduced currents in pristine and ion irradiated kapton-H polyimide have been investigated for different applied electric fields at 200°C. Particularly the effect of illumination intensity on the maximum current obtained as a result of photoinduced polarization has been studied. Samples were irradiated by using PELLETRON facility, IUAC, New Delhi. The photo-carrier charge generation depends directly on intensity of illumination. The samples irradiated at higher fluence show a decrease in the peak current with intensity of illumination. The secondary radiation induced crystallinity (SRIC) is responsible for the increase in maximum photoinduced currents generated with intensity of illumination.

  1. Biotinylated Platinum(II) Ferrocenylterpyridine Complexes for Targeted Photoinduced Cytotoxicity.

    PubMed

    Mitra, Koushambi; Shettar, Abhijith; Kondaiah, Paturu; Chakravarty, Akhil R

    2016-06-06

    Biotinylated platinum(II) ferrocenylterpyridine (Fc-tpy) complexes [Pt(Fc-tpy)(L(1))]Cl (1) and [Pt(Fc-tpy)(L(2))]Cl (2), where HL(1) and HL(2) are biotin-containing ligands, were prepared, and their targeted photoinduced cytotoxic effect in cancer cells over normal cells was studied. A nonbiotinylated complex, [Pt(Fc-tpy)(L(3))]Cl (3), was prepared as a control to study the role of the biotin moiety in cellular uptake properties of the complexes. Three platinum(II) phenylterpyridine (Ph-tpy) complexes, viz., [Pt(Ph-tpy)(L(1))]Cl (4), [Pt(Ph-tpy)(L(2))]Cl (5), and [Pt(Ph-tpy)(L(3))]Cl (6), were synthesized and explored to understand the role of a metal-bound Fc-tpy ligand over Ph-tpy as a photoinitiator. The Fc-tpy complexes displayed an intense absorption band near 640 nm, which was absent in their Ph-tpy analogues. The Fc-tpy complexes (1 mM in 0.1 M TBAP) showed an irreversible cyclic voltammetric anodic response of the Fc/Fc(+) couple near 0.25 V. The Fc-tpy complexes displayed photodegradation in red light of 647 nm involving the formation of a ferrocenium ion (Fc(+)) and reactive oxygen species (ROS). Photoinduced release of the biotinylated ligands was observed from spectral measurements, and this possibly led to the controlled generation of an active platinum(II) species, which binds to the calf-thymus DNA used for this study. The biotinylated photoactive Fc-tpy complexes showed significant photoinduced cytotoxicity, giving a IC50 value of ∼7 μM in visible light of 400-700 nm with selective uptake in BT474 cancer cells over HBL-100 normal cells. Furthermore, ferrocenyl complexes resulted in light-induced ROS-mediated apoptosis, as indicated by DCFDA, annexin V/FITC staining, and sub-G1 DNA content determined by fluorescent activated cell sorting analysis. The phenyl analogues 4 and 5 were photostable, served as DNA intercalators, and demonstrated selective cytotoxicity in the cancer cells, giving IC50 values of ∼4 μM.

  2. Photoinduced ferrimagnetic systems in Prussian blue analogues C(I)xCo4[Fe(CN)6]y (C(I) = alkali cation). 4. Characterization of the ferrimagnetism of the photoinduced metastable state in Rb1.8Co4[Fe(CN)6]3.3-13H2O by K edges X-ray magnetic circular dichroism.

    PubMed

    Champion, G; Escax, V; Cartier Dit Moulin, C; Bleuzen, A; Villain, F; Baudelet, F; Dartyge, E; Verdaguer, M

    2001-12-19

    In Part 2 of this work, the electronic and local structure of the photoinduced metastable magnetic state of the Prussian blue analogue Rb1.8Co4[Fe(CN)6]3.3-13H2O were characterized. To determine directly the relative orientation of the magnetic moments of Co(II) and Fe(III) ions in the metastable state, and the nature of the exchange interaction between them, we performed X-ray magnetic circular dichroism (XMCD) experiments at the cobalt and iron K edges. We present the first direct experimental evidence of the antiferromagnetic interaction between the cobalt and the iron ions, leading to the ferrimagnetism of the photoinduced metastable state.

  3. Photoinduced Acrylate Polymerization: Unexpected Reduction in Chain Branching.

    PubMed

    Wenn, Benjamin; Reekmans, Gunter; Adriaensens, Peter; Junkers, Thomas

    2015-08-01

    The branching stemming from midchain radical formation in n-butyl acrylate polymerization is investigated via melt-state (13) C NMR measurements. The dependence of the degree of branching (DB) on the monomer conversion of the system is examined for photoinduced polymerizations, revealing a steady increase in branching with conversion. For polymerization at moderate light intensities, an increase in branching from 0.03% to 0.37% is observed for polymerizations at 60 °C, which is fivefold below the level of branching observed in thermally initiated polymerizations under otherwise identical reaction conditions. The reason for this overall reduction in branching remains momentarily unclear; yet, a strong dependence of branching on light intensity is observed. While polymerization under a 1 W LED lamp results at almost full monomer conversion in branching degrees of 0.22%, polymerization under a 400 W lamp yields 1.81% of chain branches.

  4. Preparation of diarylethene copolymers and their photoinduced refractive index change

    NASA Astrophysics Data System (ADS)

    Cho, S. Y.; Yoo, M.; Shin, H.-W.; Ahn, K.-H.; Kim, Y.-R.; Kim, E.

    2003-01-01

    Diarylethene copolymers were synthesized from 1-(6 '-vinyl-2 '-methylbenzo[ b]thiophene-3 '-yl)-2-(2 ''-methylbenzo [ b]thiophene-3 ''-yl)hexafluorocyclopentene (VMBTF6) and 1-[6 '-(4 '''-vinylbenzoyl)-2 '-methylbenzo[ b]thiophene-3 '-yl]-2-(2 ''-methylbenzo[ b]thiophene-3 ''-yl)hexafluorocyclopentene (VBMBTF6) via living free radical techniques using stable TEMPO derivatives. The diarylethene content was controlled by the feed ratio of diarylethene derivatives and styrene. Transparent photochromic polymer films were prepared from the diarylethene copolymers with narrow molecular weight dispersion (PD˜1.3) by spin coating method. Photoinduced refractive index changes (Δ nTE) of the polymer films, with 25 mol% of diaryethene content, accompanied by the photochromic change were determined as 0.0009 and 0.0030 for poly(styrene- ran -VMBTF6) and poly(styrene- ran-VBMBTF6), respectively.

  5. Photoinduced surface voltage mapping study for large perovskite single crystals

    NASA Astrophysics Data System (ADS)

    Liu, Xiaojing; Liu, Yucheng; Gao, Fei; Yang, Zhou; Liu, Shengzhong Frank

    2016-05-01

    Using a series of illumination sources, including white light (tungsten-halogen lamp), 445-nm, 532-nm, 635-nm, and 730-nm lasers, the surface photovoltage (SPV) images were mapped for centimeter-sized CH3NH3PbX3 (X = Cl, Br, I) perovskite single crystals using Kelvin probe force microscopy. The significant SPV signals were observed to be wavelength-dependent. We attribute the appreciable SPV to the built-in electric field in the space charge region. This study shines light into the understanding of photoinduced charge generation and separation processes at nanoscale to help advance the development of perovskite solar cells, optoelectronics, laser, photodetector, and light-emitting diode (LED).

  6. Photoinduced Magnetization in a Thin Fe-CN-Co Film.

    NASA Astrophysics Data System (ADS)

    Huh, Y. D.; Talham, D. R.; Park, J.-H.; Meisel, M. W.

    2004-03-01

    We have studied the photoinduced magnetization of a new low dimensional system, a thin film of a Prussian blue derivative, Rb_jCo_k[Fe(CN)_6]_l. This film was synthesized by the sequential depositions of Rb^+/Co^2+ and [Fe(CN)_6]^3- ions on the surface of a templated Fe-CN-Co monolayer. In this novel 2D system, high spin states of the Fe and Co spins interact antiferromagnetically and experience long range ordering below 20 K. The spins form domains that exhibit behavior consistent with a cluster spin-glass description. Upon illumination with light, the population of the high spin states increases, resulting in a rapid increase of the magnetization of the film and a modification of the cluster spin-glass properties.

  7. Method for characterizing bulk recombination using photoinduced absorption

    NASA Astrophysics Data System (ADS)

    Wilson, Nora M.; Sandén, Simon; Sandberg, Oskar J.; Österbacka, Ronald

    2017-03-01

    The influence of reaction order and trap-assisted recombination on continuous-wave photoinduced absorption measurements is clarified through analytical calculations and numerical simulations. The results reveal the characteristic influence of different trap distributions and enable distinguishing between shallow exponential and Gaussian distributions and systems dominated by direct recombination by analyzing the temperature dependence of the in-phase and quadrature signals. The identifying features are the intensity dependence of the in-phase at high intensity, P A I ∝ I γ HI , and the frequency dependence of the quadrature at low frequency, P A Q ∝ ω γ LF . For direct recombination, γHI and γLF are temperature independent, and for an exponential distribution, they depend on the characteristic energy Ech as γ HI = 1 / ( 1 + E ch / k T ) and γ LF = k T / E ch , while a Gaussian distribution shows γHI and γLF as functions of I and ω, respectively.

  8. Photo-induced reflectivity in the mid and far infrared

    SciTech Connect

    Haar, P.; Harrington, K.J.; Schwettman, H.A.

    1995-12-31

    Interest in switching FEL beams has motivated studies of photo-induced reflectivity in the mid and far infrared. We are particularly interested in Ge{sup 4}, GaAs, and Si{sup 5}, materials that can be pumped with a visible or near-IR conventional laser and which together cover the wavelengths from 3-100{mu}m. We have made quantitative measurements to determine the induced reflectivity, carrier lifetime, and transient absorption of these materials at several wavelengths across this range using a variety of pump laser wavelengths and pulse lengths. These measurements allow us to determine the feasibility of single pulse selection and cavity dumping with our FELs at high repetition rates.

  9. Luminescence and photoinduced absorption in ytterbium-doped optical fibres

    SciTech Connect

    Rybaltovsky, A A; Aleshkina, S S; Likhachev, M E; Bubnov, M M; Umnikov, A A; Yashkov, M V; Gur'yanov, Aleksei N; Dianov, Evgenii M

    2011-12-31

    Photochemical reactions induced in the glass network of an ytterbium-doped fibre core by IR laser pumping and UV irradiation have been investigated by analysing absorption and luminescence spectra. We have performed comparative studies of the photoinduced absorption and luminescence spectra of fibre preforms differing in core glass composition: Al{sub 2}O{sub 3} : SiO{sub 2}, Al{sub 2}O{sub 3} : Yb{sub 2}O{sub 3} : SiO{sub 2}, and P{sub 2}O{sub 5} : Yb{sub 2}O{sub 3} : SiO{sub 2}. The UV absorption spectra of unirradiated preform core samples show strong bands peaking at 5.1 and 6.5 eV, whose excitation plays a key role in photoinduced colour centre generation in the glass network. 'Direct' UV excitation of the 5.1- and 6.5-eV absorption bands at 244 and 193 nm leads to the reduction of some of the Yb{sup 3+} ions to Yb{sup 2+}. The photodarkening of ytterbium-doped fibres by IR pumping is shown to result from oxygen hole centre generation. A phenomenological model is proposed for the IR-pumping-induced photodarkening of ytterbium-doped fibres. The model predicts that colour centre generation in the core glass network and the associated absorption in the visible range result from a cooperative effect involving simultaneous excitation of a cluster composed of several closely spaced Yb{sup 3+} ions.

  10. Photoinduced properties of nanocrystalline TiO2-anatase coating on Ti-based bone implants.

    PubMed

    Lorenzetti, Martina; Biglino, Daniele; Novak, Saša; Kobe, Spomenka

    2014-04-01

    The paper reports on the photoinduced properties of hydrothermally treated (HT) titanium used for bone implants. The anatase coatings composed of 30-100nm anatase crystals exhibited high photocatalytic activity and good photo-induced wettability, reaching a superhydrophilic state, despite the larger crystal dimensions than the previously reported optimal ones. These properties are due to a suitable combination of surface texture, roughness, thickness, crystal morphology and particle size, which allowed the two independent photo-induced phenomena to occur simultaneously. The results on caffeine degradation by photocatalysis and the prolonged effect (up to two weeks) of photo-induced wettability in dark suggested a possible applicability of the HT anatase coatings as bacteria-repelling surfaces for body implants, in favor of a better osseointegration in vivo.

  11. Photo-induced transformations in 2,2':5',2''-terthiophene thin films on silver.

    PubMed

    Alaverdyan, Yury; Johansson, Patrik; Käll, Mikael

    2006-03-28

    We report on transient photo-induced structural changes of 2,2':5',2''-terthiophene (3T) adsorbed on silver nanoparticles. Surface-enhanced Raman scattering (SERS) data show that the film thickness predetermines the eventual course of these changes. In particular, for high molecular concentrations (thick adsorbate layers), illumination leads to a photoinduced polymerization of the 3T film. For thin layers ( approximately monolayer coverage), the photoinduced spectral evolution is qualitatively different. We interpret the latter process as a cleavage of the terthiophene molecule, resulting in isolated thiophene units. Calculations of excitation energies for 3T + 3Ag+ and 1T + Ag+ revealed visible transitions, while calculated Raman frequencies indicated 1T as a possible photoproduct. As no photoinduced transformations are observed for 3T in the solid or solution phases, it is likely that the processes reported here originate in surface-enhanced charge-transfer between the Ag-surface and the organic adsorbate.

  12. Irradiance and Temperature Dependence of Photo-Induced Orientation in Two Azobenzene-Based Polymers

    DTIC Science & Technology

    1998-06-23

    and Almeria Natansohn* Department of Chemistry, Queen’s University, Kingston, Ontario, K7L 3N6 Paul Rochon Department of Physics, Royal Military...1. IRRADIANCE AND TEMPERATURE DEPENDENCE OF PHOTO-INDUCED ORIENTATION IN TWO AZOBENZENE-BASED POLYMERS Dennis Hore and Almeria Natansohn...IRRADIANCE AND TEMPERATURE DEPENDENCE OF PHOTO-INDUCED ORIENTATION IN TWO AZOBENZENE-BASED POLYMERS Dennis Hore and Almeria Natansohn Department of

  13. Alternating photoinduced mass transport triggered by light polarization in azobenzene containing sol-gel films

    NASA Astrophysics Data System (ADS)

    Fabbri, F.; Lassailly, Y.; Lahlil, K.; Boilot, J. P.; Peretti, J.

    2010-02-01

    Combined shear-force and near-field optical microscopies are used for real-time monitoring of the formation of photoinduced surface relief gratings in photochromic thin films containing azobenzene derivatives. The correlated optical and topographical images provide evidence that the direction of the photoinduced matter migration is defined by the light polarization pattern and that, for a given light intensity pattern, modulating the polarization between two orthogonal states gives rise to alternating mass transport.

  14. Mode of photo-induced toxic action of PAH in fish

    SciTech Connect

    Weinstein, J.E.; Oris, J.T.; Taylor, D.H.

    1995-12-31

    Juvenile fathead minnows (Pimephales promelas) were exposed to 0, 6, and 12 {micro}g/L fluoranthene in the presence of ultraviolet (US) light for 6, 12, 24, 48 and 96 hours. Ultrastructural pathology of the secondary gill lamellae was examined using transmission electron microscopy. Following 12 hours of exposure to 12 {micro}g/L fluoranthene and UV light, epithelial cells appeared highly vacuolated and swollen. Following 48 hours, additional morphological alterations in epithelial cells included multivesiculated blebbing of the plasma membrane into intercellular gaps, numerous cytolysosomes, myelinoid bodies, and enlarged lysosomes with lipid-like contents. The staining characteristics of these cytoplasmic inclusions were consistent with that of phospholipid autodigestion. In addition, an inflammatory-type reaction occurred in the secondary lamellae following 24 hours of exposure. This reaction was characterized by large areas of intercellular edema, which produced a lifting of the epithelium, and the occasional presence of macrophages and granulocytes within the edematous areas and the lamellar blood sinuses. No morphological changes were observed in chloride cells, mucous cells, or pillar cells. In those fish exposed to 6 {micro}g/L fluoranthene and UV light, a similar progression compared to 12 {micro}g/L exposure of epithelial cell damage and inflammatory-type reaction was evident beginning at 24 hours of exposure. The results of this study suggest that the mode of action of photo-induced fluoranthene toxicity in fish is respiratory stress.

  15. Photoinduced hydroxyl radical and photocatalytic activity of samarium-doped TiO(2) nanocrystalline.

    PubMed

    Xiao, Qi; Si, Zhichun; Zhang, Jiang; Xiao, Chong; Tan, Xiaoke

    2008-01-15

    Sm(3+)-doped TiO(2) nanocrystalline has been prepared by sol-gel auto-combustion technique and characterized by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) method, and also UV-vis diffuse reflectance spectroscopy (DRS). These Sm(3+)-doped TiO(2) samples were tested for methylene blue (MB) decomposition and *OH radical formation. The analysis of *OH radical formation on the sample surface under UV irradiation was performed by fluorescence technique with using terephthalic acid, which readily reacted with *OH radical to produce highly fluorescent product, 2-hydroxyterephthalic acid. It was observed that the presence of Sm(3+) ion as a dopant significantly enhanced the photocatalytic activity for MB degradation under UV light irradiation because both the larger specific surface area and the greater the formation rate of *OH radical were simultaneously obtained for Sm(3+)-doped TiO(2) nanocrystalline. The adsorption experimental demonstrated that Sm(3+)-TiO(2) had a higher MB adsorption capacity than undoped TiO(2) and the adsorption capacity of MB increased with the increase of samarium ion content. The results also indicated that the greater the formation rate of *OH radical was, the higher photocatalytic activity was achieved. In this study, the optimum amount of Sm(3+) doping was 0.5 mol%, at which the recombination of photo-induced electrons and holes could be effectively inhibited, the highest formation rate of *OH radicals was, and thereby the highest photocatalytic activity was achieved.

  16. Unravelling the mechanism of photoinduced charge transfer processes in lead iodide perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Marchioro, Arianna; Teuscher, Joël; Friedrich, Dennis; Kunst, Marinus; van de Krol, Roel; Moehl, Thomas; Grätzel, Michael; Moser, Jacques-E.

    2014-03-01

    Lead halide perovskites have recently been used as light absorbers in hybrid organic-inorganic solid-state solar cells, with efficiencies as high as 15% and open-circuit voltages of 1 V. However, a detailed explanation of the mechanisms of operation within this photovoltaic system is still lacking. Here, we investigate the photoinduced charge transfer processes at the surface of the perovskite using time-resolved techniques. Transient laser spectroscopy and microwave photoconductivity measurements were applied to TiO2 and Al2O3 mesoporous films impregnated with CH3NH3PbI3 perovskite and the organic hole-transporting material spiro-OMeTAD. We show that primary charge separation occurs at both junctions, with TiO2 and the hole-transporting material, simultaneously, with ultrafast electron and hole injection taking place from the photoexcited perovskite over similar timescales. Charge recombination is shown to be significantly slower on TiO2 than on Al2O3 films.

  17. Highly efficient photoinduced desorption of N{sub 2}O and CO from porous silicon

    SciTech Connect

    Toker, Gil; Sagi, Roey; Bar-Nachum, Shay; Asscher, Micha

    2013-01-28

    Photoinduced desorption (PID) of N{sub 2}O and CO from porous silicon (PSi) samples is reported. Both adsorbates exhibit unusually large cross sections for PID at 193 nm, up to 10{sup -15} cm{sup 2}, 2-3 orders of magnitude larger than the literature values for similar processes on flat Si. Under this UV irradiation, N{sub 2}O molecules undergo photodissociation (a competing process leading to surface oxidation) with a cross section that is 2 orders of magnitude smaller than photodesorption. In the case of CO desorption is the exclusive photodepletion mechanism. PID efficiency decreases with increasing CO coverage suggesting PID hindrance by interactions among the desorbing CO molecules leading to re-adsorption at higher coverage. The wavelength and fluence dependence measurements exclude the possibility of laser induced thermal desorption for both adsorbates. The proposed mechanism for this phenomenon is desorption induced by hot electron transfer from the substrate to the adsorbate. Enhanced lifetime of transient negative adsorbate due to stabilization by localized holes on PSi nanotips can explain the observed abnormally large PID efficiency on top of porous silicon.

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

    NASA Astrophysics Data System (ADS)

    Tang, Yu; Pattengale, Brian; Ludwig, John; Atifi, Abderrahman; Zinovev, Alexander V.; Dong, Bin; Kong, Qingyu; Zuo, Xiaobing; Zhang, Xiaoyi; Huang, Jier

    2015-12-01

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

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

    DOE PAGES

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

    2015-12-17

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

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

    PubMed Central

    Tang, Yu; Pattengale, Brian; Ludwig, John; Atifi, Abderrahman; Zinovev, Alexander V.; Dong, Bin; Kong, Qingyu; Zuo, Xiaobing; Zhang, Xiaoyi; Huang, Jier

    2015-01-01

    Ni(OH)2 have emerged as important functional materials for solar fuel conversion because of their potential as cost-effective bifunctional catalysts for both hydrogen and oxygen evolution reactions. However, their roles as photocatalysts in the photoinduced charge separation (CS) reactions remain unexplored. In this paper, we investigate the CS dynamics of a newly designed hybrid catalyst by integrating a Ru complex with Ni(OH)2 nanoparticles (NPs). Using time resolved X-ray absorption spectroscopy (XTA), we directly observed the formation of the reduced Ni metal site (~60 ps), unambiguously demonstrating CS process in the hybrid through ultrafast electron transfer from Ru complex to Ni(OH)2 NPs. Compared to the ultrafast CS process, the charge recombination in the hybrid is ultraslow (≫50 ns). These results not only suggest the possibility of developing Ni(OH)2 as solar fuel catalysts, but also represent the first time direct observation of efficient CS in a hybrid catalyst using XTA. PMID:26673578

  1. Photoinduced charge separation at polymer-fullerene interfaces of BHJ solar cells (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Poluektov, Oleg G.; Niklas, Jens; Mardis, Kristy

    2016-09-01

    While photovoltaic cells are highly promising man-made devices for direct solar energy utilization, a number of fundamental questions about how the organic bulk heterojunction cell enables efficient long-lived and long-range charge separation remain unanswered. These questions were address by employing an advanced suite of EPR spectroscopy in combination with DFT calculations to study mechanism of charge separation at the polymer-fullerene interfaces of photo-active BHJ. Observed charge delocalization in BHJ upon photoinduced ET is analogous to that in organic donor-acceptor material. This is an efficient mechanism of charge stabilization in photosynthetic assemblies. Time-resolved EPR spectra show a strong polarization pattern for all polymer-fullerene blends under study, which is caused by non-Boltzmann population of the electron spin energy levels in the radical pairs. The first observation of this phenomenon was reported in natural and artificial photosynthetic assemblies, and comparison with these systems allows us to better understand charge separation processes in OPVs. The spectral analysis presented here, in combination with DFT calculations, shows that CS processes in OPV materials are similar to that in organic photosynthetic systems. This work was supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences, under Contract DE-AC02-06CH11357 at Argonne National Laboratory.

  2. Photoinduced Absorption of the Monomer Derivative of a Polyphenylene Vinylene Segmented Block Copolymer

    NASA Astrophysics Data System (ADS)

    Gedelian, Cynthia; Coplin, Kim; Epstein, Arthur

    2002-10-01

    Conducting polymers are an exciting development in the fields of both physics and chemistry. They have the potential to revolutionize the electronics industry by allowing for the creation of flexible and/or transparent circuits and LED's in many applications. We present the millisecond photoinduced absorption (PA) spectrum of a methoxy-substituted monomer derivative of poly (p-phenylene vinylene) (PPV) in the near-infrared to visible region (1.1 eV to 2.5 eV). A prominent PA peak was found near 2.1 eV when the sample was excited with both 2.7 eV and ultraviolet pump energies. We also report temperature, frequency, and intensity dependence studies of the 2.1 eV PA peak. Our results indicate exciton formation consistent with previous studies of the monomer [1] and similar studies of the related segmented block copolymer [2]. [1] E. Kyllo, et al., Synth. Met. 116, 189 (2001). [2] D. Clark, et al., Bull. Am. Phys. Soc. 46, 9 (2001).

  3. Self-assembly of semiconductor organogelator nanowires for photoinduced charge separation.

    PubMed

    Wicklein, André; Ghosh, Suhrit; Sommer, Michael; Würthner, Frank; Thelakkat, Mukundan

    2009-05-26

    We investigated an innovative concept of general validity based on an organogel/polymer system to generate donor-acceptor nanostructures suitable for charge generation and charge transport. An electron conducting (acceptor) perylene bisimide organogelator forms nanowires in suitable solvents during gelation process. This phenomenon was utilized for its self-assembly in an amorphous hole conducting (donor) polymer matrix to realize an interpenetrating donor-acceptor interface with inherent morphological stability. The self-assembly and interface generation were carried out either stepwise or in a single-step. Morphology of the donor-acceptor network in thin films obtained via both routes were studied by a combination of scanning electron microscopy and atomic force microscopy. Additionally, photoinduced charge separation and charge transport in these systems were tested in organic solar cells. Fabrication steps of multilayer organogel/polymer photovoltaic devices were optimized with respect to morphology and surface roughness by introducing additional smoothening layers and charge injection/blocking layers. An inverted cell geometry was used here in which electrons are collected at the bottom electrode and holes at the top electrode. The simultaneous preparation of the interface exhibits almost 3-fold improvement in device characteristics compared to the successive method. The device characteristics under AM1.5 spectral conditions and 100 mW/cm(2) for the simultaneous preparation route are short circuit current J(sc) = 0.28 mA cm(-2), open circuit voltage V(OC) = 390 mV, fill factor FF = 38%, and a power conversion efficiency eta = 0.041%.

  4. Reversible modulated mid-infrared absorption of Ag/TiO{sub 2} by photoinduced interfacial charge transfer

    SciTech Connect

    Xu, S. C. E-mail: ghli@issp.ac.cn; Li, L.; Pan, S. S.; Luo, Y. Y.; Zhang, Y. X.; Li, G. H. E-mail: ghli@issp.ac.cn

    2014-10-06

    An enhanced mid-infrared absorption in Ag nanoparticles-decorated TiO{sub 2} microflowers was reported. It was found that the mid-infrared absorption of the Ag/TiO{sub 2} complex depends strongly on the content and size of Ag nanoparticles, the higher the Ag nanoparticles content, the stronger the infrared absorption. The average reflectivity in the entire mid-infrared region of the microflowers drops from 57.6% to 10.5% after Ag nanoparticles decoration. Reversible modulated mid-infrared absorption properties were found in the Ag/TiO{sub 2} complexes upon alternative illumination of visible and UV light due to the photoinduced interfacial electron transfer between TiO{sub 2} semiconductor and Ag nanoparticles.

  5. Determination of the structural features of a long-lived electron-transfer state of 9-mesityl-10-methylacridinium ion.

    PubMed

    Hoshino, Manabu; Uekusa, Hidehiro; Tomita, Ayana; Koshihara, Shin-ya; Sato, Tokushi; Nozawa, Shunsuke; Adachi, Shin-ichi; Ohkubo, Kei; Kotani, Hiroaki; Fukuzumi, Shunichi

    2012-03-14

    Extensive efforts have been devoted to developing electron donor-acceptor systems that mimic the utilization of solar energy that occurs in photosynthesis. X-ray crystallographic analysis shows how absorbed photon energy is stabilized in those compounds by structural changes upon photoinduced electron transfer (ET). In this study, structural changes of a simple electron donor-acceptor dyad, 9-mesityl-10-methylacridinium cation (Acr(+)-Mes), upon photoinduced ET were directly observed by laser pump and X-ray probe crystallographic analysis. The N-methyl group in Acr(+) was bent, and a weak electrostatic interaction between Mes and a counteranion in the crystal (ClO(4)) was generated by photoinduced ET. These structural changes correspond to reduction and oxidation due to photoinduced ET and directly elucidate the mechanism in Acr(+)-Mes for mimicking photosynthesis efficiently.

  6. Time-resolved EPR identifies unexpected electron transfer in cryptochrome**

    PubMed Central

    Biskup, Till; Hitomi, Kenichi; Getzoff, Elizabeth D.; Krapf, Sebastian; Koslowski, Thorsten; Schleicher, Erik

    2012-01-01

    Tuning photoinduced electron transfer: Subtle differences in local sequence and conformation can produce diversity and specificity in electron transfer (ET) in proteins, despite high structural conservation of redox partners. For individual ET steps, distance is not necessarily the decisive parameter; orientation and solvent accessibility of ET partners, and therefore, stabilization of charge-separated states contribute substantially. PMID:22086606

  7. Photoinduced charge recombination in dipolar D-A-A photonic liquid crystal polymorphs.

    PubMed

    Mazza, Mercedes M A; Yamazaki, Shiori; Mai, Dieu X; Padgaonkar, Suyog; Peurifoy, Samuel; Goncalves, Ariane; Wu, Yi-Lin; Hu, Qiaoyu; Scott, Amy M

    2017-02-08

    A hexylalkoxy dipolar D-A-A molecule [7-(4-N,N-(bis(4-hexyloxyphenyl)amino)phenyl)-2,1,3-(benzothia-diazol-4-yl)methylene]propane-dinitrile, (C6-TPA-BT-CN) has been synthesized and the photophysics studied via femtosecond transient absorption spectroscopy (FsTA) in toluene and in amorphous and liquid crystalline spherulite thin films. Two spherulite macromolecular crystalline phases (banded, and non-banded) were observed through concentration dependent, solution processing techniques and are birefringent with a negative sign of elongation. A dramatic change in the electronic absorption from blue in amorphous films to green in spherulites was observed, and the molecular orientation was determined through the combined analysis of polarized light microscopy, X-ray diffraction, and scanning electron microscopy. FsTA was performed on amorphous films and show complex charge recombination dynamics, and a Stark effect, characterized from the combined TPA+˙ and [BT-CN]-˙ spectroscopic signatures at 450 nm and 510 nm and identified through spectroelectrochemistry. Radical cation dynamics of TPA+˙ was observed selectively at 750 nm with >503.3 ps (18%) recombination kinetics resulting in a rather significant yield of free charge carriers in amorphous films and consistent with previous reports on energetically disordered blend films. However, photoexcitation on large, non-banded spherulites areas (>250 μm) reveal average monoexponential charge recombination lifetimes of 169.2 ps from delocalized states similar to those observed in amorphous films and are 5× longer-lived than previous reports [Chang et al., J. Am. Chem. Soc., 2013, 135, 8790] of a related methyl-DPAT-BT-CN whose amorphous thin films were prepared through vapor deposition. Thus, the correlation between the microstructure of the blend film and the photoinduced radical pair dynamics described here is critical for developing a fundamental understanding of how dipolar states contribute to the charge carrier

  8. Photo-induced chemical reaction of trans-resveratrol.

    PubMed

    Zhao, Yue; Shi, Meng; Ye, Jian-Hui; Zheng, Xin-Qiang; Lu, Jian-Liang; Liang, Yue-Rong

    2015-03-15

    Photo-induced chemical reaction of trans-resveratrol has been studied. UV B, liquid state and sufficient exposure time are essential conditions to the photochemical change of trans-resveratrol. Three principal compounds, cis-resveratrol, 2,4,6-phenanthrenetriol and 2-(4-hydroxyphenyl)-5,6-benzofurandione, were successively generated in the reaction solution of trans-resveratrol (0.25 mM, 100% ethanol) under 100 μW cm(-2) UV B radiation for 4h. cis-Resveratrol, originated from isomerization of trans-resveratrol, resulted in 2,4,6-phenanthrenetriol through photocyclisation reaction meanwhile loss of 2 H. 2,4,6-Phenanthrenetriol played a role of photosensitizer producing singlet oxygen in the reaction pathway. The singlet oxygen triggered [4+2] cycloaddition reaction of trans-resveratrol, and then resulted in the generation of 2-(4-hydroxyphenyl)-5,6-benzofurandione through photorearrangement and oxidation reaction. The singlet oxygen reaction was closely related to the substrate concentration of trans-resveratrol in solution.

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

    NASA Astrophysics Data System (ADS)

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

    2017-02-01

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

  10. Origin of photo-induced transmitting oscillations in chalcogenide glasses.

    PubMed

    Tao, HaiZheng; Yang, ZhiYong; Lucas, Pierre

    2009-09-28

    Light-induced oscillatory behaviors of transmission in chalcogenide glasses are investigated using a continuous wave tunable Ti-sapphire laser. It is shown that phase change, thermal fluctuation, nonlinear index change and periodic self focusing are not at the origin of light-induced oscillatory transmittance in chalcogenide glasses. Instead, results indicate that the interference of transmitting and reflecting light is at the origin of the oscillatory behaviors of transmitted light. Just like the principle of Fabry-Pérot interferometer, these interferences result in a periodic change in transmission as the related interferential beams get in and out of phase. However, this transmitting oscillatory behavior can be registered by the detector only when the change of optical path length difference initiated by photo-induced effects is slower enough compared with the corresponding response time of the detector. Several photo-structural effects contribute to that phenomenon including photo-expansion, photo-darkening, and permanent self focusing. It appears that fluctuations of the light source intensity induce a wide distribution of the oscillatory periods.

  11. Diel variations in photoinduced oxidation of Hg0 in freshwater.

    PubMed

    Garcia, Edenise; Poulain, Alexandre J; Amyot, Marc; Ariya, Parisa A

    2005-05-01

    Experiments have been conducted to determine diel variations in photoinduced Hg0 oxidation in lake water under natural Hg0(aq) concentrations. Pseudo-first-order rates of photooxidation (k') were calculated for water freshly collected in a Canadian Shield lake, Lake Croche (45 degrees 56' N, 74 degrees 00' W), at different periods of the day and subsequently incubated in the dark. Hg0 oxidation rates ranged from 0.02 to 0.07 h(-1), increasing from sunrise to noon and then decreasing throughout the remainder of the day. These changes paralleled those in sunlight intensity integrated over 1 h preceding water collection, and suggested that the water freshly collected in daylight was rich in photochemically produced Hg0 oxidants. It was also estimated that under intense solar radiation, even if oxidation rates reached a peak, reduction of Hg(II) was the prevalent redox process. Inversely, Hg0 oxidation overcame DGM production during the night or at periods of weaker light intensity. Overall, these findings explain the decreases in the DGM pool generally observed overnight. They also support previous reports that, during summer days, volatilization of Hg0 from water represent an important step in the Hg cycle in freshwater systems.

  12. Photoinduced isomerization of lycopene and application to tomato cultivation.

    PubMed

    Heymann, Thomas; Raeke, Julia; Glomb, Marcus A

    2013-11-20

    The present study aimed to investigate if growth conditions have an impact on the isomeric composition of lycopene in tomatoes. First a model system for photoinduced isomerization was established. Tomato extracts were irradiated with a halogen lamp, whose wavelength spectrum is close to the spectrum of daylight and thus mimics field-grown cultivation. Different optical filters were interposed between lamp and samples to simulate greenhouse conditions. 5-cis-Lycopene was formed preferentially while the concentration of 7-cis-lycopene decreased in field-grown model systems. The change of isomerization in greenhouse model systems led to a significantly different ratio. Consequently 5-cis- and 7-cis-lycopene were identified as potent markers for the differentiation of various lighting conditions during cultivation. This result was verified in biological samples. Authentic field-grown tomatoes (var. Lycopersicon esculentum Mill. var. commune L. H. Bailey "Harzfeuer") showed a significantly higher content of 5-cis-lycopene 5.90 ± 0.45% compared to tomatoes of the same variety grown under electric lighting 4.11 ± 0.10%. Additionally, the ratio of 7-cis-lycopene was significantly lower under field-grown conditions.

  13. Theoretical approach to photoinduced inhomogeneous anisotropy in bacteriorhodopsin films.

    PubMed

    Acebal, P; Carretero, L; Blaya, S; Murciano, A; Fimia, A

    2007-07-01

    The aim of this work was to perform a complete study of the dynamic and steady-state photoinduced processes of thick bacteriorhodopsin (bR) films, taking into account all the physical parameters and the coupling of rate equations with the energy transfer equation. The theoretical approach was compared with experimental data, and good concordance was found between both sets of data. The theoretical approach shows that the values of the rate constants for solid bR films are about two or three orders of magnitude lower than those observed in solution. It can also be noted that the temperature change during the experiment had a great influence on the final values of transmittance and, consequently, on the inhomogeneous distribution along the coordinate of light propagation. The study shows that, depending on the intensity and wavelength of the pump beam, we can obtain a very inhomogeneous profile of the population densities, which implies an inhomogeneous profile of the birefringence and dichroism. Therefore, this must be taken into account in the applications described for this system.

  14. Photoinduced Giant Dielectric Constant in Lead Halide Perovskite Solar Cells.

    PubMed

    Juarez-Perez, Emilio J; Sanchez, Rafael S; Badia, Laura; Garcia-Belmonte, Germá; Kang, Yong Soo; Mora-Sero, Ivan; Bisquert, Juan

    2014-07-03

    Organic-inorganic lead trihalide perovskites have emerged as an outstanding photovoltaic material that demonstrated a high 17.9% conversion efficiency of sunlight to electricity in a short time. We have found a giant dielectric constant (GDC) phenomenon in these materials consisting on a low frequency dielectric constant in the dark of the order of ε0 = 1000. We also found an unprecedented behavior in which ε0 further increases under illumination or by charge injection at applied bias. We observe that ε0 increases nearly linearly with the illumination intensity up to an additional factor 1000 under 1 sun. Measurement of a variety of samples of different morphologies, compositions, and different types of contacts shows that the GDC is an intrinsic property of MAPbX3 (MA = CH3NH3(+)). We hypothesize that the large dielectric response is induced by structural fluctuations. Photoinduced carriers modify the local unit cell equilibrium and change the polarizability, assisted by the freedom of rotation of MA. The study opens a way for the understanding of a key aspect of the photovoltaic operation of high efficiency perovskite solar cells.

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

    PubMed Central

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

    2017-01-01

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

  16. Photoinduced superhydrophilicity: a kinetic study of time dependent photoinduced contact angle changes on TiO2 surfaces.

    PubMed

    Foran, Philip S; Boxall, Colin; Denison, Kieth R

    2012-12-21

    Transparent TiO(2) thin films were prepared on quartz substrates via a reverse micelle, sol-gel, spin-coating technique. The time dependence of the TiO(2) film photoinduced superhydrophilicity (PISH) was measured by goniometric observation of the contact angle, θ, of sessile water drops at the film surfaces. In these measurements, the TiO(2) substrate was illuminated by 315 nm light and drops were sequentially applied at a range of illumination times. Using a model for the wetting of heterogeneous surfaces derived by Israelachvili and Gee, these measurements were used to calculate the time dependence of f(2), the fractional surface coverage of the TiO(2) surface by adventitious contaminating organics (Israelachvili, J. N.; Gee, M. L. Contact angles on chemically heterogeneous surfaces. Langmuir 1989, 5, 288). Extending this model to include a Langmuir-Hinshelwood based kinetic analysis of f(2) as a function of time allowed for calculation of an expected value for θ immediately prior to illumination, that is, at illumination time t = 0. Such expected values of θ at t = 0 were calculated using two possible values of θ(1), the contact angle on a pristine unilluminated homogeneous TiO(2) surface: (i) θ(1) = 4° as suggested by, inter alia, Zubkov et al. (Zubkov, T.; Stahl, D.; Thompson, T. L.; Panayotov, D.; Diwald, O.; Yates, J. T. Ultraviolet Light-Induced Hydrophilicity Effect on TiO(2)(110)(1 × 1). Dominant Role of the Photooxidation of Adsorbed Hydrocarbons Causing Wetting by Water Droplets. J. Phys. Chem. B2005, 109, 15454); and (ii) where θ(1) = 25°, as suggested by Fujishima et al., representative of a more hydrophobic homogeneous TiO(2) surface that reconstructs upon exposure to ultraband gap illumination into a hydrophilic surface where θ(1) → 0° (Fujishima, A.; Zhang, X.; Tryk, D. A. TiO(2) photocatalysis and related surface phenomena Surf. Sci. Rep.2008, 63, 515). Analysis of data from our experiments and from selected literature sources

  17. PREFACE: Second International Conference on Photo-Induced Phase Transitions; Cooperative, non-linear and functional properties (PIPT'05)

    NASA Astrophysics Data System (ADS)

    Buron, Marylise; Collet, Eric

    2005-01-01

    This issue is a collection of papers presented at the 2nd International Conference on Photo-Induced Phase Transitions; Cooperative, non-linear and functional properties (PIPT'05), which was held in Rennes (France) on 24-28 May 2005 and chaired by Hervé Cailleau and Tadeusz Luty. The first PIPT conference was organized by Professor Keiichiro Nasu in Tsukuba, Japan, in 2001. During 5 days, PIPT'05 provided an interdisciplinary forum for research communications between solid state physicists, photophysicists, photochemists and photobiologists, as well as material scientists. Scientists came from all around the world (Europe, Japan, USA, Canada, ...). The fascinating scientific challenge of the possibility of triggering physical properties of a material by light excitation was at the heart of the exchange of ideas between scientists of the different fields. The topics of the conference were about light-induced phenomena in functional materials, nano-particles and devices, photo-induced structural, magnetic and/or electronic phase transitions, photo-induced gauge type phase transitions, photo-induced cooperative molecular switching and chemical reactions in solids, dynamics of out-of-equilibrium processes, light-driven non-thermal processes such as coherent phonons, shock waves, surface melting and femtomagnetism, precursor phenomena, coherent, co-operative and non-linear processes in excited states and new investigations by light, x-ray and electron probes. As you will see, the collection of papers presented here cover many of the fields mentioned above. The PIPT conferences, encompassing different areas of light-induced phenomena are also meant to bridge the gap between experimentalists and theoreticians, and to promote communication between scientists working on different continents. The present conference was attended by 148 participants from 17 countries, with the total number of 87 presentations (16 invited, 27 contributed talks and 44 posters). It is encouraging

  18. Simultaneous photoinduced generation of Fe(2+) and H2O2 in rivers: An indicator for photo-Fenton reaction.

    PubMed

    Mostofa, Khan M G; Sakugawa, Hiroshi

    2016-09-01

    The photo-Fenton reaction is a key source of the highly reactive hydroxyl radical (HO) that is produced by the reaction of simultaneous photo-induced generation of Fe(2)(+)-dissolved organic matter (DOM) with H2O2 in sunlit surface waters as well as in the treatment of organic pollutants in the advanced oxidation processes (AOPs). Concentrations of both H2O2 and Fe(2)(+)-DOM were dependent on time and total solar intensity flux, and their levels were highest in the diurnal samples collected at noon compared with the samples collected during the period before sunrise and after sunset. H2O2 and Fe(2)(+)-DOM concentrations during monthly readings were also found higher in comparison with the diurnal samples, shortly before sunrise or after sunset. A π-electron bonding system is formed between Fe and the functional groups in DOM (Fe-DOM), through electron donation from the functional groups of DOM to an empty d-orbital of Fe. The π-electron is loosely bound and is highly susceptible to a rapid excitation upon light exposure that will provide better understanding of the formation of aqueous electrons, superoxide radical anions, H2O2 and finally, photo-Fenton reactions, too. Our results imply that simultaneous generation of H2O2 and Fe(2)(+)-DOM upon sunlight exposure during the daytime is most likely to be the key photo-Fenton reaction pathway, taking place in surface waters.

  19. Retardation of the orientation relaxation of azo-dye doped amorphous polymers upon photoinduced isomerization

    NASA Astrophysics Data System (ADS)

    Chan, S. W.; Quatela, A.; Casalboni, M.; Nunzi, J.-M.

    2006-08-01

    The orientation relaxation upon photo-induced isomerization of azo-dyes was studied. All-optical poling (AOP) and photo-induced birefringence, which are based on the mechanism of angular selective photo-isomerization, were employed to manipulate the angular distribution of azo-dyes (Disperse-red 1) doped in three different amorphous polymers: (poly(methyl methacrylate) PMMA, poly(carbonate) PC and poly(sulfone) PSU), with different glass transition temperature (T g). In the case of AOP, quasi-permanent macroscopic second-order nonlinear optical susceptibility χ (2) was inscribed in the dye-doped centro-symmetric polymer systems, while in the case of photo-induced birefringence, quasi-permanent birefringence Δn was inscribed in the dye-doped isotropic polymer systems. Relaxation of χ (2) and Δn were monitored upon different duration of AOP and photo-induced birefringence preparation. Experimental results show that azo-dye orientation relaxation follows the duration of the photo-nduced isomerization process: the longer the photo-induced isomerization process, the slower the relaxation of the inscribed χ (2) and Δn. In addition, retardation of the orientation relaxation does not follow a simple relation with hardness (T g) of the polymer host. Causes of the orientation relaxation retardation are discussed.

  20. Photo-induced Doping in GaN Epilayers with Graphene Quantum Dots

    PubMed Central

    Lin, T. N.; Inciong, M. R.; Santiago, S. R. M. S.; Yeh, T. W.; Yang, W. Y.; Yuan, C. T.; Shen, J. L.; Kuo, H. C.; Chiu, C. H.

    2016-01-01

    We demonstrate a new doping scheme where photo-induced carriers from graphene quantum dots (GQDs) can be injected into GaN and greatly enhance photoluminescence (PL) in GaN epilayers. An 8.3-fold enhancement of PL in GaN is observed after the doping. On the basis of time-resolved PL studies, the PL enhancement is attributed to the carrier transfer from GQDs to GaN. Such a carrier transfer process is caused by the work function difference between GQDs and GaN, which is verified by Kelvin probe measurements. We have also observed that photocurrent in GaN can be enhanced by 23-fold due to photo-induced doping with GQDs. The improved optical and transport properties from photo-induced doping are promising for applications in GaN-based optoelectronic devices. PMID:26987403

  1. Preparation and photo-induced charge transfer of the composites based on 3D structural CdS nanocrystals and MEH-PPV

    SciTech Connect

    Deng, Dan; Shi, Minmin; Chen, Fei; Chen, Lin; Jiang, Xiaoxia; Chen, Hongzheng

    2010-05-15

    We report the synthesis of 3D structural CdS nanocrystals by a simple biomolecule-assisted hydrothermal process. The CdS nanocrystals are composed of many branched nanorods with the diameter of about 50 nm, and the length of about 250 nm. The phase and crystallographic properties are characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray diffractometry (XRD). The composites based on CdS nanocrystals and poly[2-methoxy-5-(2-ethylhexyloxy-p-phenylenevinylene)] (MEH-PPV) have been prepared by spin-coating of the mixture in the common solvent. The optical properties of the composites are investigated using ultraviolet-visible (UV-Vis) absorption and photoluminescence (PL) spectroscopies. A significant fluorescence quenching of MEH-PPV in the composites is observed at high CdS nanocrystals/MEH-PPV ratios, indicating that the photo-induced charge transfer occurred due to the energy level offset between the donor MEH-PPV and the acceptor CdS nanocrystals. The obvious photovoltaic behavior of the solar cell made from this composite further demonstrates the mentioned photo-induced charge transfer process. (author)

  2. Recent advances in photoinduced donor/acceptor copolymerization

    NASA Astrophysics Data System (ADS)

    Jönsson, S.; Viswanathan, K.; Hoyle, C. E.; Clark, S. C.; Miller, C.; Morel, F.; Decker, C.

    1999-05-01

    Photoinitiated free radical polymerization of donor (D)/acceptor (A) type monomers has gained considerable interest due to the possibility to efficiently photopolymerize non-acrylate based systems. Furthermore, this photoinduced alternating copolymerization can be accomplished without the presence of a conventional free radical generating photoinitiator. In the past, we have shown that the structural influences in the direct photolysis of N-Alkyl and N-Arylmaleimides as well as their corresponding ground state charge transfer complexes (CTC) with suitable donors have carefully been investigated. For certain combinations of A and D type monomers, a direct photolysis of the ground state complex or the excitation of the acceptor, followed by the formation of an exciplex, has been shown to initiate the copolymerization. Herein, we show that the main route of initiation is based on inter or intra molecular H-abstraction from an excited state maleimide, whereby no exciplex formation takes place. H-abstraction will predominantly take place in systems where easily abstractable hydrogens are present. Our laser flash photolysis investigation, ESR [1] (A. Hiroshi, I. Takasi, T. Nosi, Macromol. Chem. 190 (1989) 2821) and phosphorescence emissions [2,3] (K.S. Chen, T. Foster, J.K.S. Wan, J. Phys. Chem. 84 (1980) 2473; C.J. Seliskar, S.P. McGlynn, J. Chem. Phys. 55 (1971) 4337) studies show that triplet excited states of N-alkyl substituted maleimides (RMI), which are well known strong precursors for direct H-abstractions from aliphatic ethers and secondary alcohols, are formed upon excitation. Rates of copolymerization and degrees of conversion for copolymerization of maleimide/vinyl ether pairs in air and nitrogen have been measured as a function of hydrogen abstractability of the excited triplet state MI as well as the influence of concentration and hydrogen donating effect of the hydrogen donor.

  3. Enhancement of Photoinduced Charge-Order Melting via Anisotropy Control by Double-Pulse Excitation in Perovskite Manganites: Pr_{0.6}Ca_{0.4}MnO_{3}.

    PubMed

    Yada, H; Ijiri, Y; Uemura, H; Tomioka, Y; Okamoto, H

    2016-02-19

    To control the efficiency of photoinduced charge-order melting in perovskite manganites, we performed femtosecond pump-probe spectroscopy using double-pulse excitation on Pr_{0.6}Ca_{0.4}MnO_{3}. The results revealed that the transfer of the spectral weight from the near-infrared to infrared region by the second pump pulse is considerably enhanced by the first pump pulse and that the suppression of crystal anisotropy, that is, the decrease of long-range lattice deformations due to the charge order by the first pump pulse is a key factor to enhance the charge-order melting. This double-pulse excitation method can be applied to various photoinduced transitions in complex materials with electronic and structural instabilities.

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

    PubMed

    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.

  5. Photoinduced phase transition in tetrathiafulvalene- p -chloranil observed in femtosecond reflection spectroscopy

    NASA Astrophysics Data System (ADS)

    Okamoto, H.; Ishige, Y.; Tanaka, S.; Kishida, H.; Iwai, S.; Tokura, Y.

    2004-10-01

    Photoinduced transitions from ionic (I) to neutral (N) and neutral (N) to ionic (I) phases in an organic charge transfer (CT) complex, tetrathiafulvalene- p -chloranil (TTF-CA), were investigated by femtosecond pump-probe reflection spectroscopy. Transient reflectivity changes of the intramolecular transition band of TTF sensitive to the degree of CT between a donor molecule of TTF and an acceptor molecule of CA are measured as a function of excitation energy, excitation density, and temperature. By adopting the multilayer model for the analysis of the obtained transient reflectivity spectra, we have derived the time characteristics of amounts and spatial distributions of photoinduced N(I) states in the I(N) phase. The results reveal that the I to N(IN) transition induced by the resonant excitation of the CT band at 4K is composed of three processes; (1) formation of a confined one-dimensional (1D) N domain, that is, a sequence of D0A0 pairs, just after the photoexcitation, (2) multiplication of the 1D N domains to the semimacroscopic N states up to 20ps within the absorption depth of the excitation light, and (3) proceeding of the IN transition along the direction normal to the sample surface. At 77K near the NI transition temperature (Tc=81K) , the size of the 1D N domain initially produced is enlarged and its multiplication process is strongly enhanced. When the excitation energy is increased, the initial photoproduct is changed from the confined 1D N domain to the positively and negatively charged N states. The spatial size of the latter is considerably larger than that of the former, indicating that the introduction of charge carriers makes the neighboring I state strongly unstable. The dynamics of the photoinduced N to I(NI) transition has also been investigated. The 1D I domains are initially produced by lights, however, they decay within 20ps even if the density of the I domains is increased. The results demonstrate that there is a clear difference of the

  6. Determination of photoinduced and intrinsic birefringences in PMMA/DR13 guest-host film

    NASA Astrophysics Data System (ADS)

    Dall'Agnol, Fernando Fuzinatto; Shimizu, Flávio Makoto; Giacometti, José A.

    2014-07-01

    We report measurements and analysis of photoinduced birefringence (PIB) in polymeric stretched films, hence, with an intrinsic birefringence (IB) associated to the polymeric chain orientation. It was found that transmittance signal is dependent on the angle between the film stretching direction and the probe light polarization, increasing or decreasing relatively to IB signal. Theoretical analysis considered that light propagates through the film having a photoinduced and intrinsic birefringences with independent optical axes. The transmittance signal dependence on the film angle is correctly accounted and our approach could give a phenomenological elucidation to the effect known as the inverse relaxation effect.

  7. Stretched exponential kinetics for photoinduced birefringence in azo dye doped PVA films

    NASA Astrophysics Data System (ADS)

    Yang, Hye Ri; Kim, Eun Ju; Lee, Sang Jo; Kim, Gun Yeup; Kwak, Chong Hoon

    2009-05-01

    We fabricated azo dye (methylorange) doped poly vinyl alcohol (MO/PVA) thin films and measured the photoinduced birefringence (PIB) kinetics for several pump beam intensities and for various MO concentrations by using the pump-probe technique. A novel approach to explain the transient behaviors of the photoinduced anisotropy is presented by employing an empirical stretched exponential time response in the course of the trans-cis-trans photoisomerization of azo molecules and is compared with the experimental data, showing excellent agreement. The stretched exponent is estimated to be β = 0.34 ± 0.04, revealing amorphous nature of the MO/PVA system.

  8. Qsars for photoinduced toxicity: 1. acute lethality of polycyclic aromatic hydrocarbons to daphnia magna'

    SciTech Connect

    Mekenyan, O.G.; Ankley, G.T.; Veith, G.D.; Call, D.J.

    1994-01-01

    Research with a variety of aquatic species has shown that while polycyclic aromatic hydrocarbons (PAHs) are generally not acutely toxic in conventional laboratory tests, many are extremely toxic in the presence of sunlight. In an effort to develop a model for predicting which PAHs may exhibit photo-induced toxicity, Newsted and Giesy (1987) reported a parabolic relationship between the toxicity and the energy of the triplet state of a variety of PAHs. The authors have reexamined these data and propose a more mechanistic explanation for the prediction of photo-induced PAH toxicity. They sought a molecular descriptor which could be computed from structure rather than measured empirically.

  9. Novel mechanism of photoinduced reversible phase transitions in molecule-based magnets.

    PubMed

    Kawamoto, T; Asai, Y; Abe, S

    2001-01-08

    A novel microscopic mechanism of bidirectional structural changes is proposed for the photoinduced magnetic phase transition in Co-Fe Prussian blue analogs on the basis of ab initio quantum chemical cluster calculations. It is shown that the local potential energies of various spin states of Co are sensitive to the number of nearest neighbor Fe vacancies. As a result, the forward and backward structural changes are most readily initiated by excitation of different local regions by different photons. This mechanism suggests an effective strategy to realize photoinduced reversible phase transitions in a general system consisting of two local components.

  10. Band Structure Simulations of the Photoinduced Changes in the MgB2:Cr Films

    PubMed Central

    Kityk, Iwan V.; Fedorchuk, Anatolii O.; Ozga, Katarzyna; AlZayed, Nasser S.

    2015-01-01

    An approach for description of the photoinduced nonlinear optical effects in the superconducting MgB2:Cr2O3 nanocrystalline film is proposed. It includes the molecular dynamics step-by-step optimization of the two separate crystalline phases. The principal role for the photoinduced nonlinear optical properties plays nanointerface between the two phases. The first modified layers possess a form of slightly modified perfect crystalline structure. The next layer is added to the perfect crystalline structure and the iteration procedure is repeated for the next layer. The total energy here is considered as a varied parameter. To avoid potential jumps on the borders we have carried out additional derivative procedure.

  11. Photo-induced structural changes in Ge-Sb-Se films

    NASA Astrophysics Data System (ADS)

    Lin, Li; Wang, Guoxiang; Shen, Xiang; Dai, Shixun; Xu, Tiefeng; Nie, Qiuhua

    2017-03-01

    Amorphous Ge-Sb-Se thin films have been prepared by the radio-frequency (RF) magnetron co-sputtering deposition technique, and their intrinsic photosensitivity and photo-induced structural changes have been investigated. The results show a crossover from photodarkening (PD) to photobleaching (PB) in the films when the film compositions change from Se-deficient to rich. Further Raman analysis on these as-prepared thin films irradiated with a laser of wavelength 655 nm in every five minutes provides direct evidence of photo-induced structure rearrangements.

  12. The nature of photoinduced changes in the magnetostriction of yttrium-iron garnet single crystals

    SciTech Connect

    Vorob'eva, N. V.

    2011-05-15

    A model of the occurrence of photoinduced changes in linear magnetostriction is proposed based on a complex experimental study of magnetostrictive strains in yttrium-iron garnets Y{sub 3}Fe{sub 5}O{sub 12} with low contents of different impurities. Analytical expressions for calculating the magnetostriction in yttrium-iron garnet single crystals with different types of doping are presented. The correlation of the photoinduced change in the magnetostriction with the crystallographic features of the samples is demonstrated. The changes in the magnetostriction constants are analyzed quantitatively for samples prepared in different ways.

  13. Photoinduced refractive index change and absorption bleaching in poly(methylphenylsilane) under varied atmospheres.

    SciTech Connect

    Potter, Barrett George, Jr.; Simmons-Potter, Kelly; Chandra, Haripin; Thomes, William Joseph, Jr.; Jamison, Gregory Marks

    2005-06-01

    Polysilane materials exhibit large photo-induced refractive index changes under low incident optical fluences, making them attractive candidates for applications in which rapid patterning of photonic device structures is desired immediately prior to their use. This agile fabrication strategy for integrated photonics inherently requires that optical exposure, and associated material response, occurs in nonlaboratory environments, motivating the study of environmental conditions on the photoinduced response of the material. The present work examines the impact of atmosphere on the photosensitive response of poly(methylphenylsilane) (PMPS) thin films in terms of both photoinduced absorption change and refractive index modification. Material was subjected to UV light exposure resonant with the lowest energy optical transition associated with the conjugated Si-Si backbone. Exposures were performed in both aerobic and anaerobic atmospheres (oxygen, air, nitrogen, and 5% H{sub 2}/95% N{sub 2}). The results clearly demonstrate that the photosensitive response of this model polysilane material was dramatically affected by local environment, exhibiting a photoinduced refractive index change, when exposed under an oxygen containing atmosphere, that was twice that observed under anaerobic conditions. This effect is discussed in terms of photo-oxidation processes within the polysilane structure and in the context of the need for predictable photosensitive refractive index change in varied photoimprinting environments.

  14. EFFECT OF IRRADIANCE SPECTRA ON THE PHOTOINDUCED TOXICITY OF THREE POLYCYCLIC AROMATIC HYDROCARBONS

    EPA Science Inventory

    Photoinduced toxicity of polycyclic aromatic hydrocarbons (PAHs) is dependent on the concentration of compounds present and the dose of light received. Of the light present, only those wavelengths absorbed by the compound have the potential to initiate the photochemical events un...

  15. Photo-induced oxidation and amorphization of trigonal tellurium: A means to engineer hybrid nanostructures and explore glass structure under spatial confinement

    SciTech Connect

    Vasileiadis, Thomas; Yannopoulos, Spyros N.

    2014-09-14

    Controlled photo-induced oxidation and amorphization of elemental trigonal tellurium are achieved by laser irradiation at optical wavelengths. These processes are monitored in situ by time-resolved Raman scattering and ex situ by electron microscopies. Ultrathin TeO₂ films form on Te surfaces, as a result of irradiation, with an interface layer of amorphous Te intervening between them. It is shown that irradiation, apart from enabling the controllable transformation of bulk Te to one-dimensional nanostructures, such as Te nanotubes and hybrid core-Te/sheath-TeO₂ nanowires, causes also a series of light-driven (athermal) phase transitions involving the crystallization of the amorphous TeO₂ layers and its transformation to a multiplicity of crystalline phases including the γ-, β-, and α-TeO₂ crystalline phases. The kinetics of the above photo-induced processes is investigated by Raman scattering at various laser fluences revealing exponential and non-exponential kinetics at low and high fluence, respectively. In addition, the formation of ultrathin (less than 10 nm) layers of amorphous TeO₂ offers the possibility to explore structural transitions in 2D glasses by observing changes in the short- and medium-range structural order induced by spatial confinement.

  16. Kinetics of a photoinduced NH tautomerism of free-base porphyrins in crystalline matrices at low temperatures: Computer simulations and experiment

    NASA Astrophysics Data System (ADS)

    Stanishevsky, I. V.; Solovyov, K. N.

    2004-03-01

    Photoinduced NH tautomerism, along with the reaction pathways of phototautomerization in tetrabenzoporphin and porphin free bases in n-octane polycrystalline matrices at 77 K, is studied by simulation of kinetic processes and their experimental observation. The simulation of the processes is performed by the numerical solution of the system of kinetic equations describing the populations of electronic levels and transitions between them. Kinetic dependences are obtained by measuring the perturbation of stationary fluorescence of one component of the 0-0 doublet origin upon pulsed selective photoexcitation of the other component. For two tautomeric forms related by the reversibility of the photochemical reaction, under the assumption of synchronism of the NH rearrangement, (i) analytical solutions governing the reaction rate are found, (ii) a method of measuring the rate constants of the proton rearrangement is suggested and the constants themselves are estimated, and (iii) direct evidence of the participation of T 1 levels in the photochemical reaction is obtained. With the aid of numerical simulations, the specific features of kinetic manifestation of an asynchronous mechanism of the photoinduced NH rearrangement are studied.

  17. Photoinduced, Copper-Catalyzed Carbon-Carbon Bond Formation with Alkyl Electrophiles: Cyanation of Unactivated Secondary Alkyl Chlorides at Room Temperature.

    PubMed

    Ratani, Tanvi S; Bachman, Shoshana; Fu, Gregory C; Peters, Jonas C

    2015-11-04

    We have recently reported that, in the presence of light and a copper catalyst, nitrogen nucleophiles such as carbazoles and primary amides undergo C-N coupling with alkyl halides under mild conditions. In the present study, we establish that photoinduced, copper-catalyzed alkylation can also be applied to C-C bond formation, specifically, that the cyanation of unactivated secondary alkyl chlorides can be achieved at room temperature to afford nitriles, an important class of target molecules. Thus, in the presence of an inexpensive copper catalyst (CuI; no ligand coadditive) and a readily available light source (UVC compact fluorescent light bulb), a wide array of alkyl halides undergo cyanation in good yield. Our initial mechanistic studies are consistent with the hypothesis that an excited state of [Cu(CN)2](-) may play a role, via single electron transfer, in this process. This investigation provides a rare example of a transition metal-catalyzed cyanation of an alkyl halide, as well as the first illustrations of photoinduced, copper-catalyzed alkylation with either a carbon nucleophile or a secondary alkyl chloride.

  18. Photoinduced, Copper-Catalyzed Carbon–Carbon Bond Formation with Alkyl Electrophiles: Cyanation of Unactivated Secondary Alkyl Chlorides at Room Temperature

    PubMed Central

    Ratani, Tanvi S.; Bachman, Shoshana; Fu, Gregory C.; Peters, Jonas C.

    2015-01-01

    We have recently reported that, in the presence of light and a copper catalyst, nitrogen nucleophiles such as carbazoles and primary amides undergo C–N coupling with alkyl halides under mild conditions. In the present study, we establish that photoinduced, copper-catalyzed alkylation can also be applied to C–C bond formation, specifically, that the cyanation of unactivated secondary alkyl chlorides can be achieved at room temperature to afford nitriles, an important class of target molecules. Thus, in the presence of an inexpensive copper catalyst (CuI; no ligand co-additive) and a readily available light source (UVC compact fluorescent light bulb), a wide array of alkyl halides undergo cyanation in good yield. Our initial mechanistic studies are consistent with the hypothesis that an excited state of [Cu(CN)2]− may play a role, via single electron transfer, in this process. This investigation provides a rare example of a transition metal-catalyzed cyanation of an alkyl halide, as well as the first illustrations of photoinduced, copper-catalyzed alkylation with either a carbon nucleophile or a secondary alkyl chloride. PMID:26491957

  19. Influence of photoinduced Bi-related self-doping on the photocatalytic activity of BiOBr nanosheets

    NASA Astrophysics Data System (ADS)

    Wu, Dan; Yue, Songtao; Wang, Wei; An, Tiacheng; Li, Guiying; Ye, Liqun; Yip, Ho Yin; Wong, Po Keung

    2017-01-01

    Under UV irradiation, self-doped Bi5+ is evidenced to be generated on the surface of BiOBr nanosheets, but with well-preserved crystal structure and morphology compared with pure counterpart. Bi5+ self-doping BiOBr (BiOBr-4) exhibits distinct photocatalytic mode for dyes degradation, as compared with pure BiOBr nanosheets. These photodegradation distinctions are mainly due to the simultaneous occurrence of two photoinduced hole (h+) mediated oxidation processes on the BiOBr surfaces: (1) a portion of photoexcited h+ participates in the photocatalytic oxidation of dyes, and (2) partial h+ involves the oxidation of Bi3+ to Bi5+. Notably, BiOBr-4 nanosheets comparatively show superior photocatalytic activity for the phenol decomposition as well as the bacterial inactivation. Besides Bi5+ induced narrowed bandgap and enhanced light adsorption capacity, significantly, the oxidative Bi5+ acts as electron traps to promote the photoexcited electron-hole separation and accelerate h+ migration, resulting in the considerable photocatalytic enhancement of BiOBr-4 nanosheets. These novel findings will not only give new insights into the photocatalytic mechanism but also explore new route to enhance photocatalytic performance of Bi-based materials.

  20. Hierarchical Sheet-on-Sheet ZnIn2S4/g-C3N4 Heterostructure with Highly Efficient Photocatalytic H2 production Based on Photoinduced Interfacial Charge Transfer.

    PubMed

    Zhang, Zhenyi; Liu, Kuichao; Feng, Zhiqing; Bao, Yanan; Dong, Bin

    2016-01-12

    We have realized in-situ growth of ultrathin ZnIn2S4 nanosheets on the sheet-like g-C3N4 surfaces to construct a "sheet-on-sheet" hierarchical heterostructure. The as-synthesized ZnIn2S4/g-C3N4 heterojunction nanosheets exhibit remarkably enhancement on the photocatalytic activity for H2 production. This enhanced photoactivity is mainly attributed to the efficient interfacial transfer of photoinduced electrons and holes from g-C3N4 to ZnIn2S4 nanosheets, resulting in the decreased charge recombination on g-C3N4 nanosheets and the increased amount of photoinduced charge carriers in ZnIn2S4 nanosheets. Meanwhile, the increased surface-active-sites and extended light absorption of g-C3N4 nanosheets after the decoration of ZnIn2S4 nanosheets may also play a certain role for the enhancement of photocatalytic activity. Further investigations by the surface photovoltage spectroscopy and transient photoluminescence spectroscopy demonstrate that ZnIn2S4/g-C3N4 heterojunction nanosheets considerable boost the charge transfer efficiency, therefore improve the probability of photoinduced charge carriers to reach the photocatalysts surfaces for highly efficient H2 production.

  1. Hierarchical Sheet-on-Sheet ZnIn2S4/g-C3N4 Heterostructure with Highly Efficient Photocatalytic H2 production Based on Photoinduced Interfacial Charge Transfer

    PubMed Central

    Zhang, Zhenyi; Liu, Kuichao; Feng, Zhiqing; Bao, Yanan; Dong, Bin

    2016-01-01

    We have realized in-situ growth of ultrathin ZnIn2S4 nanosheets on the sheet-like g-C3N4 surfaces to construct a “sheet-on-sheet” hierarchical heterostructure. The as-synthesized ZnIn2S4/g-C3N4 heterojunction nanosheets exhibit remarkably enhancement on the photocatalytic activity for H2 production. This enhanced photoactivity is mainly attributed to the efficient interfacial transfer of photoinduced electrons and holes from g-C3N4 to ZnIn2S4 nanosheets, resulting in the decreased charge recombination on g-C3N4 nanosheets and the increased amount of photoinduced charge carriers in ZnIn2S4 nanosheets. Meanwhile, the increased surface-active-sites and extended light absorption of g-C3N4 nanosheets after the decoration of ZnIn2S4 nanosheets may also play a certain role for the enhancement of photocatalytic activity. Further investigations by the surface photovoltage spectroscopy and transient photoluminescence spectroscopy demonstrate that ZnIn2S4/g-C3N4 heterojunction nanosheets considerable boost the charge transfer efficiency, therefore improve the probability of photoinduced charge carriers to reach the photocatalysts surfaces for highly efficient H2 production. PMID:26753795

  2. Hierarchical Sheet-on-Sheet ZnIn2S4/g-C3N4 Heterostructure with Highly Efficient Photocatalytic H2 production Based on Photoinduced Interfacial Charge Transfer

    NASA Astrophysics Data System (ADS)

    Zhang, Zhenyi; Liu, Kuichao; Feng, Zhiqing; Bao, Yanan; Dong, Bin

    2016-01-01

    We have realized in-situ growth of ultrathin ZnIn2S4 nanosheets on the sheet-like g-C3N4 surfaces to construct a “sheet-on-sheet” hierarchical heterostructure. The as-synthesized ZnIn2S4/g-C3N4 heterojunction nanosheets exhibit remarkably enhancement on the photocatalytic activity for H2 production. This enhanced photoactivity is mainly attributed to the efficient interfacial transfer of photoinduced electrons and holes from g-C3N4 to ZnIn2S4 nanosheets, resulting in the decreased charge recombination on g-C3N4 nanosheets and the increased amount of photoinduced charge carriers in ZnIn2S4 nanosheets. Meanwhile, the increased surface-active-sites and extended light absorption of g-C3N4 nanosheets after the decoration of ZnIn2S4 nanosheets may also play a certain role for the enhancement of photocatalytic activity. Further investigations by the surface photovoltage spectroscopy and transient photoluminescence spectroscopy demonstrate that ZnIn2S4/g-C3N4 heterojunction nanosheets considerable boost the charge transfer efficiency, therefore improve the probability of photoinduced charge carriers to reach the photocatalysts surfaces for highly efficient H2 production.

  3. Chemical Detection Based on Adsorption-Induced and Photo-Induced Stresses in MEMS Devices

    SciTech Connect

    Datskos, P.G.

    1999-04-05

    Recently there has been an increasing demand to perform real-time in-situ chemical detection of hazardous materials, contraband chemicals, and explosive chemicals. Currently, real-time chemical detection requires rather large analytical instrumentation that are expensive and complicated to use. The advent of inexpensive mass produced MEMS (micro-electromechanical systems) devices opened-up new possibilities for chemical detection. For example, microcantilevers were found to respond to chemical stimuli by undergoing changes in their bending and resonance frequency even when a small number of molecules adsorb on their surface. In our present studies, we extended this concept by studying changes in both the adsorption-induced stress and photo-induced stress as target chemicals adsorb on the surface of microcantilevers. For example, microcantilevers that have adsorbed molecules will undergo photo-induced bending that depends on the number of absorbed molecules on the surface. However, microcantilevers that have undergone photo-induced bending will adsorb molecules on their surfaces in a distinctly different way. Depending on the photon wavelength and microcantilever material, the microcantilever can be made to bend by expanding or contracting the irradiated surface. This is important in cases where the photo-induced stresses can be used to counter any adsorption-induced stresses and increase the dynamic range. Coating the surface of the microstructure with a different material can provide chemical specificity for the target chemicals. However, by selecting appropriate photon wavelengths we can change the chemical selectivity due to the introduction of new surface states in the MEMS device. We will present and discuss our results on the use of adsorption-induced and photo-induced bending of microcantilevers for chemical detection.

  4. Correlating electronic and vibrational motions in charge transfer systems

    SciTech Connect

    Khalil, Munira

    2014-06-27

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

  5. Photo-induced and electrooptic properties of (Pb,La)(Zr,Ti) O{sub 3} films for optical memories

    SciTech Connect

    Dimos, D.; Potter, B.G.; Sinclair, M.B.; Tuttle, B.A.; Warren, W.L.

    1993-09-01

    Photo-induced hysteresis changes and electrooptic effects in sol-gel Pb(Zr,Ti)0{sub 3} (PZT) and PLZT films have been studied in an effort to evaluate these materials for optical memory applications. The films exhibit two types of photo-induced changes in their hysteresis behavior which are suitable for optical storage. Both types of photo-induced hysteresis changes are due to trapping of photo-generated charge carriers at sites which minimize internal depolarizing fields. The photo-induced changes are reproducible and stable, which indicates that the charge traps are stable. However, improvements in photosensitivity will be required to develop a competitive technology for optical memories. In addition, polarization-dependent changes in the refractive indices can be the basis of a nondestructive optical readout technique. The index changes of films have been determined using a waveguide refractometry technique, which allows the extraordinary and ordinary index changes to be obtained independently.

  6. Photo-induced and electrooptic properties of (Pb,La)(Zr,Ti)O3 films for optical memories

    NASA Astrophysics Data System (ADS)

    Dimos, D.; Potter, B. G.; Sinclair, M. B.; Tuttle, B. A.; Warren, W. L.

    Photo-induced hysteresis changes and electro-optic effects in sol-gel Pb(Zr,Ti)03 (PZT) and PLZT films have been studied in an effort to evaluate these materials for optical memory applications. The films exhibit two types of photo-induced changes in their hysteresis behavior which are suitable for optical storage. Both types of photo-induced hysteresis changes are due to trapping of photo-generated charge carriers at sites which minimize internal depolarizing fields. The photo-induced changes are reproducible and stable, which indicates that the charge traps are stable. However, improvements in photosensitivity will be required to develop a competitive technology for optical memories. In addition, polarization-dependent changes in the refractive indices can be the basis of a nondestructive optical readout technique. The index changes of films have been determined using a waveguide refractometry technique, which allows the extraordinary and ordinary index changes to be obtained independently.

  7. Photo-induced current amplification in L-histidine modified nanochannels based on a highly charged photoacid in solution.

    PubMed

    Zhang, Minghui; Meng, Zheyi; Zhai, Jin; Jiang, Lei

    2013-03-21

    By UV light irradiation, we can adjust the charge of bistable photoacid molecules reversibly, so that photo-induced current amplification can be obtained, which offers a way to control nanochannels by turning the UV light on and off, alternately.

  8. Acute photo-induced toxicity and toxicokinetics of single compounds and mixtures of polycyclic aromatic hydrocarbons in zebrafish.

    PubMed

    Willis, Alison M; Oris, James T

    2014-09-01

    The present study examined photo-induced toxicity and toxicokinetics for acute exposure to selected polycyclic aromatic hydrocarbons (PAHs) in zebrafish. Photo-enhanced toxicity from co-exposure to ultraviolet (UV) radiation and PAHs enhanced the toxicity and exhibited toxic effects at PAH concentrations orders of magnitude below effects observed in the absence of UV. Because environmental exposure to PAHs is usually in the form of complex mixtures, the present study examined the photo-induced toxicity of both single compounds and mixtures of PAHs. In a sensitive larval life stage of zebrafish, acute photo-induced median lethal concentrations (LC50s) were derived for 4 PAHs (anthracene, pyrene, carbazole, and phenanthrene) to examine the hypothesis that phototoxic (anthracene and pyrene) and nonphototoxic (carbazole and phenanthrene) pathways of mixtures could be predicted from single exposures. Anthracene and pyrene were phototoxic as predicted; however, carbazole exhibited moderate photo-induced toxicity and phenanthrene exhibited weak photo-induced toxicity. The toxicity of each chemical alone was used to compare the toxicity of mixtures in binary, tertiary, and quaternary combinations of these PAHs, and a predictive model for environmental mixtures was generated. The results indicated that the acute toxicity of PAH mixtures was additive in phototoxic scenarios, regardless of the magnitude of photo-enhancement. Based on PAH concentrations found in water and circumstances of high UV dose to aquatic systems, there exists potential risk of photo-induced toxicity to aquatic organisms.

  9. Photoinduced hydrogen evolution in supramolecular devices with a rhenium photosensitizer linked to FeFe-hydrogenase model complexes.

    PubMed

    Liu, Jianhui; Jiang, Weina

    2012-08-28

    Coordination of the pyridyl-attached diiron azadithiolate hexacarbonyl complexes (2 and 3) through the pyridyl nitrogen to the Re on 10-phenanthroline rhenium (5a) and 2,9-diphenyl-1,10-phenanthroline rhenium (5b) forms novel [Re-Fe] complexes 7a, 7b and 8 respectively. Under visible light illumination using triethylamine as a sacrificial electron donor and [Re-Fe] type complexes (7a, 7b or 8) as catalysts, remarkably increased efficiency was observed for photoinduced hydrogen production with a turnover number reaching 11.8 from complex 7a and 8.75 from 7b. To the best of our knowledge, these are the best values compared to other [Re-Fe] photocatalysts reported so far. In contrast to the parent molecules, the turnover number by the intermolecular combination of complexes 6a and 2 showed a value of 5.23, and that from 6b and 2 is 3.8, while no H(2) was detected from 8a and 3 under the same experimental conditions. Obviously, the intramolecular combination of rhenium(I) and [2Fe2S] as a catalyst is promising for efficient H(2) evolution, and it is better than the intermolecular multi-component system.

  10. Exciplexes versus Loose Ion Pairs: How Does the Driving Force Impact the Initial Product Ratio of Photoinduced Charge Separation Reactions?

    PubMed Central

    2014-01-01

    Many donor–acceptor systems can undergo a photoinduced charge separation reaction, yielding loose ion pairs (LIPs). LIPs can be formed either directly via (distant) electron transfer (ET) or indirectly via the dissociation of an initially formed exciplex or tight ion pair. Establishing the prevalence of one of the reaction pathways is challenging because differentiating initially formed exciplexes from LIPs is difficult due to similar spectroscopic footprints. Hence, no comprehensive reaction model has been established for moderately polar solvents. Here, we employ an approach based on the time-resolved magnetic field effect (MFE) of the delayed exciplex luminescence to distinguish the two reaction channels. We focus on the effects of the driving force of ET and the solvent permittivity. We show that, surprisingly, the exciplex channel is significant even for an exergonic ET system with a free energy of ET of −0.58 eV and for the most polar solutions studied (butyronitrile). Our findings demonstrate that exciplexes play a crucial role even in polar solvents and at moderate driving forces, contrary to what is usually assumed. PMID:25243054

  11. Photoinduced interactions of supramolecular ruthenium(II) complexes with plasmid DNA: synthesis and spectroscopic, electrochemical, and DNA photocleavage studies.

    PubMed

    Swavey, Shawn; DeBeer, Madeleine; Li, Kaiyu

    2015-04-06

    Two new bridging ligands have been synthesized by combining substituted benzaldehydes with phenanthrolinopyrrole (php), resulting in new polyazine bridging ligands. The ligands have been characterized by (1)H NMR, mass spectroscopy, and elemental analysis. These new ligands display π-π* transitions above 500 nm with modest molar absorptivities. Upon excitation at the ligand-centered charge-transfer transition, weak emission with a maximum wavelength of 612 nm is observed. When coordinated to two ruthenium(II) bis(bipyridyl) groups, the new bimetallic complexes generated give an overall 4+ charge. The electronic transitions of the bimetallic ruthenium(II) complexes display traditional π-π* transitions at 287 nm and metal-to-ligand charge-transfer transitions at 452 nm with molar absorptivities greater than 30000 M(-1) cm(-1). Oxidation of the ruthenium(II) metal centers to ruthenium(III) occurs at potentials above 1.4 V versus the Ag/AgCl reference electrode. Spectroscopic and electrochemical measurements indicate that the ruthenium(II) moieties behave independently. Both complexes are water-soluble and show the ability to photonick plasmid DNA when irradiated with low-energy light above 550 nm. In addition, one of the complexes, [Ru(bpy)2php]2Van(4+), shows the ability to linearize plasmid DNA and gives evidence, by gel electrophoresis, of photoinduced binding to plasmid DNA.

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

    SciTech Connect

    Tang, Yu; Pattengale, Brian A.; Ludwig, John M.; Atifi, Abderrahman; Zinovev, Alexander V.; Dong, Bin; Kong, Qingyu; Zuo, Xiaobing; Zhang, Xiaoyi; Huang, Jier

    2015-12-17

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

  13. Synthesis of decacationic [60]fullerene decaiodides giving photoinduced production of superoxide radicals and effective PDT-mediation on antimicrobial photoinactivation

    PubMed Central

    Wang, Min; Maragani, Satyanarayana; Huang, Liyi; Jeon, Seaho; Canteenwala, Taizoon; Hamblin, Michael R.; Chiang, Long Y.

    2013-01-01

    We report a novel class of highly water-soluble decacationic methano[60]fullerene decaiodides C60[>M(C3N6+C3)2]-(I−)10[1-(I−)10] capable of co-producing singlet oxygen (Type-II) and highly reactive hydroxyl radicals, formed from superoxide radicals in Type-I photosensitizing reactions, upon illumination at both UVA and white light wavelengths. The O2-·-production efficiency of 1-(I−)10 was confirmed by using an O2-·-reactive bis(2,4-dinitrobenzenesulfonyl)tetrafluorofluorescein probe and correlated to the photoinduced electron-transfer event going from iodide anions to C360∗[>M(C3N6+C3)2] leading to C60-·[>M(C3N6+C3)2]. Incorporation of a defined number (ten) of quaternary ammonium cationic charges per C60 in 1 was aimed to enhance its ability to target pathogenic Gram-positive and Gram-negative bacterial cells. We used the well-characterized malonato[60]fullerene diester mono-adduct C60[>M(t-Bu)2] as the starting fullerene derivative to provide a better synthetic route to C60[>M(C3N6+C3)2] via transesterification reaction under trifluoroacetic acid catalyzed conditions. These compounds may be used as effective photosensitizers and nano-PDT drugs for photoinactivation of pathogens. PMID:23474903

  14. Photoinduced charge transfer properties and photocatalytic activity in Bi2O3/BaTiO3 composite photocatalyst.

    PubMed

    Fan, Haimei; Li, Haiyan; Liu, Bingkun; Lu, Yongchun; Xie, Tengfeng; Wang, Dejun

    2012-09-26

    A series of Bi(2)O(3)/BaTiO(3) composite photocatalysts with different mass ratios of Bi(2)O(3) vs BaTiO(3) were prepared by an impregnating-annealing method. X-ray diffraction (XRD), high-resolution transmission electron microscopic (HRTEM), and UV-vis diffuse reflection spectroscopy (DRS) confirmed that Bi(2)O(3) and BaTiO(3) coexisted in the composites. The results of surface photovoltage (SPV) experiments showed enhancements of photovoltaic response in composites, which indicated a higher separation efficiency of photoinduced charges due to the establishment of an efficient interfacial electric field between Bi(2)O(3) and BaTiO(3) in the composites. The consistency of phtocatalytic activity and photovoltaic response intensity of photocatalysts showed that the efficiency interfacial electric field between Bi(2)O(3) and BaTiO(3) played an important role in improving the degradation efficiency of Rhodamine B (RhB). The 60%-Bi(2)O(3)/BaTiO(3) sample with the best activity was found by optimizing the mass ratios of Bi(2)O(3) vs. BaTiO(3). On the basis of the work function (WF) measurements, a reasonable energy band diagram was proposed for BaTiO(3)/Bi(2)O(3) composite. It would be helpful in designing and constructing high efficiency heterogeneous semiconductor photocatalyst.

  15. Ultrafast dual photoresponse of isolated biological chromophores: link to the photoinduced mode-specific non-adiabatic dynamics in proteins.

    PubMed

    Bochenkova, Anastasia V; Andersen, Lars H

    2013-01-01

    The anionic wild-type Green Fluorescent Protein (GFP) chromophore defines an entire class of naturally occurring chromophores, which are based on the oxydized tyrosine side chain. The GFP chromophore exhibits an enriched photoinduced non-adiabatic dynamics in the multiple excited-state decay channels. Deactivation includes vibrational resonant photodetachment and internal conversion. Here, we provide detailed insight into the efficiency of different vibrational modes in promoting a selective photoresponse in the bare GFP chromophore anion. We introduce a general theoretical model that is capable of accounting for the alternative non-equivalent pathways in internal conversion, and we outline the factors, by which the photo-initiated response may be altered in this channel. The topography around the planar minimum in S1 and the two distinct types of the S1/S0 conical intersections obtained through high-level ab initio calculations provide direct support to the proposed model. There are mode-selective ways to control the photoresponse and to direct it towards a single excited-state decay channel. By tuning the excitation wavelength, the photoresponse may be directed towards the ultrafast non-statistical electron emission coupled with vibrational (de)coherence, whereas a vibrational pre-excitation in the ground state may lead to the ultrafast non-statistical internal conversion through a conical intersection. We also discuss the implication of our results to the photo-initiated non-adiabatic dynamics in the proteins.

  16. A bifunctional amorphous polymer exhibiting equal linear and circular photoinduced birefringences.

    PubMed

    Royes, Jorge; Provenzano, Clementina; Pagliusi, Pasquale; Tejedor, Rosa M; Piñol, Milagros; Oriol, Luis

    2014-11-01

    The large and reversible photoinduced linear and circular birefringences in azo-compounds are at the basis of the interest in these materials, which are potentially useful for several applications. Since the onset of the linear and circular anisotropies relies on orientational processes, which typically occur on the molecular and supramolecular length scale, respectively, a circular birefringence at least one order of magnitude lower than the linear one is usually observed. Here, the synthesis and characterization of an amorphous polymer with a dimeric repeating unit containing a cyanoazobenzene and a cyanobiphenyl moiety are reported, in which identical optical linear and circular birefringences are induced for proper light dose and ellipticity. A pump-probe technique and an analytical method based on the Stokes-Mueller formalism are used to investigate the photoinduced effects and to evaluate the anisotropies. The peculiar photoresponse of the polymer makes it a good candidate for applications in smart functional devices.

  17. Enhanced diffraction properties of photoinduced gratings in nematic liquid crystals doped with Disperse Red 1.

    PubMed

    Li, Hongjing; Wang, Jianhao; Wang, Changshun; Zeng, Pengfei; Pan, Yujia; Yang, Yifei

    2016-01-01

    Diffraction properties of photoinduced gratings recorded by overlapping two coherent beams at 532 nm in nematic liquid crystals doped with Disperse Red 1 were investigated with a probe beam at 632.8 nm. The grating was formed due to the alignment of dye molecules that leaded to the reorientation of the liquid crystal phase. The diffraction efficiency of the photoinduced grating was found to increase rapidly when the sample temperature was close to the clearing point in the nematic phase and a nearly 30-fold enhancement of the first-order diffraction efficiency was obtained. The pretransitional enhancement of the diffraction efficiency was discussed in terms of the reorientation of liquid crystals, optical nonlinearity effects and the onset of critical opalescence near the nematic-isotropic phase transition. Moreover, a peak shift of diffraction efficiency towards the lower temperature was observed with the increase of recording light intensity, which was attributed to laser induced photochemical disordering.

  18. Genetically engineered photoinducible homodimerization system with improved dimer-forming efficiency.

    PubMed

    Nihongaki, Yuta; Suzuki, Hideyuki; Kawano, Fuun; Sato, Moritoshi

    2014-03-21

    Vivid (VVD) is a photoreceptor derived from Neurospora Crassa that rapidly forms a homodimer in response to blue light. Although VVD has several advantages over other photoreceptors as photoinducible homodimerization system, VVD has a critical limitation in its low dimer-forming efficiency. To overcome this limitation of wild-type VVD, here we conduct site-directed saturation mutagenesis in the homodimer interface of VVD. We have found that the Ile52Cys mutation of VVD (VVD-52C) substantially improves its homodimer-forming efficiency up to 180%. We have demonstrated the utility of VVD-52C for making a light-inducible gene expression system more robust. In addition, using VVD-52C, we have developed photoactivatable caspase-9, which enables optical control of apoptosis of mammalian cells. The present genetically engineered photoinducible homodimerization system can provide a powerful tool to optically control a broad range of molecular processes in the cell.

  19. Enhanced diffraction properties of photoinduced gratings in nematic liquid crystals doped with Disperse Red 1

    PubMed Central

    LI, Hongjing; WANG, Jianhao; WANG, Changshun; ZENG, Pengfei; PAN, Yujia; YANG, Yifei

    2016-01-01

    Diffraction properties of photoinduced gratings recorded by overlapping two coherent beams at 532 nm in nematic liquid crystals doped with Disperse Red 1 were investigated with a probe beam at 632.8 nm. The grating was formed due to the alignment of dye molecules that leaded to the reorientation of the liquid crystal phase. The diffraction efficiency of the photoinduced grating was found to increase rapidly when the sample temperature was close to the clearing point in the nematic phase and a nearly 30-fold enhancement of the first-order diffraction efficiency was obtained. The pretransitional enhancement of the diffraction efficiency was discussed in terms of the reorientation of liquid crystals, optical nonlinearity effects and the onset of critical opalescence near the nematic-isotropic phase transition. Moreover, a peak shift of diffraction efficiency towards the lower temperature was observed with the increase of recording light intensity, which was attributed to laser induced photochemical disordering. PMID:27725471

  20. Photo-induced Modulation Doping in Graphene/Boron nitride Heterostructures

    NASA Astrophysics Data System (ADS)

    Velasco, Jairo, Jr.; Ju, Long; Hwang, Edwin; Kahn, Salman; Nosiglia, Casey; Tsai, Hsin-Zon; Yang, Wei; Zhang, Guangyu; Taniguchi, Takashi; Watanabe, Kenji; Zhang, Yuanbo; Crommie, Michael; Zettl, Alex; Wang, Feng

    2014-03-01

    Van der Waals heterostructures (VDH) provide an exciting new platform for materials engineering, where a variety of layered materials with different electrical, optical and mechanical responses can be stacked together to enable new physics and novel functionalities. We report an emerging optoelectronic phenomenon (i.e. photo-induced modulation doping) in the graphene-boron nitride VDH (G/BN heterostructure). We find it enables flexible and repeatable writing and erasing of charge doping in graphene with optical light. We show that the photo-induced modulation doping maintains the remarkable carrier mobility of the G/BN heterostructure, and it can be used to generate spatially varying doping profiles like pn junctions. Our work contributes towards understanding light matter interactions in VDHs, and introduces a simple technique for creating inhomogeneous doping in high mobility graphene devices. J. Velasco Jr. acknowledges support from UC President's Postdoctoral Fellowship.

  1. Eigenmodes of a quartz tuning fork and their application to photoinduced force microscopy

    NASA Astrophysics Data System (ADS)

    Kim, Bongsu; Jahng, Junghoon; Khan, Ryan Muhammad; Park, Sung; Potma, Eric O.

    2017-02-01

    We examine the mechanical eigenmodes of a quartz tuning fork (QTF) for the purpose of facilitating its use as a probe for multifrequency atomic force microscopy (AFM). We perform simulations based on the three-dimensional finite element method and compare the observed motions of the beams with experimentally measured resonance frequencies of two QTF systems. The comparison enabled us to assign the first seven asymmetric eigenmodes of the QTF. We also find that a modified version of single beam theory can be used to guide the assignment of mechanical eigenmodes of QTFs. The usefulness of the QTF for multifrequency AFM measurements is demonstrated through photoinduced force microscopy measurements. By using the QTF in different configurations, we show that the vectorial components of the photoinduced force can be independently assessed and that lateral forces can be probed in true noncontact mode.

  2. Photo-induced changes in a hybrid amorphous chalcogenide/silica photonic crystal fiber

    SciTech Connect

    Markos, Christos

    2014-01-06

    Photostructural changes in a hybrid photonic crystal fiber with chalcogenide nanofilms inside the inner surface of the cladding holes are experimentally demonstrated. The deposition of the amorphous chalcogenide glass films inside the silica capillaries of the fiber was made by infiltrating the nanocolloidal solution-based As{sub 25}S{sub 75}, while the photoinduced changes were performed by side illuminating the fiber near the bandgap edge of the formed glass nanofilms. The photoinduced effect of the chalcogenide glass directly red-shifts the transmission bandgap position of the fiber as high as ∼20.6 nm at around 1600 nm wavelength, while the maximum bandgap intensity change at ∼1270 nm was −3 dB.

  3. Negative signals of photoinduced current transient and thermally stimulated current spectroscopy in GaAs due to negative-U properties of oxygen

    NASA Astrophysics Data System (ADS)

    Kühnel, Günter

    2008-09-01

    Bulk GaAs grown under high oxygen potential shows an intermediate resistivity (ρ ˜3×103 Ω cm at room temperature) with an electron activation energy E =0.42 eV. The relevant defect has been identified in literature as off-centered substitutional oxygen with three different charge states. Photoelectrical measurements on such GaAs material exhibit distinctly anomalous signals. Photoinduced current transient spectroscopy (PICTS) shows a signal with a negative sign, whereas thermally stimulated currents (TSCs) are clearly lower than the dark current. By means of a set of coupled differential equations, the carrier exchange between the defect levels and the conduction band is described. Solving these rate equations, the PICTS and TSC curves are modeled. In this way, it could be demonstrated that the anomalous PICTS and TSC signals are caused by the negative-U behavior of the off-center oxygen. This is in agreement with results of infrared spectroscopy.

  4. Defects in {sup 6}LiInSe{sub 2} neutron detector investigated by photo-induced current transient spectroscopy and photoluminescence

    SciTech Connect

    Cui, Yunlong; Bhattacharya, Pijush; Buliga, Vladimir; Tupitsyn, Eugene; Rowe, Emmanuel; Wiggins, Brenden; Johnstone, Daniel; Stowe, Ashley; Burger, Arnold

    2013-08-26

    {sup 6}LiInSe{sub 2} is a promising thermal neutron semiconductor detector material. The performance of the detector is affected by the carrier mobility-lifetime products. Therefore, defects that function as carrier recombination centers need to be identified. In this letter, characterization of defect levels in {sup 6}LiInSe{sub 2} by photo-induced current transient spectroscopy (PICTS) and photoluminescence is reported. PICTS measurements revealed electron-related defects located at 0.22, 0.36, and 0.55 eV and hole-related defects at 0.19, 0.30, and 0.73 eV. Free exciton and donor-acceptor pairs (DAP) emissions were observed. The PICTS defect level values are consistent with those extracted from DAP transitions.

  5. A dinuclear Ru(II) complex capable of photoinduced ligand exchange at both metal centers.

    PubMed

    Albani, B A; Peña, B; Saha, S; White, J K; Schaeffer, A M; Dunbar, K R; Turro, C

    2015-11-28

    {[Ru(CH3CN)3]2(tppz)}(4+) (tppz = tetra-2-pyridylpyrazine) undergoes photoinduced CH3CN exchange with λirr ≥ 610 nm in H2O. In contrast, cis-{[Ru(tpy)(L)]2(bpm)}(4+) (tpy = 2,2':6',2''-terpyridine, bpm = 2,2'-bipyrimidine, L = CH3CN) is not reactive, but the complex with L = DMSO is photoactive. These complexes are potentially useful for the release of multiply caged drugs.

  6. Stochastic model for photoinduced surface relief grating formation through molecular transport in polymer films.

    SciTech Connect

    Juan, M.; Plain, J.; Bachelot, R.; Royer, P.; Gray, S. K.; Wiederrecht, G. P.; Univ. de Technologie de Troyes

    2008-09-01

    We use a stochastic model to study photoinduced surface relief grating (SRG) formation due to molecular transport in azobenzene polymer films. The model is shown to reproduce the essential experimental features of SRG formation. In particular, it predicts SRG formation under both p and s polarizations, and the double peaked topographies that can occur at early times of the process. The evolving molecular positions and orientations during exposure are also followed, providing a useful mechanistic picture of SRG dynamics.

  7. Stochastic model for photoinduced surface relief grating formation through molecular transport in polymer films

    SciTech Connect

    Juan, M. L.; Plain, J.; Bachelot, R.; Royer, P.; Gray, S. K.; Wiederrecht, G. P.

    2008-10-13

    We use a stochastic model to study photoinduced surface relief grating (SRG) formation due to molecular transport in azobenzene polymer films. The model is shown to reproduce the essential experimental features of SRG formation. In particular, it predicts SRG formation under both p and s polarizations, and the double peaked topographies that can occur at early times of the process. The evolving molecular positions and orientations during exposure are also followed, providing a useful mechanistic picture of SRG dynamics.

  8. Procedure for quantitative determination of effectiveness of photoinduced destruction of malignant tumors

    NASA Astrophysics Data System (ADS)

    Bizyuk, S. A.; Istomin, Yu. P.; Dzhagarov, B. M.

    2006-07-01

    We have developed a procedure for analysis of the functional status of blood vessels in tumor tissues using computer-assisted color scanning of tumor slices and also for a quantitative assessment of the effectiveness of photoinduced destruction of tumor tissues in animal experiments. Its major advantage is direct determination of the size of the tumor necrosis zone. The procedure has been tested in an experiment on three strains of malignant tumors with different morphologies.

  9. Monte-Carlo simulations of photoinduced fluorescence enhancement in semiconductor quantum dot arrays

    NASA Astrophysics Data System (ADS)

    Maenosono, Shinya

    2005-03-01

    Photoinduced fluorescence enhancement (PFE) in semiconductor quantum dot (QD) arrays is simulated by a Monte-Carlo method based on the distributed tunneling model. PFE, a property of a QD ensemble, is directly related to the blinking behavior of single QDs. The origin of PFE is attributed not to an increase in the emission intensity during the 'on' period, but to the prolongation of average 'on' time.

  10. Photoinduced changes in refractive index of nanostructured shungite-containing polyimide systems

    NASA Astrophysics Data System (ADS)

    Kamanina, N. V.; Serov, S. V.; Shurpo, N. A.; Rozhkova, N. N.

    2011-10-01

    Photoinduced changes in the refractive index of a conjugate polyimide (PI) matrix sensitized by shungite carbon nanoparticles have been studied for the first time. The results are compared to the data of previous investigations of the photorefractive properties of PI matrices doped with fullerenes, carbon nanotubes, and quantum dots. The nonlinear refractive index of the proposed material has been determined using the dynamic holography techniques. The position of conjugate polymer materials of this type among the other nonlinear optical systems is considered.

  11. Time-Resolved Studies of Photoinduced Birefringence in Azobenzene Dye-Doped Polymer Films

    DTIC Science & Technology

    2008-09-23

    Here we report on transient photoinduced birefrin- gence ( PIB ) measurements on several azo dye films using a nanosecond laser source with a 20ns time re...Our results show the response time of PIB to be sys- tematically related to the size of the lowest optical transition energy. Furthermore, our results...suggest that PIB effects can be used to discriminate between0003-6935/08/285074-04$15.00/0 © 2008 Optical Society of America 5074 APPLIED OPTICS / Vol

  12. 8-Methoxypsoralen photoinduced plasmid-chromosome recombination in Saccharomyces cerevisiae using a centromeric vector.

    PubMed Central

    Meira, L B; Henriques, J A; Magaña-Schwencke, N

    1995-01-01

    The characterization of a new system to study the induction of plasmid-chromosome recombination is described. Single-stranded and double-stranded centromeric vectors bearing 8-methoxypsoralen photoinduced lesions were used to transform a wild-type yeast strain bearing the leu2-3,112 marker. Using the SSCP methodology and DNA sequencing, it was demonstrated that repair of the lesions in plasmid DNA was mainly due to conversion of the chromosomal allele to the plasmid DNA. Images PMID:7784218

  13. Capturing ultrafast photoinduced local structural distortion of BiFeO3

    SciTech Connect

    Wen, Haidan; Sassi, Michel; Luo, Zhenlin; Adamo, Carolina; Schlom, Darrell G.; Rosso, Kevin M.; Zhang, Xiaoyi

    2015-10-14

    The interaction of light with materials is an intensively studied research forefront, in which the coupling of radiation energy to selective degrees of freedom offers contact-free tuning of functionalities on ultrafast time scales. Capturing the fundamental processes and understanding the mechanism of photoinduced structural rearrangement are essential to applications such as photo-active actuators and efficient photovoltaic devices. Using ultrafast x-ray absorption spectroscopy aided by density functional theory calculations, we reveal the local structural arrangement around the transition metal atom in a unit cell of the photoferroelectric archetype BiFeO3 film. The out-of-plane elongation of the unit cell is accompanied by the in-plane shrinkage with minimal change of interaxial lattice angles upon photoexcitation. This anisotropic elastic deformation of the unit cell is driven by localized electric field as a result of photoinduced charge separation, in contrast to a global lattice constant increase and lattice angle variations as a result of heating. The finding of a photoinduced elastic unit cell deformation elucidates a microscopic picture of photocarrier-mediated non-equilibrium processes in polar materials.

  14. Capturing ultrafast photoinduced local structural distortions of BiFeO3

    SciTech Connect

    Wen, Haidan; Sassi, Michel JPC; Luo, Zhenlin; Adamo, Carolina; Schlom, Darrell; Rosso, Kevin M.; Zhang, Xiaoyi

    2015-10-14

    The interaction of light with materials is an intensively studied research forefront, in which the coupling of radiation energy to selective degrees of freedom offers contact-free tuning of functionalities on ultrafast time scales. Capturing the fundamental processes and understanding the mechanism of photoinduced structural rearrangement are essential to applications such as photo-active actuators and efficient photovoltaic devices. Using ultrafast x-ray absorption spectroscopy aided by density functional theory calculations, we reveal the local structural arrangement around the transition metal atom in a unit cell of the photoferroelectric archetype BiFeO3 film. The out-of-plane elongation of the unit cell is accompanied by the in-plane shrinkage with minimal change of interaxial lattice angles upon photoexcitation. This uniaxial elastic deformation of the unit cell is driven by localized electric field as a result of photoinduced charge separation, in contrast to a global lattice constant increase and lattice angle variations as a result of heating. The finding of a photoinduced elastic unit cell deformation elucidates a microscopic picture of photocarrier-mediated nonequilibrium processes in polar materials.

  15. Capturing ultrafast photoinduced local structural distortions of BiFeO3

    DOE PAGES

    Wen, Haidan; Sassi, Michel JPC; Luo, Zhenlin; ...

    2015-10-14

    The interaction of light with materials is an intensively studied research forefront, in which the coupling of radiation energy to selective degrees of freedom offers contact-free tuning of functionalities on ultrafast time scales. Capturing the fundamental processes and understanding the mechanism of photoinduced structural rearrangement are essential to applications such as photo-active actuators and efficient photovoltaic devices. Using ultrafast x-ray absorption spectroscopy aided by density functional theory calculations, we reveal the local structural arrangement around the transition metal atom in a unit cell of the photoferroelectric archetype BiFeO3 film. The out-of-plane elongation of the unit cell is accompanied by themore » in-plane shrinkage with minimal change of interaxial lattice angles upon photoexcitation. This uniaxial elastic deformation of the unit cell is driven by localized electric field as a result of photoinduced charge separation, in contrast to a global lattice constant increase and lattice angle variations as a result of heating. The finding of a photoinduced elastic unit cell deformation elucidates a microscopic picture of photocarrier-mediated nonequilibrium processes in polar materials.« less

  16. Neuronal regulation of photo-induced pineal photoreceptor proteins in carp Catla catla.

    PubMed

    Seth, Mohua; Maitra, Saumen Kumar

    2010-08-01

    In the present in vitro study on the pineal in carp Catla catla, specific agonist and antagonists of receptors for different neuronal signals and regulators of intra-cellular Ca(++) and cAMP were used to gather basic information on the neuronal signal transduction cascade mechanisms in the photo-induced expression of rod-like opsin and alpha-transducin-like proteins in any fish pineal. Western-blot analysis followed by quantitative analysis of respective immunoblot data for both the proteins revealed that photo-induced expression of each protein was stimulated by cholinergic (both nicotinic and muscarinic) agonists and a dopaminergic antagonist, inhibited by both cholinergic antagonists and a dopaminergic agonist, but not affected by any agonists or antagonists of adrenergic (alpha(1), alpha(2) and beta(1)) receptors. Moreover, expression of each protein was stimulated by voltage gated L type calcium channel blocker, adenylate cyclase inhibitor and phosphodiesterase activator; but suppressed by the activators of both calcium channel and adenylate cyclase, and by phosphodiesterase inhibitor. Collectively, we report for the first time that both cholinergic and dopaminergic signals play an important, though antagonistic, role in the photo-induced expression of photoreceptor proteins in the fish pineal through activation of a signal transduction pathway in which both calcium and cAMP may act as the intracellular messengers.

  17. Capturing ultrafast photoinduced local structural distortions of BiFeO3

    NASA Astrophysics Data System (ADS)

    Wen, Haidan; Sassi, Michel; Luo, Zhenlin; Adamo, Carolina; Schlom, Darrell G.; Rosso, Kevin M.; Zhang, Xiaoyi

    2015-10-01

    The interaction of light with materials is an intensively studied research forefront, in which the coupling of radiation energy to selective degrees of freedom offers contact-free tuning of functionalities on ultrafast time scales. Capturing the fundamental processes and understanding the mechanism of photoinduced structural rearrangement are essential to applications such as photo-active actuators and efficient photovoltaic devices. Using ultrafast x-ray absorption spectroscopy aided by density functional theory calculations, we reveal the local structural arrangement around the transition metal atom in a unit cell of the photoferroelectric archetype BiFeO3 film. The out-of-plane elongation of the unit cell is accompanied by the in-plane shrinkage with minimal change of interaxial lattice angles upon photoexcitation. This anisotropic elastic deformation of the unit cell is driven by localized electric field as a result of photoinduced charge separation, in contrast to a global lattice constant increase and lattice angle variations as a result of heating. The finding of a photoinduced elastic unit cell deformation elucidates a microscopic picture of photocarrier-mediated non-equilibrium processes in polar materials.

  18. Highly active ppm level organic copper catalyzed photo-induced ICAR ATRP of methyl methacrylate.

    PubMed

    Jiang, Xiaowu; Wu, Jian; Zhang, Lifen; Cheng, Zhenping; Zhu, Xiulin

    2014-11-01

    A novel photo-induced homogeneous atom transfer radical polymerization (ATRP) system is constructed using an organic copper salt (Cu(SC(S)N(C2 H5 )2 )2 ) as a photo-induced catalyst at 30 °C. Herein, N,N,N',N'',N''-pentamethyldiethylenetriamine (PMDETA) is used as a ligand, ethyl 2-bromophenylacetate (EBPA) as an ATRP initiator, and (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO) as a photo-induced radical initiator to establish an ICAR (initiators for continuous activator regeneration) ATRP using methyl methacrylate (MMA) as a modal monomer. The effect of the concentration of the organic copper on the polymerization is investigated in detail. It is found that well-controlled polymerization can be obtained even with the amount of (Cu(SC(S)N(C2 H5 )2 )2 decreasing to a 1.56 ppm level, with the molecular weight of the resultant polymers increasing linearly with monomer conversion while maintaining a narrow molecular weight distribution (M¯w/M¯n < 1.3).

  19. Photo-induced toxicity of Deepwater Horizon slick oil to blue crab (Callinectes sapidus) larvae.

    PubMed

    Alloy, Matthew M; Boube, Idrissa; Griffitt, Robert J; Oris, James T; Roberts, Aaron P

    2015-09-01

    The 2010 Deepwater Horizon oil spill resulted in the accidental release of approximately 700 million L of crude oil into the Gulf of Mexico. Photo-induced toxicity after co-exposure to ultraviolet (UV) radiation is 1 mechanism by which polycyclic aromatic hydrocarbons (PAHs) from oil spills may exert toxicity. Blue crab are an important commercial and ecological resource in the Gulf of Mexico, and their largely transparent larvae may make them sensitive to PAH photo-induced toxicity. The goal of the present study was to examine the sensitivity of early lifestage blue crab (Callinectes sapidus) zoea to slick oil collected during the Deepwater Horizon spill. Blue crab zoea were exposed to 1 of several dilutions of water accommodated fractions from 1 of 2 sources of oil and gradations of natural sunlight in a factorial design. Two 7-h solar exposures were carried out with a recovery period (dark) in between. Survival was found to be UV- and PAH-dependent. Toxicity was observed within the range of surface PAH concentrations reported in the Gulf of Mexico during the Deepwater Horizon spill. These findings indicate that early lifestage blue crab are sensitive to photo-induced toxicity from Deepwater Horizon slick oil.

  20. Photoinduced currents in metal-barrier-metal junctions

    NASA Technical Reports Server (NTRS)

    Guedes, M. P.; Gustafson, T. K.; Heiblum, M.; Siu, D. P.; Slayman, C. W.; Whinnery, J. R.; Yasuoka, Y.

    1978-01-01

    The fabrication and application of metal-barrier-metal tunneling junctions for radiative interactions are discussed. Particular attention is given to the photolithographic fabrication of small area devices and the coupling to such devices via surface plasmon waves which play an important role at infrared and optical frequencies. It has been shown that the junction electron tunneling currents can be strongly coupled to surface plasmon junction modes, and spontaneous and stimulated emission of the latter are possible as well as nonlinear interactions. Finally, results demonstrating the photo-excitation of electrons with subsequent tunneling induced by ultraviolet radiation are presented. It is estimated that quantum efficiencies of the order of 5% and higher are possible in the ultraviolet region.

  1. Ultrafast photoinduced charge separation in metal-semiconductor nanohybrids.

    PubMed

    Mongin, Denis; Shaviv, Ehud; Maioli, Paolo; Crut, Aurélien; Banin, Uri; Del Fatti, Natalia; Vallée, Fabrice

    2012-08-28

    Hybrid nano-objects formed by two or more disparate materials are among the most promising and versatile nanosystems. A key parameter in their properties is interaction between their components. In this context we have investigated ultrafast charge separation in semiconductor-metal nanohybrids using a model system of gold-tipped CdS nanorods in a matchstick architecture. Experiments are performed using an optical time-resolved pump-probe technique, exciting either the semiconductor or the metal component of the particles, and probing the light-induced change of their optical response. Electron-hole pairs photoexcited in the semiconductor part of the nanohybrids are shown to undergo rapid charge separation with the electron transferred to the metal part on a sub-20 fs time scale. This ultrafast gold charging leads to a transient red-shift and broadening of the metal surface plasmon resonance, in agreement with results for free clusters but in contrast to observation for static charging of gold nanoparticles in liquid environments. Quantitative comparison with a theoretical model is in excellent agreement with the experimental results, confirming photoexcitation of one electron-hole pair per nanohybrid followed by ultrafast charge separation. The results also point to the utilization of such metal-semiconductor nanohybrids in light-harvesting applications and in photocatalysis.

  2. Photo-induced free radicals on a simulated Martian surface

    NASA Technical Reports Server (NTRS)

    Tseng, S.-S.; Chang, S.

    1974-01-01

    Results of an electron spin resonance study of free radicals in the ultraviolet irradiation of a simulated Martian surface suggest that the ultraviolet photolysis of CO or CO2, or a mixture of both, adsorbed on silica gel at minus 170 C involves the formation of OH radicals and possibly of H atoms as the primary process, followed by the formation of CO2H radicals. It is concluded that the photochemical synthesis of organic compounds could occur on Mars if the siliceous surface dust contains enough silanol groups and/or adsorbed H2O in the form of bound water.

  3. Thermally and photoinduced polymerization of ultrathin sexithiophene films

    SciTech Connect

    Sander, Anke; Hammer, Rene; Duncker, Klaus; Förster, Stefan; Widdra, Wolf

    2014-09-14

    The thermally-induced polymerization of α-sexithiophene (6T) molecules on Ag(001) and Au(001) gives rise to long unbranched polymer chains or branched polymer networks depending on the annealing parameters. There, the onset temperature for polymerization depends on the strength of interaction with the underlying substrate. Similar polymerization processes are also induced by ultraviolet radiation with photon energies between 3.0 and 4.2 eV. Radical formation by an electronic excitation in the 6T molecule is proposed as the driving mechanism that necessitates the interplay with the metallic substrate.

  4. Photoinduced conductivity of a porphyrin-gold composite nanowire

    SciTech Connect

    Kilina, Svletana; Balatsky, Alexander; Kilin, Dmitri S; Prezhdo, Oleg; Tsemekhman, Kiril

    2009-01-01

    Negatively charged phosphine groups on the backbone of DNA are known to attract gold nanoclusters from a colloid, assembling the clusters at fixed intervals. Bridging these intervals with porphyrin-dye linkers forms an infinite conducting chain, a quantum wire whose carrier mobility can be enhanced by photoexcitation. The resulting nanoassembly can be used as a gate: a wire with a controllable conductivity. The electronic structure of the porphyrin-gold wire is studied here by density functional theory, and the conductivity of the system is determined as a function of the photoexcitation energy. Photoexcitations of the dye are found to enhance the wire conductivity by orders of magnitude.

  5. Photoinduced reduction of surface states in Fe:ZnO

    SciTech Connect

    Knut, R. Palmgren, P.; Karis, O.; Lagerqvist, U.; Pohl, A.; Pal, P.; Svedlindh, P.

    2015-05-28

    We report on the electronic structure of nano-crystalline Fe:ZnO, which has recently been found to be an efficient photocatalyst. Using resonant photoemission spectroscopy, we determine the binding energy of Fe 3d states corresponding to different valencies and coordination of the Fe atoms. The photo-activity of ZnO reduces Fe from 3+ to 2+ in the surface region of the nano-crystalline material due to the formation of oxygen vacancies. Electronic states corresponding to low-spin Fe{sup 2+} are observed and attributed to crystal field modification at the surface. These states are potentially important for the photocatalytic sensitivity to visible light due to their location deep in the ZnO bandgap. X-ray absorption and x-ray photoemission spectroscopy suggest that Fe is only homogeneously distributed for concentrations up to 3%. Increased concentrations does not result in a higher concentration of Fe ions in the surface region. This is limiting the photocatalytic functionality of ZnO, where the most efficient Fe doping concentration has been shown to be 1%-4%.

  6. Photoinduced charge-transfer materials for nonlinear optical applications

    DOEpatents

    McBranch, Duncan W.

    2006-10-24

    A method using polyelectrolyte self-assembly for preparing multi-layered organic molecular materials having individual layers which exhibit ultrafast electron and/or energy transfer in a controlled direction occurring over the entire structure. Using a high molecular weight, water-soluble, anionic form of poly-phenylene vinylene, self-assembled films can be formed which show high photoluminescence quantum efficiency (QE). The highest emission QE is achieved using poly(propylene-imine) (PPI) dendrimers as cationic binders. Self-quenching of the luminescence is observed as the solid polymer film thickness is increased and can be reversed by inserting additional spacer layers of transparent polyelectrolytes between each active conjugated layer, such that the QE grows with thickness. A red shift of the luminescence is also observed as additional PPV layers are added. This effect persists as self-quenching is eliminated. Charge transfer superlattices can be formed by additionally incorporating C.sub.60 acceptor layers.

  7. Photoinduced Charge Transfer from Titania to Surface Doping Site

    PubMed Central

    Inerbaev, Talgat; Hoefelmeyer, James D.; Kilin, Dmitri S.

    2013-01-01

    We evaluate a theoretical model in which Ru is substituting for Ti at the (100) surface of anatase TiO2. Charge transfer from the photo-excited TiO2 substrate to the catalytic site triggers the photo-catalytic event (such as water oxidation or reduction half-reaction). We perform ab-initio computational modeling of the charge transfer dynamics on the interface of TiO2 nanorod and catalytic site. A slab of TiO2 represents a fragment of TiO2 nanorod in the anatase phase. Titanium to ruthenium replacement is performed in a way to match the symmetry of TiO2 substrate. One molecular layer of adsorbed water is taken into consideration to mimic the experimental conditions. It is found that these adsorbed water molecules saturate dangling surface bonds and drastically affect the electronic properties of systems investigated. The modeling is performed by reduced density matrix method in the basis of Kohn-Sham orbitals. A nano-catalyst modeled through replacement defect contributes energy levels near the bottom of the conduction band of TiO2 nano-structure. An exciton in the nano-rod is dissipating due to interaction with lattice vibrations, treated through non-adiabatic coupling. The electron relaxes to conduction band edge and then to the Ru cite with faster rate than hole relaxes to the Ru cite. These results are of the importance for an optimal design of nano-materials for photo-catalytic water splitting and solar energy harvesting. PMID:23795229

  8. A molecular shift register based on electron transfer

    NASA Technical Reports Server (NTRS)

    Hopfield, J. J.; Onuchic, Josenelson; Beratan, David N.

    1988-01-01

    An electronic shift-register memory at the molecular level is described. The memory elements are based on a chain of electron-transfer molecules and the information is shifted by photoinduced electron-transfer reactions. This device integrates designed electronic molecules onto a very large scale integrated (silicon microelectronic) substrate, providing an example of a 'molecular electronic device' that could actually be made. The design requirements for such a device and possible synthetic strategies are discussed. Devices along these lines should have lower energy usage and enhanced storage density.

  9. Sequential Assembly of Magnetic Prussian Blue Films with Photo-Induced Magnetism

    NASA Astrophysics Data System (ADS)

    Meisel, Mark W.

    2004-11-01

    Despite interest in the area of molecule-based magnets, there are few efforts to investigate magnetism in monolayers, surface layers, and other thin films based on these materials. New synthetic methods developed by our groups now permit deposition of single layer and multilayer thin films of cyanometallate molecule-based magnet systems. These monolayers and surface films are inherently anisotropic, thereby allowing magnetic characterizations that are only possible because of our method of fabrication. Two examples will be presented. The distance dependence of dipolar interactions on magnetic order is illustrated by comparing a monolayer, bilayer, and multilayers of a mixed organic/inorganic Fe^3+/Ni^2+ cyanometallate two-dimensional network. The magnetometry results demonstrate the influence of dipolar interactions at an interlayer separation of greater than 35 ÅSecondly, anisotropic response of the photoinduced magnetism in a thin film of Rb_jCo_k[Fe(CN)_6]l \\cdot nH_2O, which experiences a ferrimagnetic transition near 20 K, has been discovered. The photo-induced magnetism may result in a net increase or decrease of the total magnetization of the sample when the externally applied magnetic field is oriented parallel or perpendicular to the plane of the films. The strength of this anisotropy depends on the thickness of the film and the size of the magnetic domains, and the photo-induced magnetism was effective in magnetic fields up to 27 T while at 4.7 K. This work, co-authored with D. R. Talham, was performed with J.-H. Park, F. Frye, Y.-D. Huh, E. Čižmár, and S. Lane, and was supported, in part, by NSF DMR-0305371.

  10. Electron accumulation on metal nanoparticles in plasmon-enhanced organic solar cells.

    PubMed

    Salvador, Michael; MacLeod, Bradley A; Hess, Angela; Kulkarni, Abhishek P; Munechika, Keiko; Chen, Jennifer I L; Ginger, David S

    2012-11-27

    Plasmonic metal nanoparticles have been used to enhance the performance of thin-film devices such as organic photovoltaics based on polymer/fullerene blends. We show that silver nanoprisms accumulate long-lived negative charges when they are in contact with a photoexcited bulk heterojunction blend composed of poly(3-hexylthiophene)/phenyl-C61-butyric acid methyl ester (P3HT/PCBM). We report both the charge modulation and electroabsorption spectra of silver nanoprisms in solid-state devices and compare these spectra with the photoinduced absorption spectra of P3HT/PCBM blends containing silver nanoprisms. We assign a previously unidentified peak in the photoinduced absorption spectra to the presence of photoinduced electrons on the silver nanoprisms. We show that coating the nanoprisms with a 2.5 nm thick insulating layer can completely inhibit this charging. These results may inform methods for limiting metal-mediated losses in plasmonic solar cells.

  11. Deuterium enrichment by selective photoinduced dissociation of a multihalogenated organic compound

    DOEpatents

    Marling, John B.; Herman, Irving P.

    1981-01-01

    A method for deuterium enrichment by photoinduced dissociation which uses as the deuterium source a multihalogenated organic compound selected from the group consisting of a dihalomethane, a trihalomethane, a 1,2-dihaloethene, a trihaloethene, a tetrahaloethane and a pentahaloethane. The multihalogenated organic compound is subjected to intense infrared radiation at a preselected wavelength to selectively excite and thereby induce dissociation of substantially only those molecules containing deuterium to provide a deuterium enriched dissociation product. The deuterium enriched product may be combusted with oxygen to provide deuterium enriched water. The deuterium depleted undissociated molecules may be redeuterated by treatment with a deuterium source such as water.

  12. Image storage in coumarin-based copolymer thin films by photoinduced dimerization.

    PubMed

    Gindre, Denis; Iliopoulos, Konstantinos; Krupka, Oksana; Champigny, Emilie; Morille, Yohann; Sallé, Marc

    2013-11-15

    We report a technique to encode grayscale digital images in thin films composed of copolymers containing coumarins. A nonlinear microscopy setup was implemented and two nonlinear optical processes were used to store and read information. A third-order process (two-photon absorption) was used to photoinduce a controlled dimer-to-monomer ratio within a defined tiny volume in the material, which corresponds to each recorded bit of data. Moreover, a second-order process (second-harmonic generation) was used to read the stored information, which has been found to be highly dependent upon the monomer-to-dimer ratio.

  13. Graphene/CdTe heterostructure solar cell and its enhancement with photo-induced doping

    SciTech Connect

    Lin, Shisheng Chen, Hongsheng; Li, Xiaoqiang; Zhang, Shengjiao; Wang, Peng; Xu, Zhijuan; Zhong, Huikai; Wu, Zhiqian

    2015-11-09

    We report a type of solar cell based on graphene/CdTe Schottky heterostructure, which can be improved by surface engineering as graphene is atomic thin. By coating a layer of ultrathin CdSe quantum dots onto graphene/CdTe heterostructure, the power conversion efficiency is increased from 2.08% to 3.10%. Photo-induced doping is mainly accounted for this enhancement, as evidenced by field effect transport, Raman, photoluminescence, and quantum efficiency measurements. This work demonstrates a feasible way of improving the performance of graphene/semiconductor heterostructure solar cells by combining one dimensional with two dimensional materials.

  14. Photoinduced Barkhausen effect in the ferromagnetic semiconductor (Ga,Mn)As.

    PubMed

    Astakhov, G V; Schwittek, J; Schott, G M; Gould, C; Ossau, W; Brunner, K; Molenkamp, L W

    2011-01-21

    Magnetization of ferromagnetic materials commonly occurs via random jumps of domain walls between pinning sites, a phenomenon known as the Barkhausen effect. Using strongly focused light pulses of appropriate power and duration we demonstrate the ability to selectively activate single jumps in the domain wall propagation in (Ga,Mn)As, manifesting itself as a discrete photoinduced domain wall creep as a function of illumination time. The propagation velocity can be increased over 7 orders of magnitude varying the illumination power density and the magnetic field.

  15. Decay of photoinduced oscillations of the optical reflection coefficient of bismuth

    SciTech Connect

    Semenov, A. L.

    2013-07-15

    A model describing the decay of photoinduced oscillations of the optical reflection coefficient R of bismuth is constructed, taking the crystal lattice anharmonicity into account. The decay time of oscillations of R is calculated as a function of the energy density of a laser pulse. The results of calculations explain the experimental data on the anomalously strong decay of oscillations of the optical reflection coefficient of bismuth (the decay time decreases by more than an order of magnitude with an increase in the laser pulse energy density from 0 to 4 mJ/cm{sup 2})

  16. Time-Resolved Studies of Photoinduced Birefringence in Azobenzene Dye-Doped Polymer Films

    DTIC Science & Technology

    2008-10-01

    state, where the fairly limited work has been done [8,9]. Here we report on transient photoinduced birefrin- gence ( PIB ) measurements on several azo...response time ranges from within 20ns to more than 200 μs. Our results show the response time of PIB to be sys- tematically related to the size of the...lowest optical transition energy. Furthermore, our results suggest that PIB effects can be used to discriminate between0003-6935/08/285074-04$15.00/0

  17. Photoinduced Intramolecular Cyclopentanation vs Photoprotolytic Oxametathesis in Polycyclic Alkenes Outfitted with Conformationally Constrained Aroylmethyl Chromophores‡

    PubMed Central

    Valiulin, Roman A.; Arisco, Teresa M.; Kutateladze, Andrei G.

    2012-01-01

    Intramolecular photoinduced cyclizations are investigated in photoprecursors assembled in a modular fashion via a Diels-Alder reaction of acetylenic dienophiles with subsequent Michael additions of aromatic ketones to install a chromophore capable of initiating Paternò-Büchi cycloadditions or radical cyclization cascades. The protolytic oxametathesis in these systems allows for rapid access to novel polycyclic scaffolds decorated by formyl groups and carboxylates suitable for subsequent modifications. In conformationally constrained photoprecursors a radical rearrangement takes place resulting in intramolecular 1,3-diradical cyclopentanation of the double bond. PMID:23106813

  18. Spontaneous photoinduced patterning of azo-dye polymer films: the facts

    SciTech Connect

    Hubert, Christophe

    2007-08-15

    We describe the spontaneous photoinduced patterning of azo-dye polymer films. We have observed that the illumination of an azo-dye polymer film by a uniform single laser beam with normal incidence leads to a self-structurization process that results in the formation of well-ordered submicrometer-sized structures whose organization depends on the light polarization direction. A modulation depth as high as 100 nm can be achieved. The influence of several experimental parameters on the structure formation is studied. Results are discussed and confronted to different models and phenomena already investigated in the literature. A physical origin to this peculiar photopatterning process is proposed.

  19. Deuterium enrichment by selective photo-induced dissociation of an organic carbonyl compound

    DOEpatents

    Marling, John B.

    1981-01-01

    A method for producing a deuterium enriched material by photoinduced dissociation which uses as the working material a gas phase photolytically dissociable organic carbonyl compound containing at least one hydrogen atom bonded to an atom which is adjacent to a carbonyl group and consisting of molecules wherein said hydrogen atom is present as deuterium and molecules wherein said hydrogen atom is present as another isotope of hydrogen. The organic carbonyl compound is subjected to intense infrared radiation at a preselected wavelength to selectively excite and thereby induce dissociation of the deuterium containing species to yield a deuterium enriched stable molecular product. Undissociated carbonyl compound, depleted in deuterium, is preferably redeuterated for reuse.

  20. Photoinduced holographic surface relief gratings in thin self-developing dichromated polymer films: parametric study

    NASA Astrophysics Data System (ADS)

    Beaulieu, Rene M.; Lessard, Roger A.; Bolte, Michel

    1998-09-01

    Photoinduced holographic surface relief gratings have been fabricate din dichromated poly(acrylic acid) films. These gratings are formed in darkness subsequent to the illumination at 442 nm and they are obtained without any chemical treatment or wet processing. The influence of chemical parameters, such as ammonium dichromate and dimethylformamide concentrations, on the holographic characteristics of these gratings have been investigated. Holographic characteristics of the recording medium such as diffraction efficiency as a function of exposure, ammonium dichromate and dimethylformamide concentrations, and spatial frequency are presented in this paper.

  1. Photoinduced self-structured surface pattern on a molecular azo glass film: structure-property relationship and wavelength correlation.

    PubMed

    Wang, Xiaolin; Yin, Jianjun; Wang, Xiaogong

    2011-10-18

    In this study, three series of star-shaped molecular azo glasses were synthesized, and self-structured surface pattern formation on the azo compound films was studied by laser irradiation at different wavelengths. The molecular azo glasses were synthesized from three core precursors (Tr-AN, Tr-35AN, Tr-H35AN), which were prepared by ring-opening reactions between 1,3,5-triglycidyl isocyanurate and corresponding aniline derivatives. The star-shaped azo compounds were obtained through azo-coupling reactions between the core precursors and diazonium salts of 4-chloroaniline, 4-aminobenzonitrile, and 4-nitroaniline, respectively. By using the two-step reaction scheme, three series of azo compounds with different structures were obtained. The core precursors and azo compounds were characterized by using (1)H NMR, FT-IR, UV-vis, mass spectrometry, and thermal analyses. The self-structured surface pattern formation on films of the azo compounds was studied by irradiating the azo compound films with a normal-incident laser beam at different wavelengths (488, 532, and 589 nm). The results show that the photoinduced surface pattern formation behavior is closely related to the structure of the azo compounds, excitation wavelength, and light polarization conditions. The absorption band position of the π-π* transition is mainly determined by the electron-withdrawing groups on the azo chromophores. When the excitation wavelength is between λ(max) and the band tail at the longer wavelength side, the self-structured surface patterns can be more efficiently induced to form on the films. The 3,5-dimethyl substitution on azo chromophores inhibits the surface pattern formation for certain excitation wavelengths. Increasing molecular interaction also shows an effect of restraining the surface pattern formation. The irradiations with linearly and circularly polarized light cause significant differences in the alignment manner of the pillarlike structures and their saturated height.

  2. Erasable photoinduced change of carrier density and coherence lengths in oxygen-deficient YBa 2Cu 3O x

    NASA Astrophysics Data System (ADS)

    Göb, W.; Lang, W.; Markowitsch, W.; Schlosser, V.; Kula, W.; Soblewski, Roman

    1995-11-01

    We report on the persistent and erasable photoinduced change of normal-state transport and superconducting properties of oxygen-deficient YBa 2Cu 3O 6.6 thin films. After illumination with white light for several hours at 150K, a decrease of the electrical resistivity, an increase of the number of mobile holes, and a change of the magnetoresistance caused by superconducting order-parameter fluctuations, were observed. From the latter measurement, we find a photoinduced enhancement of the superconducting coherence lengths in both in-plane and out-of-plane directions.

  3. Preparation of TiO2 thin films using water-soluble titanium complexes and their photoinduced properties.

    PubMed

    Katsumata, Ken-ichi; Ohno, Yukiaki; Tomita, Koji; Sakai, Munetoshi; Nakajima, Akira; Kakihana, Masato; Fujishima, Akira; Matsushita, Nobuhiro; Okada, Kiyoshi

    2011-01-01

    Titanium dioxide thin films were prepared by using four water-soluble titanium complexes of titanium-lactate, tartalate, malate and salicylate complex solutions. The crystalline phases detected in the films were anatase. The surface microstructures of the four film samples were different in their grain sizes. Photocatalytic decomposition activity of the four films was almost the same, but their photoinduced hydrophilicities were different. The film prepared using titanium-salicylate complex exhibited lower hydrophilic conversion rate than the other films. Grain size and stress yielded to the film are considered to be important factors on the photoinduced hydrophilicity.

  4. Electron Transport Modeling of Molecular Nanoscale Bridges Used in Energy Conversion Schemes

    SciTech Connect

    Dunietz, Barry D.

    2016-08-09

    The goal of the research program is to reliably describe electron transport and transfer processes at the molecular level. Such insight is essential for improving molecular applications of solar and thermal energy conversion. We develop electronic structure models to study (1) photoinduced electron transfer and transport processes in organic semiconducting materials, and (2) charge and heat transport through molecular bridges. We seek fundamental understanding of key processes, which lead to design new experiments and ultimately to achieve systems with improved properties.

  5. Electron transfer and catalysis with high-valent metal-oxo complexes.

    PubMed

    Fukuzumi, Shunichi

    2015-04-21

    High-valent metal-oxo complexes are produced by reductive activation of dioxygen via reduction of metal complexes with reductants and dioxygen. Photoinduced electron transfer from substrates to metal complexes with dioxygen also leads to the generation of high-valent metal-oxo complexes that can oxygenate substrates. In such a case metal complexes act as a photocatalyst to oxygenate substrates with dioxygen. High-valent metal-oxo complexes are also produced by proton-coupled electron-transfer oxidation of metal complexes by one-electron oxidants with water, oxygenating substrates to regenerate metal complexes. In such a case metal complexes act as a catalyst for electron-transfer oxygenation of substrates by one-electron oxidants with water that acts as an oxygen source. The one-electron oxidants which can oxidize metal complexes can be replaced by much weaker oxidants by a combination of redox photocatalysts and metal complexes. Thus, photocatalytic oxygenation of substrates proceeds via photoinduced electron transfer from a photocatalyst to reductants followed by proton-coupled electron transfer oxidation of metal complexes with the oxidized photocatalyst to produce high-valent metal-oxo complexes that oxygenate substrates. Thermal and photoinduced electron-transfer catalytic reactions of high-valent metal-oxo complexes for oxygenation of substrates using water or dioxygen as an oxygen source are summarized in this perspective.

  6. Photoinduced Enhancement of Anisotropic Charge Correlations on Triangular Lattices with Trimers

    NASA Astrophysics Data System (ADS)

    Yonemitsu, Kenji

    2017-02-01

    To explore nontrivial photoinduced modulations of charge correlations, we theoretically study photoinduced dynamics in quarter-filled extended Hubbard models with competing intersite repulsive interactions on triangular lattices with trimers, where the end points are crystallographically equivalent. The exact diagonalization method is used and the time-dependent Schrödinger equation is numerically solved during and after photoexcitation. Time-averaged double occupancy and intersite density-density correlations can be interpreted as due to effective on-site and intersite repulsive interactions, respectively, relative to transfer energies. In the case where the intersite repulsive interactions compete with each other, the anisotropy of their effective interactions can be enhanced with the help of the trimers, irrespective of whether the trimers are linear or bent. In particular, in the case where the arrangement of the trimers is close to that in α-(bis[ethylenedithio]-tetrathiafulvalene)2I3 [α-(BEDT-TTF)2I3] in the metallic phase, the effective on-site repulsion is enhanced relative to the transfer energies. The relevance of this theoretical finding to the experimentally observed optical freezing of charge motion is discussed.

  7. Photo-induced reactions in the ion-molecule complex Mg+-OCNC2H5

    NASA Astrophysics Data System (ADS)

    Sun, Ju-Long; Liu, Haichuan; Han, Ke-Li; Yang, Shihe

    2003-06-01

    Ion-molecule complexes of magnesium cation with ethyl isocyanate were produced in a laser-ablation supersonic expansion nozzle source. Photo-induced reactions in the 1:1 complexes have been studied in the spectral range of 230-410 nm. Photodissociation mass spectrometry revealed the persistent product Mg+ from nonreactive quenching throughout the entire wavelength range. As for the reactive channels, the photoproducts, Mg+OCN and C2H5+, were produced only in the blue absorption band of the complex with low yields. The action spectrum of Mg+(OCNC2H5) consists of two pronounced peaks on the red and blue sides of the Mg+ 32P←32S atomic transition. The ground state geometry of Mg+-OCNC2H5 was fully optimized at B3LYP/6-31+G** level by using GAUSSIAN 98 package. The calculated absorption spectrum of the complex using the optimized structure of its ground state agrees well with the observed action spectrum. Photofragment branching fractions of the products are almost independent of the photolysis photon energy for the 3Px,y,z excitations. The very low branching ratio of reactive products to nonreactive fragment suggests that evaporation is the main relaxation pathway in the photo-induced reactions of Mg+(OCNC2H5).

  8. Photo-induced bending in a light-activated polymer laminated composite.

    PubMed

    Mu, Xiaoming; Sowan, Nancy; Tumbic, Julia A; Bowman, Christopher N; Mather, Patrick T; Qi, H Jerry

    2015-04-07

    Light activated polymers (LAPs) have attracted increasing attention since these materials change their shape and/or behavior in response to light exposure, which serves as an instant, remote and precisely controllable stimulus that enables non-contact control of the material shape and behavior through simple variation in light intensity, wavelength and spatially controlled exposure. These features distinguish LAPs from other active polymers triggered by other stimuli such as heat, electrical field or humidity. Previous examples have resulted in demonstrations in applications such as surface patterning, photo-induced shape memory behavior, and photo-origami. However, in many of these applications, an undesirable limitation has been the requirement to apply and maintain an external load during light irradiation. In this paper, a laminated structure is introduced to provide a pre-programmed stress field, which is then used for photo-induced deformation. This laminated structure is fabricated by bonding a stretched elastomer (NOA65) sheet between two LAP layers. Releasing the elastomer causes contraction and introduces a compressive stress in the LAPs, which are relaxed optically to trigger the desired deformation. A theoretical model is developed to quantitatively examine the laminated composite system, allowing exploration of the design space and optimum design of the laminate.

  9. Effect of natural organic matter on the photo-induced toxicity of titanium dioxide nanoparticles.

    PubMed

    Wormington, Alexis M; Coral, Jason; Alloy, Matthew M; Damarè, Carmen L; Mansfield, Charles M; Klaine, Stephen J; Bisesi, Joseph H; Roberts, Aaron P

    2016-12-07

    Nano-titanium dioxide (TiO2 ) is the most widely used form of nanoparticles in commercial industry and comes in 2 main configurations: rutile and anatase. Rutile TiO2 is used in ultraviolet (UV) screening applications, whereas anatase TiO2 crystals have a surface defect that makes them photoreactive. There are numerous reports in the literature of photo-induced toxicity to aquatic organisms following coexposure to anatase nano-TiO2 and UV. All natural freshwater contains varying amounts of natural organic matter (NOM), which can drive UV attenuation and quench reactive oxygen species (ROS) in aquatic ecosystems. The present research examined how NOM alters the photo-induced toxicity of anatase nano-TiO2 . Daphnia magna neonates were coexposed to NOM and photoexcited anatase nano-TiO2 for 48 h. Natural organic matter concentrations as low as 4 mg/L reduced anatase nano-TiO2 toxicity by nearly 100%. These concentrations of NOM attenuated UV by <10% in the exposure system. However, ROS production measured using a fluorescence assay was significantly reduced in a NOM concentration--dependent manner. Taken together, these data suggest that NOM reduces anatase nano-TiO2 toxicity via an ROS quenching mechanism and not by attenuation of UV. Environ Toxicol Chem 2016;9999:1-6. © 2016 SETAC.

  10. OPTICAL FIBRES: Photoinduced and thermal reactions involving hydrogen in high-germania-core optical fibres

    NASA Astrophysics Data System (ADS)

    Rybaltovskii, A. O.; Koltashev, V. V.; Medvedkov, O. I.; Rybaltovsky, A. A.; Sokolov, V. O.; Klyamkin, Semen N.; Plotnichenko, V. G.; Dianov, Evgenii M.

    2008-12-01

    We report a Raman scattering study of photoinduced and thermal reactions between H2 and germanosilicate optical fibres with 22 mol % and 97 mol % GeO2 in the core (F1 and F2, respectively) after H2 loading at 150 MPa (1500 atm). The mechanisms of photoreactions are investigated in a wide range of incident laser wavelengths (244, 333, 354, 361 and 514 nm). Thermal reactions are studied at 500 °C. The results indicate that the main mechanism behind the formation of hydrogen-containing defects with Raman bands at 700, 750, 2190, 3600 and 3680 cm-1 involves ≡Ge—O—Ge≡ or ≡Ge—O—Si≡ bond breaking and formation of hydride and hydroxyl species: =GeH2 (700, 750 cm-1), ≡Ge—H (2190 cm-1), ≡GeO—H (3600 cm-1) and ≡SiO—H (3680 cm-1). The key features of the reactions in the F1 and F2 fibres are analysed. In particular, photoinduced reactions give ≡Si—OH groups only in the F1 fibres, whereas the formation of germanium nanoclusters at a relatively low temperature (~500 °C) or ≡GeO—H and ≡Ge—H defects under 514-nm irradiation has only been observed in the F2 fibres.

  11. Effects of photoinduced toxicity of fluoranthene on amphibian embryos and larvae

    SciTech Connect

    Hatch, A.C.; Burton, G.A. Jr.

    1998-09-01

    Embryos and newly hatched larvae of three amphibian species, the spotted salamander (Ambystoma maculatum), the northern leopard frog (Rana pipiens), and the African clawed frog (Xenopus laevis), were exposed to fluoranthene and ultraviolet (UV) light in two scenarios. Embryos were exposed in a laboratory setting from an early developmental stage through hatching under artificial UV light, and newly hatched larvae were exposed outdoors in varying sunlight intensity levels. Outdoor exposures indicated greater sensitivity in the toxic response than did laboratory exposures. In the laboratory, mortality and malformation of X. laevis were the most sensitive indicators of exposure. Xenopus laevis was also the most sensitive species tested to the effects of UV light alone. Hatching success of R. pipiens was monitored outdoors and was not a useful predictive endpoint in the determination of photoinduced toxicity; however, newly hatched larvae were sensitive to the effects of photoinduced toxicity. Amybstoma maculatum and X. laevis larvae were affected by low ({micro}g/L) concentrations of fluoranthene in sunlight. These findings suggest that low levels of polycyclic aromatic hydrocarbons could be acting synergistically with environmental factors such as UV light to place young amphibians at risk.

  12. Tracking of the molecular motion in the primary event of photoinduced reactions of a phytochromobilin model.

    PubMed

    Zhuang, Xuhui; Wang, Jun; Lan, Zhenggang

    2013-12-19

    The photoinduced processes of phytochromes have received great research interest for their important biological functions. Phytochromobilin (PΦB), one of the most important phytochrome chromophores, was selected as the prototype to study its photoinduced isomerization. The nonadiabatic dynamics of PΦB from the Pr configuration in the gas phase was investigated by the surface hopping method at the OM2/MRCI level. In the excited state, isolated PΦB does not display the rotation of the two terminal five-membered rings (ring A and ring D), which is assumed to govern the Pr → Pfr process in the protein. Instead, two S1/S0 conical intersection seams (CI01α and CI01β) characterized by the rotation of the two central rings (ring B and ring C) were proven to play essential roles for the photoisomerization of PΦB in the gas phase. These two conical intersections (CI01α and CI01β) are accessible by the twisting motions of the C9-C10 and C10-C11 bonds, respectively. The CI01α and CI01β seams, instead of their minimum-energy points, are responsible for the nonadiabatic dynamics. For both channels, the trajectories may propagate forward to the isomerization products or backward to the original Pr configuration after the S1 → S0 hops.

  13. Kinetics of photoinduced ordering in azo-dye films: two-state and diffusion models.

    PubMed

    Kiselev, Alexei D; Chigrinov, Vladimir G; Kwok, Hoi-Sing

    2009-07-01

    We theoretically study the kinetics of photoinduced ordering in azo-dye photoaligning layers and present the results of modeling performed using two different phenomenological approaches. A phenomenological two-state model is deduced from the master equation for the one-particle distribution functions of an ensemble of two-level molecular systems by specifying the angular redistribution probabilities and by expressing the order parameter correlation functions in terms of the order parameter tensor. Using an alternative approach that describes light-induced reorientation of azo-dye molecules in terms of a rotational Brownian motion, we formulate the two-dimensional diffusion model as the free energy Fokker-Planck equation simplified for the limiting regime of purely in-plane reorientation. The models are employed to interpret the irradiation time dependence of the absorption order parameters defined in terms of the principal extinction (absorption) coefficients. Using the exact solution to the light transmission problem for a biaxially anisotropic absorbing layer, these coefficients are extracted from the absorbance-vs-incidence angle curves measured at different irradiation doses for the probe light linearly polarized parallel and perpendicular to the plane of incidence. It is found that, in the azo-dye films, the transient photoinduced structures are biaxially anisotropic whereas the photosteady and the initial states are uniaxial.

  14. Kinetics of photoinduced ordering in azo-dye films: Two-state and diffusion models

    SciTech Connect

    Kiselev, Alexei D.; Chigrinov, Vladimir G.; Kwok, Hoi-Sing

    2009-07-15

    We theoretically study the kinetics of photoinduced ordering in azo-dye photoaligning layers and present the results of modeling performed using two different phenomenological approaches. A phenomenological two-state model is deduced from the master equation for the one-particle distribution functions of an ensemble of two-level molecular systems by specifying the angular redistribution probabilities and by expressing the order parameter correlation functions in terms of the order parameter tensor. Using an alternative approach that describes light-induced reorientation of azo-dye molecules in terms of a rotational Brownian motion, we formulate the two-dimensional diffusion model as the free energy Fokker-Planck equation simplified for the limiting regime of purely in-plane reorientation. The models are employed to interpret the irradiation time dependence of the absorption order parameters defined in terms of the principal extinction (absorption) coefficients. Using the exact solution to the light transmission problem for a biaxially anisotropic absorbing layer, these coefficients are extracted from the absorbance-vs-incidence angle curves measured at different irradiation doses for the probe light linearly polarized parallel and perpendicular to the plane of incidence. It is found that, in the azo-dye films, the transient photoinduced structures are biaxially anisotropic whereas the photosteady and the initial states are uniaxial.

  15. Photoinduced toxicity of PrF3 and LaF3 nanoparticles

    NASA Astrophysics Data System (ADS)

    Pudovkin, M. S.; Zelenikhin, P. V.; Krasheninnikova, A. O.; Korableva, S. L.; Nizamutdinov, A. S.; Alakshin, E. M.; Semashko, V. V.; Safiullin, R. A.; Kadirov, M. K.

    2016-10-01

    PrF3 and LaF3 nanoparticles were synthesized by the hydrothermal method. The size distribution of these nanoparticles in the colloidal solution produced was studied by photon correlation spectroscopy. The mean diameter of the nanoparticles was 42 ± 1 nm. During the study of the toxicity of the nanoparticles, the mixture of a colloidal solution of the nanoparticles with cells to be studied was irradiated by 30-mW continuous lasers at wavelengths of 532 and 473 nm. The concentration of salmonella cells in normal saline was 106 cell/mL, while that of nanoparticles was 0.1 g/L. The cell survival percentage was 39, 34, and 20% for the irradiation times of 5, 10, and 15 min, respectively, at an optimal laser radiation power density of 0.4 W/cm at a wavelength of 532 nm. It was ascertained that LaF3 nanoparticles do not possess the property of photoinduced toxicity and the apoptosing effect. Moreover, the property of photoinduced toxicity is not shared by microparticles, in contrast to nanoparticles.

  16. Crystallinity effects on scaling properties of photoinduced modes in silver nanoprisms

    SciTech Connect

    Ng, Ming-Yaw; Ho, I-Lin; Chang, Yia-Chung

    2015-02-21

    The crystallinity effects on scaling properties of photoinduced modes in crystalline silver nanoprisms with C{sub 3v} symmetry are studied using a realistic atomistic model and group theory. Among all vibrational modes, photoinduced modes can be identified as those vibrational modes which possess larger in-phase radial atomic displacement and can be projected out by the projected density of states method. We found that the properties of vibrations in silver nanoprisms strongly depend on the particle’s aspect ratio (bisector length over thickness). By considering crystallinity of silver nanoprisms, the dominant modes with the in-plane oscillation become several closely spaced modes, and become obvious for nanoprisms with a smaller aspect ratio. The oscillation spectra show that the dominant planar modes are insensitive to thickness change. On the contrary, the atomic displacements show significantly different patterns for nanoprisms of different thicknesses. We also found that, for nanoprisms with same aspect ratio that is larger than 4, the vibrational properties of dominant modes exhibit scaling similarity. By using a simple linear transformation, the vibration frequencies for large-sized nanoprisms of aspect ratio 6 can be obtained by a corresponding scaling factor. The calculated results are in good agreement with experimental data.

  17. Quantification of photoinduced order increase in liquid crystals with naphthopyran guests

    NASA Astrophysics Data System (ADS)

    Rumi, Mariacristina; Cazzell, Seth A.; Kosa, Tamas; Sukhomlinova, Ludmila; Taheri, Bahman; White, Timothy J.; Bunning, Timothy J.

    2016-03-01

    Photoinduced order-increasing phase transitions can occur in dye-liquid crystal mixtures when the photoproduct of the excitation of the dye molecules is more compatible with the liquid crystalline medium than the initial dye species. A detailed investigation of the photoinduced changes of the phase behavior and optical properties of mixtures of liquid crystals with naphthopyran guests upon exposure to light at 365 nm is presented here. In these guest-host systems, the nematic-to-isotropic phase transition temperature is increased upon irradiation. We show that the nematic range can be extended up to 2.9 °C by illumination in 5CB (4 -n -pentyl-4'-cyanobiphenyl) liquid crystal mixtures. The order parameter is significantly increased by illumination at all temperatures within the nematic range and the changes are larger at higher concentrations of the guests. In particular, the illuminated guest-host mixtures exhibit order parameters close to those of the neat liquid crystal host at the same temperature relative to the clearing point. An improved understanding of the photophysical processes taking place at the molecular level in these material systems can inform the design of photoresponsive materials and enhance their potential utility in optical or photonic devices.

  18. Photoinduced charge generation rates in soluble P3HT : PCBM nano-aggregates predict the solvent-dependent film morphology

    NASA Astrophysics Data System (ADS)

    Roy, Palas; Jha, Ajay; Dasgupta, Jyotishman

    2016-01-01

    The device efficiency of bulk heterojunction (BHJ) solar cells is critically dependent on the nano-morphology of the solution-processed polymer : fullerene blend. Active control on blend morphology can only emanate from a detailed understanding of solution structures during the film casting process. Here we use photoinduced charge transfer (CT) rates to probe the effective length scale of the pre-formed solution structures and their energy disorder arising from a mixture of poly(3-hexylthiophene-2,5-diyl) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) in three different organic solvents. The observed solvent-dependent ultrafast biphasic rise of the transient polaron state in solution along with changes detected in the C&z.dbd;C stretching frequency of bound PCBM provides direct evidence for film-like P3HT : PCBM interfaces in solution. Using the diffusive component of the charge transfer rate, we deduce ~3-times larger functional nano-domain size in toluene than in chlorobenzene thereby correctly predicting the relative polymer nanofiber widths observed in annealed films. We thus provide first experimental evidence for the postulated polymer : fullerene : solvent ternary phase that seeds the eventual morphology in spin-cast films. Our work motivates the design of new chemical additives to tune the grain size of the evolving polymer : fullerene domains within the solution phase.The device efficiency of bulk heterojunction (BHJ) solar cells is critically dependent on the nano-morphology of the solution-processed polymer : fullerene blend. Active control on blend morphology can only emanate from a detailed understanding of solution structures during the film casting process. Here we use photoinduced charge transfer (CT) rates to probe the effective length scale of the pre-formed solution structures and their energy disorder arising from a mixture of poly(3-hexylthiophene-2,5-diyl) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) in three

  19. Photo-induced hydrogen production in a helical peptide incorporating a [FeFe] hydrogenase active site mimic.

    PubMed

    Roy, Anindya; Madden, Christopher; Ghirlanda, Giovanna

    2012-10-11

    There is growing interest in the development of hydrogenase mimics for solar fuel production. Here, we present a bioinspired mimic designed by anchoring a diiron hexacarbonyl cluster to a model helical peptide via an artificial dithiol amino acid. The [FeFe]-peptide complex catalyses photo-induced production of hydrogen in water.

  20. Photoinduced Graft-Polymerization of Acrylic Acid on Polyethylene and Polypropylene Surfaces: Comparative Study Using IR-ATR Spectroscopy

    NASA Astrophysics Data System (ADS)

    Gorbachev, A. A.; Tretinnikov, O. N.; Shkrabatovskaya, L. V.; Prikhodchenko, L. K.

    2014-11-01

    Photoinduced graft-polymerization of acrylic acid on the surface of polyethylene and polypropylene films containing a photoinitiator pre-adsorbed from a thin layer of non-de-aerated aqueous monomer solution was investigated. Data about the monomer conversion and grafting depth as functions of the UV irradiation time and polymer nature were obtained using IR-ATR spectroscopy.

  1. Facile Synthesis of Stapled, Structurally Reinforced Peptide Helices via A Photoinduced Intramolecular 1,3-Dipolar Cycloaddition Reaction†

    PubMed Central

    Madden, Michael M.; Vera, Claudia I. Rivera; Song, Wenjiao; Lin, Qing

    2009-01-01

    We report the first use of a photoinduced 1,3-dipolar cycloaddition reaction in “stapling” peptide side chains to reinforce a model peptide helical structure with moderate to excellent yields. The resulting pyrazoline “staplers” exhibit unique fluorescence useful in a cell permeability study. PMID:19753366

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

    PubMed

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

    2017-03-02

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

  3. PHOTO-INDUCED POLYCYCLIC AROMATIC HYDROCARBON TOXIC POTENTIALS OF NEAR SHORE LARVAL FISH HABITAT IN THE GREAT LAKES, USA

    EPA Science Inventory

    Photo-induced toxicity (PIT) of polycyclic aromatic hydrocarbons (PAH) has been documented in laboratory studies for both invertebrate and vertebrate aquatic organisms. PIT has not been verified in field studies for larval fish to date. Filtered water samples and larval fish were...

  4. Photoinduced processes in hybrid structures on the basis of TiO2 nanoparticles and CdSe/ZnS quantum dots

    NASA Astrophysics Data System (ADS)

    Kolesova, E. P.; Orlova, A. O.; Maslov, V. G.; Gun'ko, Yu. K.; Cleary, O.; Baranov, A. V.; Fedorov, A. V.

    2017-01-01

    The morphology of and photoinduced changes in the luminescent properties of hybrid structures on the basis of TiO2 nanoparticles and CdSe/ZnS quantum dots are studied. It is established that the morphology of the structures depends on the method of their formation and the type of stabilizer of the CdSe/ZnS surface. It is shown that a photoinduced decrease in the efficiency of nonradiative relaxation of the excitation in the quantum dots leads to an increase in the quantum yield of their luminescence and an increase in the efficiency of photoinduced charge transfer in hybrid structures.

  5. Applications of time-domain spectroscopy to electron-phonon coupling dynamics at surfaces.

    PubMed

    Matsumoto, Yoshiyasu

    2014-10-01

    Photochemistry is one of the most important branches in chemistry to promote and control chemical reactions. In particular, there has been growing interest in photoinduced processes at solid surfaces and interfaces with liquids such as water for developing efficient solar energy conversion. For example, photoinduced charge transfer between adsorbates and semiconductor substrates at the surfaces of metal oxides induced by photogenerated holes and electrons is a core process in photovoltaics and photocatalysis. In these photoinduced processes, electron-phonon coupling plays a central role. This paper describes how time-domain spectroscopy is applied to elucidate electron-phonon coupling dynamics at metal and semiconductor surfaces. Because nuclear dynamics induced by electronic excitation through electron-phonon coupling take place in the femtosecond time domain, the pump-and-probe method with ultrashort pulses used in time-domain spectroscopy is a natural choice for elucidating the electron-phonon coupling at metal and semiconductor surfaces. Starting with a phenomenological theory of coherent phonons generated by impulsive electronic excitation, this paper describes a couple of illustrative examples of the applications of linear and nonlinear time-domain spectroscopy to a simple adsorption system, alkali metal on Cu(111), and more complex photocatalyst systems.

  6. Synthesis and Characterization of Coumarin-Containing Cyclic Polymer and Its Photoinduced Coupling/Dissociation.

    PubMed

    Li, Min; Fan, Wei; Hong, Chunyan; Pan, Caiyuan

    2015-12-01

    Cyclic polystyrene (PS) with a pendant coumarin group is prepared by the combination of atom transfer radical polymerization and "click" chemistry. Fluorescence resonance energy transfer process is observed in the fluorescence measurement of coumarin-containing PS, and cyclic PS exhibits stronger emission than that of its linear precursor. When cyclic PS is irradiated under UV light at λ = 365 nm, 8-shaped PS is achieved due to the dimerization of pendant coumarin group. Subsequently, 8-shaped PS can be divided into single macrocycle under UV irradiation at λ = 254 nm via the photocleavage of coumarin dimer. The photoinduced coupling and dissociation are monitored by UV/vis spectra and gel permeation chromatography (GPC).

  7. Dependence of photoinduced bending behavior of diarylethene crystals on irradiation wavelength of ultraviolet light.

    PubMed

    Kitagawa, Daichi; Tanaka, Rika; Kobatake, Seiya

    2015-11-07

    The dependence of the photoinduced bending behavior of diarylethene crystals on the ultraviolet light irradiation wavelength was investigated. When irradiated with 365 nm light, a crystal of 1,2-bis(5-methyl-2-phenyl-4-thiazolyl)perfluorocyclopentene (1a) bends toward the incident light. On the other hand, when irradiated with 380 nm light, the crystal of 1a first bends away from the light source and then bends toward the incident light. To explain this bending behavior, we propose a comprehensive mechanism based on the depth of the photochromic reaction from the crystal surface. This mechanism is successfully supported by the change of cell parameters associated with the photochromic reaction upon irradiation with 380 nm light, which was determined by in situ X-ray crystallographic analysis.

  8. Protein secondary-shell interactions enhance the photoinduced hydrogen production of cobalt protoporphyrin IX.

    PubMed

    Sommer, Dayn Joseph; Vaughn, Michael David; Ghirlanda, Giovanna

    2014-12-28

    Hydrogen is an attractive fuel with potential for production scalability, provided that inexpensive, efficient molecular catalysts utilizing base metals can be developed for hydrogen production. Here we show for the first time that cobalt myoglobin (CoMyo) catalyzes hydrogen production in mild aerobic conditions with turnover number of 520 over 8 hours. Compared to free Co-protoporphyrin IX, incorporation into the myoglobin scaffold results in a 4-fold increase in photoinduced hydrogen production activity. Engineered variants in which specific histidine resides in proximity of the active site were mutated to alanine result in modulation of the catalytic activity, with the H64A/H97A mutant displaying activity 2.5-fold higher than wild type. Our results demonstrate that protein scaffolds can augment and modulate the intrinsic catalytic activity of molecular hydrogen production catalysts.

  9. Photo-induced current transient spectroscopy of single crystal Tl6I4Se

    NASA Astrophysics Data System (ADS)

    Liu, Z.; Peters, J. A.; Sebastian, M.; Kanatzidis, M. G.; Im, J.; Freeman, A. J.; Wessels, B. W.

    2014-11-01

    The compound Tl6I4Se is a promising wide band gap semiconductor for hard radiation detection at room temperature. To further improve its detection efficiency, native defects have been investigated using photo-induced current transient spectroscopy (PICTS). We observe two shallow acceptor levels with mean activation energies of 76, 175 meV, and two shallow donor defects 62, and 96 meV, respectively. No deeper donor levels are observed. The levels are attributed to native point defects. Defect capture cross sections in the range 10-21 to 10-18 cm2 were measured. The small capture cross sections are attributed to the effective screening of the defects due to a large static dielectric constant.

  10. Photoinduced DNA damage and cytotoxicity by a triphenylamine-modified platinum-diimine complex.

    PubMed

    Zhang, Zhigang; Dai, Ruihui; Ma, Jiajia; Wang, Shuying; Wei, Xuehong; Wang, Hongfei

    2015-02-01

    Many planar photosensitizers tend to self-aggregate via van der Waals interactions between π-conjugated systems. The self-aggregation of the photosensitizer may reduce the efficiency of the photosensitizer to generate singlet oxygen, thereby diminishing its photodynamic activity. Efforts have been made to improve the photodynamic activity of bis-(o-diiminobenzosemiquinonato)platinum(II) which has planar geometry by the introduction of the sterically hindered triphenylamine moiety into the ligand. Herein we report the photoinduced DNA damage and cytotoxicity by a triphenylamine-modified platinum-diimine complex in red light studied by fluorescence spectra, agarose gel assay and cell viability assay. The results suggest that the triphenylamine-modified platinum-diimine complex has better capability to generate singlet oxygen than bis-(o-diiminobenzosemiquinonato)platinum(II), and it can induce DNA damage in red light, causing high photocytotoxicity in HepG-2 cells in vitro.

  11. Photoinduced formation of peroxyl radicals in aqueous solutions of nucleobase derivatives at 77 K

    NASA Astrophysics Data System (ADS)

    Lozinova, T. A.; Lander, A. V.

    2015-05-01

    It is shown that the formation of free radicals photoinduced by near-UV irradiation at 77 K in aqueous solutions of guanosine-5'-monophosphate (GMP), adenosine (Ado), adenine (A), and thymine (T) containing NaCl (0.1 M) is intensified in the presence of O2. Signals of peroxyl radicals O{2/-·} and HO{2/·} are indicated in analyzing EPR spectra, and their overall yield is 20-40% of the total amount of the formed paramagnetic products. It is found that the concentration ratio of O{2/-·} and HO{2/·} radicals depends not only on pH of the solutions before freezing but also on the duration of irradiation and method of freezing the samples. Plausible mechanisms of the processes are discussed.

  12. Photoinduced Formation of Colloidal Silver in Nitrocellulose Solutions Containing Titanium Alkoxides

    NASA Astrophysics Data System (ADS)

    Kulak, A. I.; Branitsky, G. A.

    2016-07-01

    The study shows the possibility of photo-induced reduction of silver nitrate and formation of stable colloidal silver particles in an isopropanol-N,N-dimethylacetamide solution of titanium alkoxide (polybutyl titanate) stabilized by nitrocellulose. It is established that titanium alkoxide and the products of its partial hydrolysis in the liquid composition play the role of a photocatalyst for the reduction of silver ions; the introduction of nitric or acetic acid additives to the composition significantly increases its photosensitivity. The films deposited from the liquid composition, previously irradiated with visible or UV light, consist of hydrated titanium dioxide and nitrocellulose with incorporated colloidal silver. Thermal treatment of the films at 150-245°C leads to the decomposition of nitrocellulose and an increase in the absorption by silver particles.

  13. Control of photoinduced fluorescence enhancement of colloidal quantum dots using metal oxides

    NASA Astrophysics Data System (ADS)

    Sadeghi, Seyed M.; Wing, Waylin J.; Patty, Kira; Campbell, Quinn

    2015-10-01

    It is well known that irradiation of colloidal quantum dots can dramatically enhance their emission efficiencies, leading to so-called photoinduced fluorescence enhancement (PFE). This process is the result of the photochemical and photophysical properties of quantum dots and the way they interact with the environment in the presence of light. It has been shown that such properties can be changed significantly using metal oxides. Using spectroscopic techniques, in this paper we investigate emission of different types of quantum dots (with and without shell) in the presence of metal oxides with opposing effects. We observed significant increase of PFE when quantum dots are deposited on about one nanometer of aluminum oxide, suggesting such oxide can profoundly increase quantum yield of such quantum dots. On the other hand, copper oxide can lead to significant suppression of emission of quantum dots, making them nearly completely dark instantly.

  14. Photoinduced reduction of divalent mercury by quinones in the presence of formic acid under anaerobic conditions.

    PubMed

    Berkovic, Andrea M; Bertolotti, Sonia G; Villata, Laura S; Gonzalez, Mónica C; Pis Diez, Reinaldo; Mártire, Daniel O

    2012-11-01

    The laser flash photolysis technique (λ(exc)=355 nm) was used to investigate the mechanism of the HgCl(2) reduction mediated by CO(2)(-) radicals generated from quenching of the triplet states of 1,4-naphthoquinone (NQ) by formic acid. Kinetic simulations of the experimental signals support the proposed reaction mechanism. This system is of potential interest in the development of UV-A photoinduced photolytic procedures for the treatment of Hg(II) contaminated waters. The successful replacement of NQ with a commercial fulvic acid, as a model compound of dissolved organic matter, showed that the method is applicable to organic matter-containing waters without the addition of quinones.

  15. Dynamics of photoinduced processes in liquid-crystal polymer films containing azo compounds

    SciTech Connect

    Simonov, A N; Larichev, A V

    1999-07-31

    The photoinduced processes in azo-compound-containing side-chain polymer films with liquid-crystal properties are examined theoretically. A model is proposed whereby it is possible to consider the dynamics of the optical response of a medium taking into account the anisotropic saturation in the angular distribution of the azo-dye isomers as well as the intermolecular interaction. The influence of the liquid-crystal ordering in the polymer is taken into account by introducing a phenomenological mean-field factor. Analytical solutions describing changes in the optical properties of a polymer film during the initial illumination stages are in good agreement with experimental data. (this issue is dedicated to the memory of s a akhmanov)

  16. Photo-induced potential barrier in As-Se-Ge films

    NASA Astrophysics Data System (ADS)

    Katyal, S. C.; Okano, S.; Suzuki, M.; Bando, T.

    1988-05-01

    Photo-excited effects in AsSeGe and AsSeGeSn amorphous films have been studied under illumination of different light sources. AsSeGe system exhibited rectifying characteristics under illumination of the light with hν > E g, while AsSeGeSn film did not show such phenomena. The illumination of the IR light along with the light of hν > E g weakened the rectification behavior. The photovoltage and I-V characteristics results suggest the existence of "photo-induced" potential barrier in AsSeGe system, which is considered to concern the creation and destruction of neutral defect states D°.

  17. An Explanation of the Photoinduced Giant Dielectric Constant of Lead Halide Perovskite Solar Cells.

    PubMed

    Almond, Darryl P; Bowen, Chris R

    2015-05-07

    A photoinduced giant dielectric constant of ~10(6) has been found in impedance spectroscopy measurements of lead halide perovskite solar cells. We report similar effects in measurements of a porous lead zirconate titanate (PZT) sample saturated with water. The principal effect of the illumination of the solar cell and of the introduction of water into the pore volume of the PZT sample is a significant increase in conductivity and dielectric loss. This is shown to exhibit low frequency power law dispersion. Application of the Kramers-Kronig relationships show the large measured values of permittivity to be related to the power law changes in conductivity and dielectric loss. The power law dispersions in the electrical responses are consistent with an electrical network model of microstructure. It is concluded that the high apparent values of permittivity are features of the microstructural networks and not fundamental effects in the two perovskite materials.

  18. Photo-induced toxicity of titanium dioxide nanoparticles to Daphnia magna under natural sunlight.

    PubMed

    Mansfield, C M; Alloy, M M; Hamilton, J; Verbeck, G F; Newton, K; Klaine, S J; Roberts, A P

    2015-02-01

    Titanium dioxide nanoparticles (TiO2 NP) are one of the most abundantly utilized nanoparticles in the world. Studies have demonstrated the ability of the anatase crystal of TiO2 NP to produce reactive oxygen species (ROS) in the presence of ultraviolet radiation (UVR), a co-exposure likely to occur in aquatic ecosystems. The goal of this study was to examine the photo-induced toxicity of anatase TiO2 NP under natural sunlight to Daphnia magna. D. magna were exposed to a range of UVR intensities and anatase TiO2 concentrations in an outdoor exposure system using the sun as the source of UVR. Different UVR intensities were achieved using UVR opaque and transparent plastics. AnataseTiO2-NP demonstrated the reciprocal relationship seen in other phototoxic compounds such as polycyclic aromatic hydrocarbons (PAHs) at higher UVR treatments. The calculated 8h LC50 of anatase TiO2 NP was 139 ppb under full intensity ambient natural sunlight, 778 ppb under 50% natural sunlight, and >500 ppm under 10% natural sunlight. Mortality was also compared between animals allowed to accumulate a body burden of anatase TiO2 for 1h and organisms whose first exposure to anatase TiO2 aqueous suspensions occurred under UVR. A significantly greater toxic effect was observed in aqueous, low body burden suspensions than that of TiO2 1h body burdens, which is dissimilar from the model presented in PAHs. Anatase TiO2 presents a unique photo-induced toxic model that is different than that of established phototoxic compounds.

  19. Ab initio spectroscopy and photoinduced cooling of the trans-stilbene molecule.

    PubMed

    Tatchen, Jörg; Pollak, Eli

    2008-04-28

    We present a theoretical study of the S(0)-->S(1) and S(0)<--S(1) vibronic spectra for trans-stilbene. Franck-Condon spectra in the harmonic approximation are generated for the complete system with 72 degrees of freedom by means of an analytic time-dependent approach accounting for Dushinsky rotations and thermal effects. The force fields are computed by means of density functional theory (DFT) and time-dependent DFT, on the one hand, and ab initio complete active space self-consistent field theory, on the other hand. The B3LYP functional shows that almost planar potential energy surface minima are found for the S(0) and S(1) state. Imposing C(2h) symmetry constraints, we obtain low-temperature high-resolution Franck-Condon spectra for both absorption and emission which are in reasonably good agreement with the experimental spectra measured by Syage et al. [J. Chem. Phys. 81, 4685 (1984)] in supersonic jets. Due to thermal population of low-energy modes, the room temperature absorption spectrum is very broad. An almost structureless band which extends over several thousand cm(-1) is obtained from the present theory and agrees with the experimental absorption band shape. Finally, within the harmonic model, we study the effect of photoexcitation on the energy distribution in the excited S(1) state. We find noticeable cooling of approximately 20 K within a frequency interval spanning from -400 to 200 cm(-1) around the 0-0 transition. This indicates that photoinduced cooling must be taken into account when considering the dynamics of the photoinduced isomerization of trans-stilbene. Moreover, this is not the final word, as anharmonicity of the low frequency modes must be taken into account to obtain a full picture which would explain both the energy dependence of the isomerization rates as well as the dependence on the pressure of an external buffer gas.

  20. Effect of irradiance spectra on the photoinduced toxicity of three polycyclic aromatic hydrocarbons

    SciTech Connect

    Diamond, S.A.; Mount, D.R.; Burkhard, L.P.; Ankley, G.T.; Makynen, E.A.; Leonard, E.N.

    2000-05-01

    Photoinduced toxicity of polycyclic aromatic hydrocarbons (PAHs) is dependent on the concentration of compounds present and the dose of light received. Of the light present, only those wavelengths absorbed by the compound have the potential to initiate the photochemical events underlying phototoxicity. This suggests that variation in light spectra present in natural waters, arising from variation in dissolved organic carbon composition, is an important determinant of phototoxicity risk in specific, PAH-contaminated waterbodies. To quantify the effect of environmentally realistic variation in light spectra on toxicity, brine shrimp (Artemia salina) assays were conducted under various light spectra and with three PAHs (pyrene, fluoranthene, and anthracene) of known phototoxicity potential. In these spectral assays, the total ultraviolet light present was equivalent; only the spectral characteristics varied. Based on the absorbance spectra of these PAHs, it was predicted that toxicity, quantified using immobilization as the endpoint, would vary significantly among light spectra in pyrene assays, but not in anthracene assays, and that variation in toxicity in fluoranthene assays would be intermediate. The results supported these assumptions. In the pyrene exposures, the glass filter time to 50% population immobilization (IT50) (39.5 min) was 117% longer than the KCr filter IT50 (18.2 min). In the fluoranthene exposures, the glass filter IT50 (49.5 min) was 27% longer than the KCr filter IT50 (39.1 min). In the anthracene exposures, the glass filter IT50 (62.2 min) was not statistically different from the KCr filter IT50 (63.8 min). Comparison of these results with the results of assays conducted under neutral-density filters (that change intensity but not spectral distribution) demonstrate that multiplying spectral intensity by wavelength-specific absorbance accurately predicts relative photoinduced toxicity among the experimental treatments. These results indicate

  1. Photoinduced aging and viscosity evolution in Se-rich Ge-Se glasses

    SciTech Connect

    Gueguen, Yann; Sangleboeuf, Jean-Christophe; Rouxel, Tanguy; King, Ellyn A.; Lucas, Pierre; Keryvin, Vincent; Bureau, Bruno

    2013-08-21

    We propose here to investigate the non-equilibrium viscosity of Ge-Se glasses under and after light irradiation. Ge{sub 10}Se{sub 90} and Ge{sub 20}Se{sub 80} fibers have been aged in the dark and under ambient light, over months. During aging, both the relaxation of enthalpy and the viscosity have been investigated. The viscosity was measured by shear relaxation-recovery tests allowing the measurement of non-equilibrium viscosity. When Ge{sub 10}Se{sub 90} glass fibers are aged under irradiation, a relatively fast fictive temperature decrease is observed. Concomitantly, during aging under irradiation, the non-equilibrium viscosity increases and reaches an equilibrium after two months of aging. This viscosity increase is also observed in Ge{sub 20}Se{sub 80} fibers. Nevertheless, this equilibrium viscosity is far below the viscosity expected at the configurational equilibrium. As soon as the irradiation ceases, the viscosity increases almost instantaneously by about one order of magnitude. Then, if the fibers are kept in the dark, their viscosity slowly increases over months. The analysis of the shear relaxation functions shows that the aging is thermorheologically simple. On the other side, there is no simple relaxation between the shear relaxation functions measured under irradiation and those measured in the dark. These results clearly suggest that a very specific photoinduced aging process occurs under irradiation. This aging is due to photorelaxation. Nevertheless, the viscosity changes are not solely correlated to photoaging and photorelaxation. A scenario is proposed to explain all the observed viscosity evolutions under and after irradiation, on the basis of photoinduced transient defects.

  2. Influence of adduct stereochemistry and hydrogen-bonding solvents on photoinduced charge transfer in a covalent benzo[a]pyrene diol epoxide-nucleoside adduct on picosecond time scales

    SciTech Connect

    O'Connor, D. ); Shafirovich, V.Y.; Geacintov, N.E. )

    1994-09-29

    Photoinduced electron transfer occurs with different rate constants upon picosecond laser pulse excitation of the stereoisomeric (+)-trans- and (-)-cis-benzo[a]pyrene diol epoxide-N[sup 2]-deoxyguanosine covalently linked adducts (BPDE-N[sup 2]-dG, bond with 10S absolute configuration) in polar solvents (N,N[prime]-dimethylformamide (DMF), and the hydrogen-bonding liquids H[sub 2]O, D[sub 2]O, formamide (FA), and N-methylformamide (NMF)). In the case of (+)-trans-BPDE-dG in DMF, photoinduced electron transfer occurs in the normal Marcus region, from dG to the pyrenyl residue singlet with a rate constant k[sub s] = (9.1 [+-] 0.9) x 10[sup 9] s[sup [minus]1], which is followed by a slower recombination (k[sub r] = (1.8 + 0.5) x 10[sup 9] s[sup [minus]1]) in the inverted Marcus region. In the cis-stereoisomeric adduct, both rate constants are enhanced by a factor of approximately 5. The presence of the hydrogen-bonding network in NMF and FA exerts opposite effects on these rate constants, decreasing k[sub s] and increasing k[sub r] by factors of 2-5. In aqueous solutions these effects are even more pronounced, and radical ions are not observed since k[sub r] [much gt] k[sub s]. A kinetic isotope effect on the delay of the pyrenyl singlets in H[sub 2]O and D[sub 2]O (k[sub s](H[sub 2]O)/k[sub s](D[sub 2]O) = 1.3-1.5) suggests that a proton-coupled electron transfer mechanism may be operative in aqueous solutions. 51 refs., 10 figs., 2 tabs.

  3. INTERACTION OF LASER RADIATION WITH MATTER. LASER PLASMA: Photoinduced anisotropy of the refractive index of an azopolymer with liquid-crystal properties

    NASA Astrophysics Data System (ADS)

    Andreeva, M. S.; Shmalgauzen, V. I.

    2004-01-01

    The formation of a photoinduced refractive-index grating in a photosensitive azopolymer with liquid-crystal (LC) properties is theoretically studied. Equations for photoinduced additions to the refractive index of the LC and amorphous polymers are obtained from balance equations for the distribution densities of trans- and cis-isomers of azodyes. The frequency characteristics of the response of the refractive index to a harmonic perturbation are calculated for different values of the LC order parameter.

  4. Ultrafast photoinduced charge separation in naphthalene diimide based multichromophoric systems in liquid solutions and in a lipid membrane.

    PubMed

    Banerji, Natalie; Fürstenberg, Alexandre; Bhosale, Sheshanath; Sisson, Adam L; Sakai, Naomi; Matile, Stefan; Vauthey, Eric

    2008-07-31

    The photophysical properties of multichromophoric systems consisting of eight red or blue naphthalene diimides (NDIs) covalently attached to a p-octiphenyl scaffold, as well as a blue bichromophoric system with a biphenyl scaffold, have been investigated in detail using femtosecond time-resolved spectroscopy. The blue octachromophoric systems have been recently shown to self-assemble as supramolecular tetramers in lipid bilayer membranes and to enable generation of a transmembrane proton gradient upon photoexcitation ( Bhosale, S. ; Sisson, A. L. ; Talukdar, P. ; Fürstenberg, A. ; Banerji, N. ; Vauthey, E. ; Bollot, G. ; Mareda, J. ; Röger, C. ; Würthner, F. ; Sakai, N. ; Matile, S. Science 2006, 313, 84 ). A strong reduction of the fluorescence quantum yield was observed when going from the single NDI units to the multichromophoric systems in methanol, the effect being even stronger in a vesicular lipid membrane. Fluorescence up-conversion measurements reveal ultrafast self-quenching in the multichromophoric systems, whereas the formation of the NDI radical anion, evidenced by transient absorption measurements, points to the occurrence of photoinduced charge separation. The location of the positive charge could not be established unambiguously from the transient absorption measurements, but energetic considerations indicate that charge separation should occur between two NDI units in the blue systems, whereas both an NDI unit and the p-octiphenyl scaffold could act as electron donor in the red system. The lifetime of the charge-separated state was found to increase from 22 to 45 ps by going from the bi- to the octachromophoric blue systems in methanol, while a 400 ps decay component was observed in the lipid membrane. This lifetime lengthening is explained in terms of charge migration that is most efficient when the octachromophoric systems are assembled as supramolecular tetramers in the lipid membrane. Furthermore, the average charge-separated state lifetime

  5. Quantum Ising model coupled with conducting electrons

    NASA Astrophysics Data System (ADS)

    Yamashita, Yasufumi; Yonemitsu, Kenji

    2005-01-01

    The effect of photo-doping on the quantum paraelectric SrTiO3 is studied by using the one-dimensional quantum Ising model, where the Ising spin describes the effective lattice polarization of an optical phonon. Two types of electron-phonon couplings are introduced through the modulation of transfer integral via lattice deformations. After the exact diagonalization and the perturbation studies, we find that photo-induced low-density carriers can drastically alter quantum fluctuations when the system locates near the quantum critical point between the quantum para- and ferro-electric phases.

  6. ESIPT and photodissociation of 3-hydroxychromone in solution: photoinduced processes studied by static and time-resolved UV/Vis, fluorescence, and IR spectroscopy.

    PubMed

    Chevalier, Katharina; Grün, Anneken; Stamm, Anke; Schmitt, Yvonne; Gerhards, Markus; Diller, Rolf

    2013-11-07

    The spectral properties of fluorescence sensors such as 3-hydroxychromone (3-HC) and its derivatives are sensitive to interaction with the surrounding medium as well as to substitution. 3-HC is a prototype system for other derivatives because it is the basic unit of all flavonoides undergoing ESIPT and is not perturbed by a substituent. In this study, the elementary processes and intermediate states in the photocycle of 3-HC as well as its anion were identified and characterized by the use of static and femtosecond time-resolved spectroscopy in different solvents (methylcyclohexane, acetonitrile, ethanol, and water at different pH). Electronic absorption and fluorescence spectra and lifetimes of the intermediate states were obtained for the normal, tautomer and anionic excited state, while mid-IR vibrational spectra yielded structural information on ground and excited states of 3-HC. A high sensitivity on hydrogen-bonding perturbations was observed, leading to photoinduced anion formation in water, while in organic solvents, different processes are suggested, including slow picosecond ESIPT and contribution of the trans-structure excited state or a different stable solvation state with different direction of OH. The formation of the latter could be favored by the lack of a substituent increasing contact points for specific solute-solvent interactions at the hydroxyl group compared to substituted derivatives. The effect of substituents has to be considered for the design of future fluorescence sensors based on 3-HC.

  7. Characterization of defect levels in semi-insulating 6H-SiC by means of photoinduced transient spectroscopy and modulated photocurrent technique.

    PubMed

    Longeaud, C; Kleider, J P; Kaminski, P; Kozlowski, R; Miczuga, M

    2009-01-28

    Parameters of electrically active defect centres in vanadium-doped 6H silicon carbide (6H-SiC:V) were investigated by means of the photoinduced transient spectroscopy (PITS) and modulated photocurrent (MPC) method. After a short description of the two techniques, experimental results are presented and briefly compared. Our aim is mainly to understand and explain these experimental results. In particular, in the PITS technique a shallow level seems to be at the origin of negative photoconductivity. Besides, in the same temperature range hole and electron levels can be detected at the same time. Finally, the detection of a given level seems to depend on the photon flux used to perform the PITS experiment. As far as the MPC experiment is concerned, it has put into evidence a very efficient shallow level. A numerical calculation was developed to simulate both experiments in order to understand the experimental results. By means of this simulation, we have explained all the phenomena observed experimentally in each technique and we propose a simple model for the distribution of electrically active defect centres in 6H-SiC:V crystals.

  8. Study of asymmetries of Cd(Zn)Te devices investigated using photo-induced current transient spectroscopy, Rutherford backscattering, surface photo-voltage spectroscopy, and gamma ray spectroscopies

    SciTech Connect

    Crocco, J.; Bensalah, H.; Zheng, Q.; Dieguez, E.; Corregidor, V.; Avles, E.; Castaldini, A.; Fraboni, B.; Cavalcoli, D.; Cavallini, A.; Vela, O.

    2012-10-01

    Despite these recent advancements in preparing the surface of Cd(Zn)Te devices for detector applications, large asymmetries in the electronic properties of planar Cd(Zn)Te detectors are common. Furthermore, for the development of patterned electrode geometries, selection of each electrode surface is crucial for minimizing dark current in the device. This investigation presented here has been carried out with three objectives. Each objective is oriented towards establishing reliable methods for the selection of the anode and cathode surfaces independent of the crystallographic orientation. The objectives of this study are (i) investigate how the asymmetry in I-V characteristics of Cd(Zn)Te devices may be associated with the TeO2 interfacial layer using Rutherford backscattering to study the structure at the Au-Cd(Zn)Te interface, (ii) develop an understanding of how the concentration of the active traps in Cd(Zn)Te varies with the external bias, and (iii) propose non-destructive methods for selection of the anode and cathode which are independent of crystallographic orientation. The spectroscopic methods employed in this investigation include Rutherford backscattering spectroscopy, photo-induced current transient spectroscopy, and surface photo-voltage spectroscopy, as well as gamma ray spectroscopy to demonstrate the influence on detector properties.

  9. Role of polytypism and degree of hexagonality on the photoinduced optical second harmonic generation in SiC nanocrystalline films

    NASA Astrophysics Data System (ADS)

    Semenov, A.; Puziko, V.; Skorik, S.; Wojciechowski, A.; Fedorchuk, A. O.; Maciąg, A.

    2015-05-01

    Photoinduced optiсal second harmonic generation was studied in nanocrystalline SiC films prepared by the method of direct ion deposition. For the studies were chosen three types of polytypes (with different degree of hexagonality) - 24R with degree hexagonality G=25, 27R-G=44, 33R with - G=36. The bicolor photoinduced treatment was performed by the wavelengths 1064nm/532 nm by 15 ns YAG:Nd laser. The efficiency of the output SHG was evaluated by ratio of the corresponding signal intensities with respect to the references and by the time delay between the SHG and the fundamental maxima. Explanation of the observed effect is given within a framework of the occurrence of the nano-trapping levels in the film crystalline interfaces.

  10. Ultrafast in cellulo photoinduced dynamics processes of the paradigm molecular light switch [Ru(bpy)2dppz]2+

    NASA Astrophysics Data System (ADS)

    de La Cadena, Alejandro; Davydova, Dar’Ya; Tolstik, Tatiana; Reichardt, Christian; Shukla, Sapna; Akimov, Denis; Heintzmann, Rainer; Popp, Jürgen; Dietzek, Benjamin

    2016-09-01

    An in cellulo study of the ultrafast excited state processes in the paradigm molecular light switch [Ru(bpy)2dppz]2+ by localized pump-probe spectroscopy is reported for the first time. The localization of [Ru(bpy)2dppz]2+ in HepG2 cells is verified by emission microscopy and the characteristic photoinduced picosecond dynamics of the molecular light switch is observed in cellulo. The observation of the typical phosphorescence stemming from a 3MLCT state suggests that the [Ru(bpy)2dppz]2+ complex intercalates with the DNA in the nucleus. The results presented for this benchmark coordination compound reveal the necessity to study the photoinduced processes in coordination compounds for intracellular use, e.g. as sensors or as photodrugs, in the actual biological target environment in order to derive a detailed molecular mechanistic understanding of the excited-state properties of the systems in the actual biological target environment.

  11. Ultrafast in cellulo photoinduced dynamics processes of the paradigm molecular light switch [Ru(bpy)2dppz]2+

    PubMed Central

    De la Cadena, Alejandro; Davydova, Dar’ya; Tolstik, Tatiana; Reichardt, Christian; Shukla, Sapna; Akimov, Denis; Heintzmann, Rainer; Popp, Jürgen; Dietzek, Benjamin

    2016-01-01

    An in cellulo study of the ultrafast excited state processes in the paradigm molecular light switch [Ru(bpy)2dppz]2+ by localized pump-probe spectroscopy is reported for the first time. The localization of [Ru(bpy)2dppz]2+ in HepG2 cells is verified by emission microscopy and the characteristic photoinduced picosecond dynamics of the molecular light switch is observed in cellulo. The observation of the typical phosphorescence stemming from a 3MLCT state suggests that the [Ru(bpy)2dppz]2+ complex intercalates with the DNA in the nucleus. The results presented for this benchmark coordination compound reveal the necessity to study the photoinduced processes in coordination compounds for intracellular use, e.g. as sensors or as photodrugs, in the actual biological target environment in order to derive a detailed molecular mechanistic understanding of the excited-state properties of the systems in the actual biological target environment. PMID:27644587

  12. Sequence-specific photoinduced c-fos gene damage mediated by triple stranded-forming oligonucleotide conjugated to psoralen

    NASA Astrophysics Data System (ADS)

    Cao, En-Hua; Wang, Ju-jun; Ma, Wenjian; Qin, Jingfen

    1999-09-01

    A psoralen-oligonucleotide conjugate was designed to photoinduce a cross-link at a specific sequence of c-fos oncogene. Psoralen was attached to its C-3 position of a 20-base mer oligonucleotide, which binds to a synthetic 49 bp duplex containing the c-fos gene polypurine site, where it forms a triple stranded DNA. Upon near-UV-irradiation, the two strand of DNA are crosslinked at the TpA step present at the triple-duplex junction. Results show that the yield of the photoinduce cross- linking reaction is quite high. We treated HeLa cells with above 2-mer oligonucleotide conjugated to psoralen. The expression of c-fos oncogene was significant reduced, no significant effect on the level of c-myc mRNA. These data indicate that such psoralen- oligonucleotide conjugates could be used to selectively control gene expression or to induce sequence-specific damages.

  13. Photoinduced fluorescence enhancement in colloidal CdSeTe /ZnS core/shell quantum dots

    NASA Astrophysics Data System (ADS)

    Yuan, C. T.; Chou, W. C.; Chuu, D. S.; Chen, Y. N.; Lin, C. A.; Chang, W. H.

    2008-05-01

    Photoinduced fluorescence enhancement (PFE) in colloidal CdSeTe /ZnS core/shell quantum dots (QDs) was investigated by monitoring ensemble fluorescence and single-QD fluorescence blinking behavior upon illumination. Ensemble fluorescence was increased in air and in vacuum with different enhanced factors. At the single-QD levels, fluorescence was also enhanced for some individual QDs. Relatively long on times, high quantum yields within the on times, and multilevel on states were found in fluorescence time traces. We suggest that the PFE origin from single-QD viewpoint is attributed to the contributions of surface passivation by photoinduced charged carriers and the formation of neutral core/charged shell QD states.

  14. Specific features of photoconductivity and photoinduced piezoelectricity in AgGaGe3Se8 doped crystals

    NASA Astrophysics Data System (ADS)

    Kityk, I. V.; Myronchuk, G. L.; Parasyuk, O. V.; Krymus, A. S.; Rakus, P.; El-Naggar, A. M.; Albassam, A. A.; Lakshminarayana, G.; Fedorchuk, A. O.

    2017-01-01

    In this work, complex photoconductivity and photo-induced piezoelectricity studies were performed for the AgGaGe3Se8 single crystals doped by In, Sn and Cu with content 5% in weighting units. The principal role of the intrinsic cationic and anionic defects is demonstrated. The photoconductivity and optical absorption spectra show substantial changes of effective energy gap and steepness of absorption edge. The role of optical transitions between the localized states in the presence of Sn, Cu, In impurities is explored. Piezoelectric studies under external laser illumination have shown significant role of dopants on the piezoelectric constants values and their anisotropy. Clear photo-induced jumps were discovered. The discussion is performed within the framework of crystallochemistry analysis and quantum chemical evaluations. Possibility of production of optically operated piezoelectric triggers is proposed.

  15. Cyclic performance and photo-induced crystalline growth of nanostructured AgI/TiO2 visible light photocatalyst.

    PubMed

    He, Ke Feng; Feng, Lu; Wang, Lin; Chen, Wan Ping

    2012-03-01

    Nanostructured AgI/TiO2 visible light photocatalyst was prepared with AgNO3, KI, and Ti(OBu)4 as precursors. The photocatalyst was used repeatedly to degrade methylene blue and methyl orange in water with visible light irradiation. Though a high photocatalytic efficiency was observed for the photocatalyst in the first cycle, the photocatalytic efficiency was found to decrease dramatically in subsequent cycles. X-ray diffraction and SEM analyses revealed an obvious crystalline growth of AgI in AgI/TiO2 nanocomposite after photocatalysis or visible light irradiation. It was proposed that photo-induced crystalline growth had occurred to AgI in the course of photocatalysis and resulted in dramatic decrease in the photocatalytic efficiency of the photocatalyst. Photo-induced crystalline growth may be a limiting factor for the lifetime of photocatalysts and should be examined as an important aspect of photostability when new photocatalysts are developed.

  16. Photoinduced bending behavior of cross-linked azobenzene liquid-crystalline polymer films with a poly(oxyethylene) backbone.

    PubMed

    Lv, Jiu-an; Wang, Weiru; Xu, Jixiang; Ikeda, Tomiki; Yu, Yanlei

    2014-07-01

    Cross-linked azobenzene liquid-crystalline polymer films with a poly(oxyethylene) backbone are synthesized by photoinitiated cationic copolymerization. Azobenzene moieties in the film surface toward the light source are simultaneously photoaligned during photopolymerization with unpolarized 436 nm light and thus form a splayed alignment in the whole film. The prepared films show reversible photoinduced bending behavior with opposite bending directions when different surfaces of one film face to ultraviolet light irradiation.

  17. Electron transfer through rigid organic molecular wires enhanced by electronic and electron-vibration coupling.

    PubMed

    Sukegawa, Junpei; Schubert, Christina; Zhu, Xiaozhang; Tsuji, Hayato; Guldi, Dirk M; Nakamura, Eiichi

    2014-10-01

    Electron transfer (ET) is a fundamental process in a wide range of biological systems, photovoltaics and molecular electronics. Therefore to understand the relationship between molecular structure and ET properties is of prime importance. For this purpose, photoinduced ET has been studied extensively using donor-bridge-acceptor molecules, in which π-conjugated molecular wires are employed as bridges. Here, we demonstrate that carbon-bridged oligo-p-phenylenevinylene (COPV), which is both rigid and flat, shows an 840-fold increase in the ET rate compared with the equivalent flexible molecular bridges. A 120-fold rate enhancement is explained in terms of enhanced electronic coupling between the electron donor and the electron acceptor because of effective conjugation through the COPVs. The remainder of the rate enhancement is explained by inelastic electron tunnelling through COPV caused by electron-vibration coupling, unprecedented for organic molecular wires in solution at room temperature. This type of nonlinear effect demonstrates the versatility and potential practical utility of COPVs in molecular device applications.

  18. Photoinduced anisotropy of push-pull chromophores incorporating 5-(1,3-benzodithiol-2-ylidene)-1-(4-nitrophenyl) penta-1,3-diene embedded into photopolymer oligoetheracrylate matrices

    NASA Astrophysics Data System (ADS)

    Sahraoui, B.; Kityk, I. V.; Kasperczyk, J.; Salle, M.; Nguyen, T. T.

    2000-04-01

    Photoinduced (PI) birefringence (Δ n) and phototransparency ( T) have been studied for a wavelength of 633 nm (He-Ne laser) under photoillumination by doubled-frequency YAG:Nd pulse laser polarized beam ( λ=0.53 μm; pulse duration τ=10-50 ps). The push-pull chromophore 5-(1,3-benzodithiol-2-ylidene)-1-(4-nitrophenyl) penta-1,3-diene was incorporated into an oligoetheracrylate photopolymer matrix in a concentration of about 2.5 wt.%. Special properties of the molecule are connected with substantial role played by electron-vibration interactions in the observed PI effects. The Δ n decreases with decreasing temperature. Optical density D depends non-linearly on the PI beam power. With increasing photoinducing power (up to 0.41 GW/cm 2), the PI birefringence Δ n and the optical density D approaches (1.4-1.7)×10 -3 and 1.5%, respectively. The intensity dependence of intramolecular (669 cm -1) and intermolecular (89.5 cm -1) vibration mode has a maximum and a broad minimum (at a PI power of about 0.45 GW/cm 2), respectively. Such behavior correlates well with the PI dependencies of the Δ n and the optical density D. Description of the obtained results is based on quantum chemical calculations with taking into account an electron-vibration anharmonicity of the chromophore. Essential role of the PI electrostatic potential redistribution under influence of the PI polarized light beam has been demonstrated. Possible mechanisms of the observed phenomena are discussed within a phenomenological as well as microscopic approach.

  19. A Comparison of Photo-Induced Hysteresis Between Hydrogenated Amorphous Silicon and Amorphous IGZO Thin-Film Transistors.

    PubMed

    Ha, Tae-Jun; Cho, Won-Ju; Chung, Hong-Bay; Koo, Sang-Mo

    2015-09-01

    We investigate photo-induced instability in thin-film transistors (TFTs) consisting of amorphous indium-gallium-zinc-oxide (a-IGZO) as active semiconducting layers by comparing with hydrogenated amorphous silicon (a-Si:H). An a-IGZO TFT exhibits a large hysteresis window in the illuminated measuring condition but no hysteresis window in the dark condition. On the contrary, a large hysteresis window measured in the dark condition in a-Si:H was not observed in the illuminated condition. Even though such materials possess the structure of amorphous phase, optical responses or photo instability in TFTs looks different from each other. Photo-induced hysteresis results from initially trapped charges at the interface between semiconductor and dielectric films or in the gate dielectric which possess absorption energy to interact with deep trap-states and affect the movement of Fermi energy level. In order to support our claim, we also perform CV characteristics in photo-induced hysteresis and demonstrate thermal-activated hysteresis. We believe that this work can provide important information to understand different material systems for optical engineering which includes charge transport and band transition.

  20. Characteristics of light-induced electron transport from P3HT to ZnO-nanowire field-effect transistors

    NASA Astrophysics Data System (ADS)

    Choe, Minhyeok; Hoon Lee, Byoung; Park, Woojin; Kang, Jang-Won; Jeong, Sehee; Cho, Kyungjune; Hong, Woong-Ki; Hun Lee, Byoung; Lee, Kwanghee; Park, Seong-Ju; Lee, Takhee

    2013-11-01

    We fabricated ZnO-nanowire (NW) field-effect transistors (FETs) coated with poly(3-hexylthiophene) (P3HT) and characterized the electron-transfer characteristics from the P3HT to the ZnO NWs. Under irradiation by laser light with a wavelength of 532 nm, photo-induced electrons were created in the P3HT and then transported to the ZnO NWs, constituting a source-drain current in the initially enhancement-mode P3HT-coated ZnO-NW FETs. As the intensity of the light increased, the current increased, and its threshold voltage shifted to the negative gate-bias direction. We estimated the photo-induced electron density and the electron-transfer characteristics, which will be helpful for understanding organic-inorganic hybrid optoelectronic devices.

  1. Photoinduced oxygen release and persistent photoconductivity in ZnO nanowires

    NASA Astrophysics Data System (ADS)

    Bao, Jiming; Shalish, Ilan; Su, Zhihua; Gurwitz, Ron; Capasso, Federico; Wang, Xiaowei; Ren, Zhifeng

    2011-05-01

    Photoconductivity is studied in individual ZnO nanowires. Under ultraviolet (UV) illumination, the induced photocurrents are observed to persist both in air and in vacuum. Their dependence on UV intensity in air is explained by means of photoinduced surface depletion depth decrease caused by oxygen desorption induced by photogenerated holes. The observed photoresponse is much greater in vacuum and proceeds beyond the air photoresponse at a much slower rate of increase. After reaching a maximum, it typically persists indefinitely, as long as good vacuum is maintained. Once vacuum is broken and air is let in, the photocurrent quickly decays down to the typical air-photoresponse values. The extra photoconductivity in vacuum is explained by desorption of adsorbed surface oxygen which is readily pumped out, followed by a further slower desorption of lattice oxygen, resulting in a Zn-rich surface of increased conductivity. The adsorption-desorption balance is fully recovered after the ZnO surface is exposed to air, which suggests that under UV illumination, the ZnO surface is actively "breathing" oxygen, a process that is further enhanced in nanowires by their high surface to volume ratio.

  2. Steady-state and femtosecond photoinduced processes of blepharismins bound to alpha-crystallin.

    PubMed

    Youssef, T; Brazard, J; Ley, C; Lacombat, F; Plaza, P; Martin, M M; Sgarbossa, A; Checcucci, G; Lenci, F

    2008-07-01

    The interaction of blepharismin (BP) and oxyblepharismin (OxyBP) with bovine alpha-crystallin (BAC) has been studied both by steady-state and femtosecond spectroscopy, with the aim of assessing the possible phototoxicity of these compounds toward the eye tissues. We showed that these pigments form with BAC potentially harmful ground-state complexes, the dissociation constants of which have been estimated to be 6 +/- 2 micromol L(-1) for OxyBP and 9 +/- 4 micromol L(-1) for BP. Irradiation with steady-state visible light of solutions of blepharismins in the presence of BAC proved to induce a quenching of both the pigment and the intrinsic protein fluorescences. These effects were tentatively rationalized in terms of structural changes of alpha-crystallin. On the other hand, femtosecond transient absorption spectroscopy was used to check the occurrence of any type I photoactivity of oxyblepharismin bound to alpha-crystallin. The existence of a particular type of fast photoinduced reaction, not observed in former studies with human serum albumin but present in the natural oxyblepharismin-binding protein, could here be evidenced but no specific reaction was observed during the first few nanoseconds after excitation. Partial denaturation of alpha-crystallin was however found to alter the excited-state behaviour of its complex with oxyblepharismin, making it partly resemble that of free oxyblepharismin in solution.

  3. Ultrafast nano-imagining of the photoinduced phase transition dynamics in VO2

    NASA Astrophysics Data System (ADS)

    Doenges, Sven A.; Khatib, Omar; O'Callahan, Brian T.; Atkin, Joanna M.; Park, Jae Hyung; Cobden, David H.; Raschke, Markus B.

    Many quantum phase transitions in correlated matter exhibit spatial inhomogeneities with expected yet unexplored effects on the associated ultrafast dynamics. Here we demonstrate the combination of ultrafast non-degenerate pump-probe spectroscopy with scattering scanning near-field optical microscopy (s-SNOM) for ultrafast nano-imaging. In a femtosecond near-field non-degenerate near-IR (NIR) pump and mid-IR (MIR) probe experiment, we study the photoinduced insulator-to-metal (IMT) transition in nominally homogeneous VO2 micro-crystals using far-from equilibrium excitation. We observe spatial heterogeneity on 50-100 nm length scales in the fluence dependent IMT dynamics, ranging from sub-100 fs to 1 ps. With pump fluences as high as nominally 10 mJ/cm2 we can reach distinct excitation and saturation regimes. These results suggest a large sensitivity of the IMT with respect to local variations in strain, doping, or defects difficult to discern microscopically.

  4. Capturing photoinduced structural distortion within a unit cell of BiFeO3

    NASA Astrophysics Data System (ADS)

    Wen, Haidan; Sassi, Michel; Luo, Zhenlin; Adamo, Carolina; Schlom, Darrell; Kevin, Rosso; Zhang, Xiaoyi

    2015-03-01

    The interaction of light with correlated materials has been an intensely studied research forefront in which the coupling of radiation energy to selective degrees of freedom offers a novel contact-free control knob to tune functionalities on ultrafast time scales. We studied a photoexcited multiferroic BiFeO3 thin film using time-resolved x-ray absorption spectroscopy aided by density functional theory calculations. The study revealed a uniaxial deformation of the unit cell at a constant volume with a minimal oxygen octahedron rotation, consistent with the influence of photoinduced carriers to the ferroelectric polarization. These important findings illustrate a microscopic picture of local structural reconfiguration around iron atoms at atomistic length scales during a photocarrier-mediated nonequilibrium process in polar materials. Work was supported by the U.S. DOE Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357 (ANL) and from the Division of Chemical Sciences, Geosciences and Biosciences (PNNL).

  5. Spectroscopic imaging of photopotentials and photoinduced potential fluctuations in a bulk heterojunction solar cell film.

    PubMed

    Luria, Justin L; Hoepker, Nikolas; Bruce, Robert; Jacobs, Andrew R; Groves, Chris; Marohn, John A

    2012-11-27

    We present spatially resolved photovoltage spectra of a bulk heterojunction solar cell film composed of phase-separated 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) polymers prepared on ITO/PEDOT:PSS and aluminum substrates. Over both PFB- and F8BT-rich domains, the photopotential spectra were found to be proportional to a linear combination of the polymers' absorption spectra. Charge trapping in the film was studied using photopotential fluctuation spectroscopy, in which low-frequency photoinduced electrostatic potential fluctuations were measured by observing noise in the oscillation frequency of a nearby charged atomic force microscope cantilever. Over both F8BT- and PFB-rich regions, the magnitude, distance dependence, frequency dependence, and illumination wavelength dependence of the observed cantilever frequency noise are consistent with photopotential fluctuations arising from stochastic light-driven trapping and detrapping of charges in F8BT. Taken together, our findings suggest a microscopic mechanism by which intermixing of phases leads to charge trapping and thereby to suppressed open-circuit voltage and decreased efficiency in this prototypical bulk heterojunction solar cell film.

  6. Determination of the herbicide benfuresate by its photo-induced chemiluminescence using flow multicommutation methodology.

    PubMed

    Albert-García, J R; Calatayud, J Martínez

    2008-05-15

    The present paper deals with an analytical strategy based on coupling photo-induced chemiluminescence in a multicommutation continuous-flow methodology for the determination of the herbicide benfuresate. The solenoid valve inserted as small segments of the analyte solution was sequentially alternated with segments of the NaOH solution for adjusting the medium for the photodegradation. Both flow rates (sample and medium) were adjusted to required time for photodegradation, 90 s; and then, the resulting solution was also sequentially inserted as segments alternated with segments of the oxidizing solution system, hexacyanoferrate (III) in alkaline medium. The calibration range from 1 microg L(-1) to 95 mg L(-1), resulted in a linear behaviour over the range 1 microg L(-1) to 4 mg L(-1) and fitting the linear equation: I=4555.7x+284.2, correlation coefficient 0.9999. The limit of detection was 0.1 microg L(-1) (n=5, criteria 3 sigma) and the sample throughput was 22 h(-1). The consumption of solutions was very small; per peak were 0.66 mL, 0.16 mL and 0. 32 mL sample, medium and oxidant, respectively. Inter- and intra-day reproducibility resulted in a R.S.D. of 3.9% and 3.4%, respectively. After testing the influence of a large series of potential interferents the method is applied to water samples obtained from different places, human urine and to one formulation.

  7. Raising the barrier for photoinduced DNA charge injection with a cyclohexyl artificial base pair.

    PubMed

    Singh, Arunoday P N; Harris, Michelle A; Young, Ryan M; Miller, Stephen A; Wasielewski, Michael R; Lewis, Frederick D

    2015-01-01

    The effects of an artificial cyclohexyl base pair on the quantum yields of fluorescence and dynamics of charge separation and charge recombination have been investigated for several synthetic DNA hairpins. The hairpins possess stilbenedicarboxamide, perylenediimide, or naphthalenediimide linkers and base-paired stems. In the absence of the artificial base pair hole injection into both adenine and guanine purine bases is exergonic and irreversible, except in the case of stilbene with adenine for which it is slightly endergonic and reversible. Insertion of the artificial base pair renders hole injection endergonic or isoergonic except in the case of the powerful naphthalene acceptor for which it remains exergonic. Both hole injection and charge recombination are slower for the naphthalene acceptor in the presence of the artificial base pair than in its absence. The effect of an artificial base pair on charge separation and charge recombination in hairpins possessing stilbene and naphthalene acceptor linkers and a stilbenediether donor capping group has also been investigated. In the case of the stilbene acceptor-stilbene donor capped hairpins photoinduced charge separation across six base pairs is efficient in the absence of the artificial base pair but does not occur in its presence. In the case of the naphthalene acceptor-stilbene donor capped hairpins the artificial base pair slows but does not stop charge separation and charge recombination, leading to the formation of long-lived charge separated states.

  8. Probing photoinduced spin states in spin-crossover molecules with neutron scattering

    NASA Astrophysics Data System (ADS)

    Ridier, K.; Craig, G. A.; Damay, F.; Fennell, T.; Murrie, M.; Chaboussant, G.

    2017-03-01

    We report a neutron-scattering investigation of the spin-crossover compound [Fe (ptz) 6] (BF4)2 , which undergoes an abrupt thermal spin transition from high spin (HS), S =2 , to low spin (LS), S =0 , around 135 K. The HS magnetic state can be restored at low temperature under blue/green light irradiation. We have developed a specially designed optical setup for neutron scattering to address the magnetic properties of the light-induced HS state. By using neutron diffraction, we demonstrate that significant HS/LS ratios (of up to 60%) can be obtained with this experimental setup on a sample volume considered large (400 mg), while a complete recovery of the LS state is achieved using near-infrared light. Finally, with inelastic neutron scattering (INS) we have observed magnetic transitions arising from the photo-induced metastable HS S =2 state split by crystal-field and spin-orbit coupling. We interpret the INS data assuming a spin-only model with a zero-field splitting of the S =2 ground state. The obtained parameters are D ≈-1.28 ±0.03 meV and |E |≈0.08 ±0.03 meV. The present results show that in situ magnetic inelastic neutron-scattering investigations on a broad range of photomagnetic materials are now possible.

  9. Hot-carrier cooling and photoinduced refractive index changes in organic-inorganic lead halide perovskites

    NASA Astrophysics Data System (ADS)

    Price, Michael B.; Butkus, Justinas; Jellicoe, Tom C.; Sadhanala, Aditya; Briane, Anouk; Halpert, Jonathan E.; Broch, Katharina; Hodgkiss, Justin M.; Friend, Richard H.; Deschler, Felix

    2015-09-01

    Metal-halide perovskites are at the frontier of optoelectronic research due to solution processability and excellent semiconductor properties. Here we use transient absorption spectroscopy to study hot-carrier distributions in CH3NH3PbI3 and quantify key semiconductor parameters. Above bandgap, non-resonant excitation creates quasi-thermalized carrier distributions within 100 fs. During carrier cooling, a sub-bandgap transient absorption signal arises at ~1.6 eV, which is explained by the interplay of bandgap renormalization and hot-carrier distributions. At higher excitation densities, a `phonon bottleneck' substantially slows carrier cooling. This effect indicates a low contribution from inelastic carrier-impurity or phonon-impurity scattering in these polycrystalline materials, which supports high charge-carrier mobilities. Photoinduced reflectivity changes distort the shape of transient absorption spectra and must be included to extract physical constants. Using a simple band-filling model that accounts for these changes, we determine a small effective mass of mr=0.14 mo, which agrees with band structure calculations and high photovoltaic performance.

  10. Linearly and circularly polarized laser photoinduced molecular order in azo dye doped polymer films

    NASA Astrophysics Data System (ADS)

    Saad, Bendaoud

    2017-03-01

    Photo-induced behavior of Azo Disperse one (AZD1) doped Poly(Methyl MethAcrylate) (PMMA) using both linear and circular polarized light is studied. The anisotropy is not erased by the circular polarization light. The circular polarization light combined with relatively long lifetime of the cis state in azo dye doped polymers activate all transverse directions of the angular hole burning through the spot in the film inducing anisotropy. Under circular polarized light, there is no orientation perpendicularly to the helex described by the rotating electric field vector, trans molecules reorients in the propagation direction of the pump beam. The polarization state of the probe beam after propagation through the pumped spot depends strongly on the angle of incidence of both pump and probe beams on the input face. In the case where circular polarized pump and probe beams are under the same angle of incidence, the probe beam "sees" anisotropic film as if it is isotropic. Results of this work shows the possibility to reorient azobenzene-type molecules in two orthogonal directions using alternately linearly and circularly polarized beams.

  11. Formation mechanism of photo-induced nested wrinkles on siloxane-photomonomer hybrid film

    SciTech Connect

    Suzuki, Kazumasa; Tokudome, Yasuaki Takahashi, Masahide

    2014-10-21

    Nested wrinkle structures, hierarchical surface wrinkles of different periodicities of sub-μm and tens-μm, have been fabricated on a siloxane-photomonomer hybrid film via a photo-induced surface polymerization of acrylamide. The formation mechanism of the nested wrinkle structures is examined based on a time-dependent structure observation and chemical composition analyses. In-situ observation of the evolving surface structure showed that sub-μm scale wrinkles first formed, subsequently the tens-μm scale ones did. In-situ FT-IR analysis indicated that the nested wrinkles formation took place along with the development of siloxane network of under layer. A cross sectional observation of the film revealed that the film was composed of three layers. FT-IR spectra of the film revealed that the surface and interior layers were polyacrylamide rich layer and siloxane-polymer rich layer, respectively. The intermediate layer formed as a diffusion layer by migration of acrylamide from interior to the surface. These three layers have different chemical compositions and therefore different mechanical characteristics, which allows the wrinkle formation. Shrinkage of siloxane-polymer interior layers, as a result of polycondensation of siloxane network, induced mechanical instabilities at interlayers, to form the nested wrinkle structures.

  12. Hierarchical pattern formation through photo-induced disorder in block copolymer/additive composite films

    NASA Astrophysics Data System (ADS)

    Yao, Li; Watkins, James

    2013-03-01

    Segregation strength in hybrid materials can be increased through selective hydrogen bonding between organic or nanoparticle additives and one block of weakly segregated block copolymers to generate well ordered hybrid materials. Here, we report the use of enantiopure tartaric acid as the additive to dramatically improve ordering in poly(ethylene oxide-block-tert-butyl acrylate) (PEO-b-PtBA) copolymers. Phase behavior and morphologies within both bulk and thin films were studied by TEM, AFM and X-ray scattering. Suppression of PEO crystallization by the interaction between tartaric acid and the PEO block enables the formation of well ordered smooth thin films. With the addition of a photo acid generator, photo-induced disorder in PEO-b-PtBA/tartaric acid composite system can be achieved upon UV exposure to deprotect PtBA block to yield poly(acrylic acid) (PAA), which is phase-miscible with PEO. Due to the strong interaction of tartaric acid with both blocks, the system undergoes a disordering transition within seconds during a post-exposure baking. With the assistance of trace-amounts of base quencher, high resolution, hierarchical patterns of sub-micron regions of ordered and disordered domains were achieved in thin films through area-selective UV exposure using a photo-mask. Funding from Center for Hierarchical Manufacturing (CHM); Facility support from Materials Research Science and Engineering Center at UMass Amherst and Cornell High Energy Synchrotron Source

  13. Relaxation in photo-induced conductivity of polycrystalline BiFeO3 film

    NASA Astrophysics Data System (ADS)

    Peng, Zengwei; Liu, Baoting

    2015-08-01

    Polycrystalline BiFeO3 (BFO) film is deposited on Pt(1 1 1)/Ti/SiO2/Si(0 0 1) substrate via magnetron sputtering. Integrated Pt/SrRuO3 (SRO) are used to be top electrode to produce the Pt/SRO/BFO/Pt thin film capacitor. The remanent polarization is 59.5, 69.3, 77 and 89.8 μC/cm2 measured at 22.5, 25, 27.5 and 30 V, respectively. The photoconductivity is reported in BFO film under the illumination by the 5 mW/cm2 purple light of 404 nm. It is found that the leakage current density in purple light displays the tendency of decline with the increased illumination times, which can be explained by the recombination and capture of the photo-induced charges by the ionized vacancies. The relaxation time for the illuminated leakage current density reaching the steady state is 210 and 570 s at positive and negative bias, respectively. The obtained large relaxation time at negative bias is considered to be that negative bias is in the same direction as the SRO/BFO interface field.

  14. Characterisation of TiO 2 deposited by photo-induced chemical vapour deposition

    NASA Astrophysics Data System (ADS)

    Kaliwoh, Never; Zhang, Jun-Ying; Boyd, Ian W.

    2002-01-01

    We report the deposition of thin TiO 2 films on crystalline Si and quartz by photo-induced chemical vapour deposition (CVD) using UV excimer lamps employing a dielectric barrier discharge in krypton chloride (KrCl ∗) to provide intense narrow band radiation at λ=222 nm. The precursor used was titanium isopropoxide (TTIP). Films from around 20-510 nm in thickness with refractive indices from 2.20 to 2.54 were grown at temperatures between 50 and 350 °C. The higher refractive index values compare favourably with the value of 2.58 recorded for the bulk material. The measured deposition rate was around 50 nm/min at 350 °C. Fourier transform infrared spectroscopy (FTIR) revealed the presence of TiO 2 through the observation of a Ti-O absorption peak and the absence of OH in films deposited at 250-350 °C indicated relatively good quality films. The phase of films deposited at 200-350 °C was anatase as determined by X-ray diffraction.

  15. Photoinduced grating formation in a polymer containing azo-carbazole dyes.

    PubMed

    Kawabe, Yutaka; Fukuzawa, Kodai; Uemura, Takuya; Matsuura, Katsufumi; Yoshikawa, Toshio; Nishide, Jun-ichi; Sasabe, Hiroyuki

    2012-09-20

    Although some azo-carbazole derivatives attached on or doped into inert polymers are known to show photorefractive effect without external electric field, the origin of their asymmetric energy transfer in two-beam coupling experiments were unknown. We made the two-beam coupling experiment followed by sample translation and one-beam diffraction at 633 nm for thick films composed of 3-[(4-nitrophenyl)]azo-9H-carbazole-9-ethanol (NACzEtOH) and poly(methylmethacrylate), finding that photoinduced gratings grew in several minutes accompanied with phase displacement of the gratings, but the phase shift was not always synchronized with the refractive index modulation. We reformulated the Kogelnik's coupled-wave theory with strict energy conservation law for analysis. Comparison of the grating growth and erasure at 532 nm to Disperse Red 1 (DR1), the most well-known azo dye showed that the photoisomerization was dominant at this wavelength and that the azo-carbazole dyes were faster in response time and more resistive to erasure than DR1.

  16. Study of the photoinduced supramolecular chirality in columnar liquid crystals by infrared and VCD spectroscopies.

    PubMed

    Avilés Moreno, Juan Ramón; López González, Juan Jesús; Partal Ureña, Francisco; Vera, Francisco; Ros, M Blanca; Sierra, Teresa

    2012-04-26

    IR and VCD spectroscopies are employed to clarify the molecular origins of supramolecular chirality in azobenzene-containing columnar liquid crystals. The different columnar mesomorphic assemblies, Colr and Colh, of an achiral and a chiral propeller-like hydrogen-bonded complex, respectively, are used for this study. The mesomorphic behavior of the achiral complex is studied here for the first time, and the structural parameters of its Colr mesophase are determined by X-ray diffraction. Both complexes bear azobenzene units and this makes it possible to implement photoresponsive columnar architectures, the chirality of which can be induced and modulated by irradiation with 488 nm circularly polarized light (CPL). Thin films of the respective rectangular and hexagonal columnar phases of these complexes have been processed in order to study the IR absorption spectra and the vibrational circular dichroism responses upon irradiation with CPL. These studies allow confirming that the outer part of the columns, consisting on azobenzene groups, is mainly involved in the photoinduced supramolecular chirality, rather than the inner part of the columns where a melamine core is located. This supports a structural model based on the helical disposition of the azobenzene groups along the stacked propeller-like complexes.

  17. Exploiting Photo-induced Reactions in Polymer Blends to Create Hierarchically Ordered, Defect-free Materials

    ScienceCinema

    Balazs, Anna [University of Pittsburgh, Pittsburgh, Pennsylvania, United States

    2016-07-12

    Computer simulations reveal how photo-induced chemical reactions can be exploited to create long-range order in binary and ternary polymeric materials. The process is initiated by shining a spatially uniform light over a photosensitive AB binary blend, which undergoes both a reversible chemical reaction and phase separation. We then introduce a well-collimated, higher-intensity light source. Rastering this secondary light over the sample locally increases the reaction rate and causes formation of defect-free, spatially periodic structures. These binary structures resemble either the lamellar or hexagonal phases of microphase-separated di-block copolymers. We measure the regularity of the ordered structures as a function of the relative reaction rates for different values of the rastering speed and determine the optimal conditions for creating defect-free structures in the binary systems. We then add a non-reactive homo-polymer C, which is immiscible with both A and B. We show that this component migrates to regions that are illuminated by the secondary, higher-intensity light, allowing us to effectively write a pattern of C onto the AB film. Rastering over the ternary blend with this collimated light now leads to hierarchically ordered patterns of A, B, and C. The findings point to a facile, non-intrusive process for manufacturing high-quality polymeric devices in a low-cost, efficient manner.

  18. Hot-carrier cooling and photoinduced refractive index changes in organic-inorganic lead halide perovskites.

    PubMed

    Price, Michael B; Butkus, Justinas; Jellicoe, Tom C; Sadhanala, Aditya; Briane, Anouk; Halpert, Jonathan E; Broch, Katharina; Hodgkiss, Justin M; Friend, Richard H; Deschler, Felix

    2015-09-25

    Metal-halide perovskites are at the frontier of optoelectronic research due to solution processability and excellent semiconductor properties. Here we use transient absorption spectroscopy to study hot-carrier distributions in CH3NH3PbI3 and quantify key semiconductor parameters. Above bandgap, non-resonant excitation creates quasi-thermalized carrier distributions within 100 fs. During carrier cooling, a sub-bandgap transient absorption signal arises at ∼ 1.6 eV, which is explained by the interplay of bandgap renormalization and hot-carrier distributions. At higher excitation densities, a 'phonon bottleneck' substantially slows carrier cooling. This effect indicates a low contribution from inelastic carrier-impurity or phonon-impurity scattering in these polycrystalline materials, which supports high charge-carrier mobilities. Photoinduced reflectivity changes distort the shape of transient absorption spectra and must be included to extract physical constants. Using a simple band-filling model that accounts for these changes, we determine a small effective mass of mr=0.14 mo, which agrees with band structure calculations and high photovoltaic performance.

  19. Hot-carrier cooling and photoinduced refractive index changes in organic–inorganic lead halide perovskites

    PubMed Central

    Price, Michael B.; Butkus, Justinas; Jellicoe, Tom C.; Sadhanala, Aditya; Briane, Anouk; Halpert, Jonathan E.; Broch, Katharina; Hodgkiss, Justin M.; Friend, Richard H.; Deschler, Felix

    2015-01-01

    Metal-halide perovskites are at the frontier of optoelectronic research due to solution processability and excellent semiconductor properties. Here we use transient absorption spectroscopy to study hot-carrier distributions in CH3NH3PbI3 and quantify key semiconductor parameters. Above bandgap, non-resonant excitation creates quasi-thermalized carrier distributions within 100 fs. During carrier cooling, a sub-bandgap transient absorption signal arises at ∼1.6 eV, which is explained by the interplay of bandgap renormalization and hot-carrier distributions. At higher excitation densities, a ‘phonon bottleneck' substantially slows carrier cooling. This effect indicates a low contribution from inelastic carrier-impurity or phonon–impurity scattering in these polycrystalline materials, which supports high charge-carrier mobilities. Photoinduced reflectivity changes distort the shape of transient absorption spectra and must be included to extract physical constants. Using a simple band-filling model that accounts for these changes, we determine a small effective mass of mr=0.14 mo, which agrees with band structure calculations and high photovoltaic performance. PMID:26404048

  20. Contributions of conduction band offset to the enhanced separation efficiency of photoinduced charges for SrTiO{sub 3}/Bi{sub 2}O{sub 3} heterojunction semiconductor

    SciTech Connect

    Zhang, Zhenlong; Zhu, Jichun; Li, Shengjun; Mao, Yanli

    2014-03-15

    SrTiO{sub 3}/Bi{sub 2}O{sub 3} heterojunction semiconductor was prepared and characterized by X-ray diffraction, UV–vis absorption spectrum, and scanning electron microscope, surface photovoltage spectroscopy, and photoluminescence spectroscopy. The surface photovoltage spectra indicate that the separation efficiency of photoinduced charges for SrTiO{sub 3}/Bi{sub 2}O{sub 3} was enhanced compared with that of SrTiO{sub 3} or Bi{sub 2}O{sub 3}. The energy band diagram of SrTiO{sub 3}/Bi{sub 2}O{sub 3} heterojunction was directly determined with X-ray photoelectron spectroscopy, and the conduction band offset between SrTiO{sub 3} and Bi{sub 2}O{sub 3} was quantified to be 0.28±0.03 eV. The photoluminescence spectra display that the recombination rate of photoinduced carriers for SrTiO{sub 3}/Bi{sub 2}O{sub 3} decreases compared with that of SrTiO{sub 3} or Bi{sub 2}O{sub 3}, which is mainly due to the energy levels matching between them. Therefore the enhanced separation efficiency of photoinduced charges is resulting from the energy difference between the conduction band edges of SrTiO{sub 3} and Bi{sub 2}O{sub 3}. -- Graphical abstract: Enhanced separation efficiency for SrTiO{sub 3}/Bi{sub 2}O{sub 3} is resulting from the energy difference between the conduction band edges. Highlights: ●Heterojunction semiconductor of SrTiO{sub 3}/Bi{sub 2}O{sub 3} was prepared. ●SrTiO{sub 3}/Bi{sub 2}O{sub 3} presents enhanced separation efficiency. ●Conduction band offset between SrTiO{sub 3} and Bi{sub 2}O{sub 3} is quantified. ●Recombination rate of SrTiO{sub 3}/Bi{sub 2}O{sub 3} decreases compared with single phases.