Measurement of fluorophore concentrations and fluorescence quantum yield in tissue-simulating phantoms using three diffusion models of steady-state spatially resolved fluorescence.

PubMed

Diamond, Kevin R; Farrell, Thomas J; Patterson, Michael S

2003-12-21

Steady-state diffusion theory models of fluorescence in tissue have been investigated for recovering fluorophore concentrations and fluorescence quantum yield. Spatially resolved fluorescence, excitation and emission reflectance Carlo simulations, and measured using a multi-fibre probe on tissue-simulating phantoms containing either aluminium phthalocyanine tetrasulfonate (AlPcS4), Photofrin meso-tetra-(4-sulfonatophenyl)-porphine dihydrochloride The accuracy of the fluorophore concentration and fluorescence quantum yield recovered by three different models of spatially resolved fluorescence were compared. The models were based on: (a) weighted difference of the excitation and emission reflectance, (b) fluorescence due to a point excitation source or (c) fluorescence due to a pencil beam excitation source. When literature values for the fluorescence quantum yield were used for each of the fluorophores, the fluorophore absorption coefficient (and hence concentration) at the excitation wavelength (mu(a,x,f)) was recovered with a root-mean-square accuracy of 11.4% using the point source model of fluorescence and 8.0% using the more complicated pencil beam excitation model. The accuracy was calculated over a broad range of optical properties and fluorophore concentrations. The weighted difference of reflectance model performed poorly, with a root-mean-square error in concentration of about 50%. Monte Carlo simulations suggest that there are some situations where the weighted difference of reflectance is as accurate as the other two models, although this was not confirmed experimentally. Estimates of the fluorescence quantum yield in multiple scattering media were also made by determining mu(a,x,f) independently from the fitted absorption spectrum and applying the various diffusion theory models. The fluorescence quantum yields for AlPcS4 and TPPS4 were calculated to be 0.59 +/- 0.03 and 0.121 +/- 0.001 respectively using the point source model, and 0.63 +/- 0.03 and 0.129 +/- 0.002 using the pencil beam excitation model. These results are consistent with published values.

Homeotropic alignment and Förster resonance energy transfer: The way to a brighter luminescent solar concentrator

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

Tummeltshammer, Clemens; Taylor, Alaric; Kenyon, Anthony J.

2014-11-07

We investigate homeotropically aligned fluorophores and Förster resonance energy transfer (FRET) for luminescent solar concentrators using Monte-Carlo ray tracing. The homeotropic alignment strongly improves the trapping efficiency, while FRET circumvents the low absorption at homeotropic alignment by separating the absorption and emission processes. We predict that this design doped with two organic dye molecules can yield a 82.9% optical efficiency improvement compared to a single, arbitrarily oriented dye molecule. We also show that quantum dots are prime candidates for absorption/donor fluorophores due to their wide absorption band. The potentially strong re-absorption and low quantum yield of quantum dots is notmore » a hindrance for this design.« less

Photophysical properties gallium octacarboxy phthalocyanines conjugated to CdSe@ZnS quantum dots.

PubMed

Tshangana, Charmaine; Nyokong, Tebello

2015-01-01

L-Glutathione (GSH) capped core CdSe (2.3 nm) and core shell CdSe@ZnS quantum dots (QDs) (3.0 nm and 3.5 nm) were coordinated to gallium octacarboxy phthalocyanine (ClGaPc(COOH)8) to form ClGaPc(COOH)8-QDs conjugates. An efficient transfer of energy from the QDs to the Pcs was demonstrated through Förster resonance energy transfer (FRET), the FRET efficiencies in all cases was above 50%. The photophysical parameters (triplet state and fluorescence quantum yields and lifetimes) were also determined for the conjugates. There was a decrease in the fluorescence lifetimes of ClGaPc(COOH)8 in the presence of all the QDs, due to the heavy atom effect. The triplet quantum yields increased in the conjugates. The lifetimes also became longer for the conjugates compared to Pc alone. Copyright © 2015 Elsevier B.V. All rights reserved.

Synthesis and characterization of near-infrared absorbing water soluble squaraines and study of their photodynamic effects in DLA live cells.

PubMed

Shafeekh, Kulathinte M; Soumya, Mohanannair S; Rahim, Moochikkadavath A; Abraham, Annie; Das, Suresh

2014-01-01

Here, we report the synthesis, photophysical properties and photodynamic effects in DLA live cells of three water soluble squaraine dyes, viz. bisbenzothiazolium squaraine dyes SQMI and SQDI with iodine in one and both benzothiazolium units, respectively, and an unsymmetrical squaraine dye ASQI containing iodinated benzothiazolium and aniline substituents. The diiodinated SQDI showed an anomalous trend in both fluorescence and triplet quantum yields over the monoiodinated SQMI, with SQDI showing higher fluorescence and lower triplet quantum yields compared to SQMI. Nanosecond laser flash photolysis of SQDI and SQMI indicated the formation of triplet excited states with quantum yield of 0.19 and 0.26, respectively. On photoirradiation, both the SQDI and SQMI generate singlet oxygen and it was observed that both dyes undergoing oxidation reactions with the singlet oxygen generated. ASQI which exhibited a lower triplet quantum yield of 0.06 was, however, stable and did not react with the singlet oxygen generated. In vitro cytotoxicity studies of these dyes in DLA live cells were performed using Trypan blue dye exclusion method and it reflect an order of cytotoxicity of SQDI>SQMI>ASQI. Intracellular generation of the ROS was confirmed by dichlorofluorescein assay after the in vitro PDT. © 2014 The American Society of Photobiology.

Efficiencies of induction of DNA double strand breaks in solution by photoabsorption at phosphorus and platinum.

PubMed

Maeda, Munetoshi; Kobayashi, Katsumi; Hieda, Kotaro

2004-01-01

This paper aims at determining and comparing the cross sections and quantum yields for DNA strand break induction by the Auger effect at the K-shell of phosphorus and at the LIII-shell of platinum. Using synchrotron radiation, free and Pt-bound pBR322 plasmid DNA were irradiated in solution with monochromatic X-rays, the energies of which were 2.153 and 2.147 keV, corresponding to "on" and "below" the phosphorus K-shell photoabsorption, and 11.566 and 11.542 keV for "above" and "below" the L(III)-shell photoabsorption of platinum, respectively. To suppress indirect effects by hydroxyl radicals, DMSO (1M) was used as a scavenger. The inner-shell photoabsorption of phosphorus and of platinum significantly increased the induction of DNA double strand breaks (DSB), whereas it had little effect on single strand break (SSB) induction. The quantum yields for the induction of DSB were calculated to be 0.017 and 1.13, in the case of phosphorus and platinum, respectively. CONCLSIONS: The value of the quantum yield for the DSB induction of platinum was about 66-fold larger than that for the phosphorus. These results clearly demonstrate that the quantum yield of DSB depends upon the magnitude of the Auger cascade.

Size-Dependent Biexciton Quantum Yields and Carrier Dynamics of Quasi-Two-Dimensional Core/Shell Nanoplatelets

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

Ma, Xuedan; Diroll, Benjamin T.; Cho, Wooje

Quasi-two-dimensional nanoplatelets (NPLs) possess fundamentally different excitonic properties from zero-dimensional quantum dots. We study lateral size-dependent photon emission statistics and carrier dynamics of individual NPLs using second-order photon correlation (g( 2)(τ)) spectroscopy and photoluminescence (PL) intensity-dependent lifetime analysis. Room-temperature radiative lifetimes of NPLs can be derived from maximum PL intensity periods in PL time traces. It first decreases with NPL lateral size and then stays constant, deviating from the electric dipole approximation. Analysis of the PL time traces further reveals that the single exciton quantum yield in NPLs decreases with NPL lateral size and increases with protecting shell thickness, indicatingmore » the importance of surface passivation on NPL emission quality. Second-order photon correlation (g( 2)(τ)) studies of single NPLs show that the biexciton quantum yield is strongly dependent on the lateral size and single exciton quantum yield of the NPLs. In large NPLs with unity single exciton quantum yield, the corresponding biexciton quantum yield can reach unity. In conclusion, these findings reveal that by careful growth control and core–shell material engineering, NPLs can be of great potential for light amplification and integrated quantum photonic applications.« less

Size-Dependent Biexciton Quantum Yields and Carrier Dynamics of Quasi-Two-Dimensional Core/Shell Nanoplatelets

DOE PAGES

Ma, Xuedan; Diroll, Benjamin T.; Cho, Wooje; ...

2017-08-08

Quasi-two-dimensional nanoplatelets (NPLs) possess fundamentally different excitonic properties from zero-dimensional quantum dots. We study lateral size-dependent photon emission statistics and carrier dynamics of individual NPLs using second-order photon correlation (g( 2)(τ)) spectroscopy and photoluminescence (PL) intensity-dependent lifetime analysis. Room-temperature radiative lifetimes of NPLs can be derived from maximum PL intensity periods in PL time traces. It first decreases with NPL lateral size and then stays constant, deviating from the electric dipole approximation. Analysis of the PL time traces further reveals that the single exciton quantum yield in NPLs decreases with NPL lateral size and increases with protecting shell thickness, indicatingmore » the importance of surface passivation on NPL emission quality. Second-order photon correlation (g( 2)(τ)) studies of single NPLs show that the biexciton quantum yield is strongly dependent on the lateral size and single exciton quantum yield of the NPLs. In large NPLs with unity single exciton quantum yield, the corresponding biexciton quantum yield can reach unity. In conclusion, these findings reveal that by careful growth control and core–shell material engineering, NPLs can be of great potential for light amplification and integrated quantum photonic applications.« less

Nonlinear quantum Rabi model in trapped ions

NASA Astrophysics Data System (ADS)

Cheng, Xiao-Hang; Arrazola, Iñigo; Pedernales, Julen S.; Lamata, Lucas; Chen, Xi; Solano, Enrique

2018-02-01

We study the nonlinear dynamics of trapped-ion models far away from the Lamb-Dicke regime. This nonlinearity induces a blockade on the propagation of quantum information along the Hilbert space of the Jaynes-Cummings and quantum Rabi models. We propose to use this blockade as a resource for the dissipative generation of high-number Fock states. Also, we compare the linear and nonlinear cases of the quantum Rabi model in the ultrastrong and deep strong-coupling regimes. Moreover, we propose a scheme to simulate the nonlinear quantum Rabi model in all coupling regimes. This can be done via off-resonant nonlinear red- and blue-sideband interactions in a single trapped ion, yielding applications as a dynamical quantum filter.

A comparative photophysicochemical study of phthalocyanines encapsulated in core-shell silica nanoparticles.

PubMed

Fashina, Adedayo; Amuhaya, Edith; Nyokong, Tebello

2015-02-25

This work presents the synthesis and characterization of a new zinc phthalocyanine complex tetrasubstituted with 3-carboxyphenoxy in the peripheral position. The photophysical properties of the new complex are compared with those of phthalocyanines tetra substituted with 3-carboxyphenoxy or 4-carboxyphenoxy at non-peripheral positions. Three phthalocyanine complexes were encapsulated within silica matrix to form a core shell and the hybrid nanoparticles particles obtained were spherical and mono dispersed. When encapsulated within the silica shell nanoparticles, phthalocyanines showed improved triplet quantum yields and singlet oxygen quantum yields than surface grafted derivatives. The improvements observed could be attributed to the protection provided for the phthalocyanine complexes by the silica matrix. Copyright © 2014 Elsevier B.V. All rights reserved.

Absolute I(asterisk) quantum yields for the ICN A state by diode laser gain-vs-absorption spectroscopy

NASA Technical Reports Server (NTRS)

Hess, Wayne P.; Leone, Stephen R.

1987-01-01

Absolute I(asterisk) quantum yields have been measured as a function of wavelength for room temperature photodissociation of the ICN A state continuum. The yields are obtained by the technique of time-resolved diode laser gain-vs-absorption spectroscopy. Quantum yields are evaluated at seven wavelengths from 248 to 284 nm. The yield at 266 nm is 66.0 + or - 2 percent and it falls off to 53.4 + or - 2 percent and 44.0 + or - 4 percent at 284 and 248 nm, respectively. The latter values are significantly higher than those obtained by previous workers using infrared fluorescence. Estimates of I(asterisk) quantum yields obtained from analysis of CN photofragment rotational distributions, as discussed by other workers, are in good agreement with the I(asterisk) yields reported here. The results are considered in conjunction with recent theoretical and experimental work on the CN rotational distributions and with previous I(asterisk) quantum yield results.

Unity quantum yield of photogenerated charges and band-like transport in quantum-dot solids.

PubMed

Talgorn, Elise; Gao, Yunan; Aerts, Michiel; Kunneman, Lucas T; Schins, Juleon M; Savenije, T J; van Huis, Marijn A; van der Zant, Herre S J; Houtepen, Arjan J; Siebbeles, Laurens D A

2011-09-25

Solid films of colloidal quantum dots show promise in the manufacture of photodetectors and solar cells. These devices require high yields of photogenerated charges and high carrier mobilities, which are difficult to achieve in quantum-dot films owing to a strong electron-hole interaction and quantum confinement. Here, we show that the quantum yield of photogenerated charges in strongly coupled PbSe quantum-dot films is unity over a large temperature range. At high photoexcitation density, a transition takes place from hopping between localized states to band-like transport. These strongly coupled quantum-dot films have electrical properties that approach those of crystalline bulk semiconductors, while retaining the size tunability and cheap processing properties of colloidal quantum dots.

Experimental demonstration of a quantum annealing algorithm for the traveling salesman problem in a nuclear-magnetic-resonance quantum simulator

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

Chen Hongwei; High Magnetic Field Laboratory, Hefei Institutes of Physical Science, Chinese Academy of Sciences, Hefei 230031; Kong Xi

The method of quantum annealing (QA) is a promising way for solving many optimization problems in both classical and quantum information theory. The main advantage of this approach, compared with the gate model, is the robustness of the operations against errors originated from both external controls and the environment. In this work, we succeed in demonstrating experimentally an application of the method of QA to a simplified version of the traveling salesman problem by simulating the corresponding Schroedinger evolution with a NMR quantum simulator. The experimental results unambiguously yielded the optimal traveling route, in good agreement with the theoretical prediction.

Control of Emission Color of High Quantum Yield CH3NH3PbBr3 Perovskite Quantum Dots by Precipitation Temperature.

PubMed

Huang, He; Susha, Andrei S; Kershaw, Stephen V; Hung, Tak Fu; Rogach, Andrey L

2015-09-01

Emission color controlled, high quantum yield CH 3 NH 3 PbBr 3 perovskite quantum dots are obtained by changing the temperature of a bad solvent during synthesis. The products for temperatures between 0 and 60 °C have good spectral purity with narrow emission line widths of 28-36 nm, high absolute emission quantum yields of 74% to 93%, and short radiative lifetimes of 13-27 ns.

Fluorescent quantum dot hydrophilization with PAMAM dendrimer

NASA Astrophysics Data System (ADS)

Potapkin, Dmitry V.; Geißler, Daniel; Resch-Genger, Ute; Goryacheva, Irina Yu.

2016-05-01

Polyamidoamine (PAMAM) dendrimers were used to produce CdSe core/multi-shell fluorescent quantum dots (QDs) which are colloidally stable in aqueous solutions. The size, charge, and optical properties of QDs functionalized with the 4th (G4) and 5th (G5) generation of PAMAM were compared with amphiphilic polymer-covered QDs and used as criteria for the evaluation of the suitability of both water solubilization methods. As revealed by dynamic and electrophoretic light scattering (DLS and ELS), the hydrodynamic sizes of the QDs varied from 30 to 65 nm depending on QD type and dendrimer generation, with all QDs displaying highly positive surface charges, i.e., zeta potentials of around +50 mV in water. PAMAM functionalization yielded stable core/multi-shell QDs with photoluminescence quantum yields ( Φ) of up to 45 %. These dendrimer-covered QDs showed a smaller decrease in their Φ upon phase transfer compared with QDs made water soluble via encapsulation with amphiphilic brush polymer bearing polyoxyethylene/polyoxypropylene chains.

Creating high yield water soluble luminescent graphene quantum dots via exfoliating and disintegrating carbon nanotubes and graphite flakes.

PubMed

Lin, Liangxu; Zhang, Shaowei

2012-10-21

We have developed an effective method to exfoliate and disintegrate multi-walled carbon nanotubes and graphite flakes. With this technique, high yield production of luminescent graphene quantum dots with high quantum yield and low oxidization can be achieved.

Note: Measuring instrument of singlet oxygen quantum yield in photodynamic effects

NASA Astrophysics Data System (ADS)

Li, Zhongwei; Zhang, Pengwei; Zang, Lixin; Qin, Feng; Zhang, Zhiguo; Zhang, Hongli

2017-06-01

Using diphenylisobenzofuran (C20H14O) as a singlet oxygen (1O2) reporter, a comparison method, which can be used to measure the singlet oxygen quantum yield (ΦΔ) of the photosensitizer quantitatively, is presented in this paper. Based on this method, an automatic measuring instrument of singlet oxygen quantum yield is developed. The singlet oxygen quantum yield of the photosensitizer hermimether and aloe-emodin is measured. It is found that the measuring results are identical to the existing ones, which verifies the validity of the measuring instrument.

Chemical processing of three-dimensional graphene networks on transparent conducting electrodes for depleted-heterojunction quantum dot solar cells.

PubMed

Tavakoli, Mohammad Mahdi; Simchi, Abdolreza; Fan, Zhiyong; Aashuri, Hossein

2016-01-07

We present a novel chemical procedure to prepare three-dimensional graphene networks (3DGNs) as a transparent conductive film to enhance the photovoltaic performance of PbS quantum-dot (QD) solar cells. It is shown that 3DGN electrodes enhance electron extraction, yielding a 30% improvement in performance compared with the conventional device.

Quantum Yields in Mixed-Conifer Forests and Ponderosa Pine Plantations

NASA Astrophysics Data System (ADS)

Wei, L.; Marshall, J. D.; Zhang, J.

2008-12-01

Most process-based physiological models require canopy quantum yield of photosynthesis as a starting point to simulate carbon sequestration and subsequently gross primary production (GPP). The quantum yield is a measure of photosynthetic efficiency expressed in moles of CO2 assimilated per mole of photons absorbed; the process is influenced by environmental factors. In the summer 2008, we measured quantum yields on both sun and shade leaves for four conifer species at five sites within Mica Creek Experimental Watershed (MCEW) in northern Idaho and one conifer species at three sites in northern California. The MCEW forest is typical of mixed conifer stands dominated by grand fir (Abies grandis (Douglas ex D. Don) Lindl.). In northern California, the three sites with contrasting site qualities are ponderosa pine (Pinus ponderosa C. Lawson var. ponderosa) plantations that were experimentally treated with vegetation control, fertilization, and a combination of both. We found that quantum yields in MCEW ranged from ~0.045 to ~0.075 mol CO2 per mol incident photon. However, there were no significant differences between canopy positions, or among sites or tree species. In northern California, the mean value of quantum yield of three sites was 0.051 mol CO2/mol incident photon. No significant difference in quantum yield was found between canopy positions, or among treatments or sites. The results suggest that these conifer species maintain relatively consistent quantum yield in both MCEW and northern California. This consistency simplifies the use of a process-based model to accurately predict forest productivity in these areas.

Absolute 1* quantum yields for the ICN A state by diode laser gain versus absorption spectroscopy

NASA Technical Reports Server (NTRS)

Hess, Wayne P.; Leone, Stephen R.

1987-01-01

Absolute I* quantum yields were measured as a function of wavelength for room temperature photodissociation of the ICN A state continuum. The temperature yields are obtained by the technique of time-resolved diode laser gain-versus-absorption spectroscopy. Quantum yields are evaluated at seven wavelengths from 248 to 284 nm. The yield at 266 nm is 66.0 +/- 2% and it falls off to 53.4 +/- 2% and 44.0 +/- 4% at 284 and 248 respectively. The latter values are significantly higher than those obtained by previous workers using infrared fluorescence. Estimates of I* quantum yields obtained from analysis of CN photofragment rotational distributions, as discussed by other workers, are in good agreement with the I* yields. The results are considered in conjunction with recent theoretical and experimental work on the CN rotational distributions and with previous I* yield results.

Comparison of exciplex generation under optical and X-ray excitation

NASA Astrophysics Data System (ADS)

Kipriyanov, A. A.; Melnikov, A. R.; Stass, D. V.; Doktorov, A. B.

2017-09-01

Exciplex generation under optical and X-ray excitation in identical conditions is experimentally compared using a specially chosen model donor-acceptor system, anthracene (electron acceptor) and N,N-dimethylaniline (electron donor) in non-polar solution, and the results are analyzed and interpreted based on analytically calculated luminescence quantum yields. Calculations are performed on the basis of kinetic equations for multistage schemes of bulk exciplex production reaction under optical excitation and combination of bulk and geminate reactions of radical ion pairs under X-ray excitation. These results explain the earlier experimentally found difference in the ratio of the quantum yields of exciplexes and excited electron acceptors (exciplex generation efficiency) and the corresponding change in the exciplex generation efficiency under X-irradiation as compared to the reaction under optical excitation.

Comparison of exciplex generation under optical and X-ray excitation.

PubMed

Kipriyanov, A A; Melnikov, A R; Stass, D V; Doktorov, A B

2017-09-07

Exciplex generation under optical and X-ray excitation in identical conditions is experimentally compared using a specially chosen model donor-acceptor system, anthracene (electron acceptor) and N,N-dimethylaniline (electron donor) in non-polar solution, and the results are analyzed and interpreted based on analytically calculated luminescence quantum yields. Calculations are performed on the basis of kinetic equations for multistage schemes of bulk exciplex production reaction under optical excitation and combination of bulk and geminate reactions of radical ion pairs under X-ray excitation. These results explain the earlier experimentally found difference in the ratio of the quantum yields of exciplexes and excited electron acceptors (exciplex generation efficiency) and the corresponding change in the exciplex generation efficiency under X-irradiation as compared to the reaction under optical excitation.

High quantum yield ZnO quantum dots synthesizing via an ultrasonication microreactor method.

PubMed

Yang, Weimin; Yang, Huafang; Ding, Wenhao; Zhang, Bing; Zhang, Le; Wang, Lixi; Yu, Mingxun; Zhang, Qitu

2016-11-01

Green emission ZnO quantum dots were synthesized by an ultrasonic microreactor. Ultrasonic radiation brought bubbles through ultrasonic cavitation. These bubbles built microreactor inside the microreactor. The photoluminescence properties of ZnO quantum dots synthesized with different flow rate, ultrasonic power and temperature were discussed. Flow rate, ultrasonic power and temperature would influence the type and quantity of defects in ZnO quantum dots. The sizes of ZnO quantum dots would be controlled by those conditions as well. Flow rate affected the reaction time. With the increasing of flow rate, the sizes of ZnO quantum dots decreased and the quantum yields first increased then decreased. Ultrasonic power changed the ultrasonic cavitation intensity, which affected the reaction energy and the separation of the solution. With the increasing of ultrasonic power, sizes of ZnO quantum dots first decreased then increased, while the quantum yields kept increasing. The effect of ultrasonic temperature on the photoluminescence properties of ZnO quantum dots was influenced by the flow rate. Different flow rate related to opposite changing trend. Moreover, the quantum yields of ZnO QDs synthesized by ultrasonic microreactor could reach 64.7%, which is higher than those synthesized only under ultrasonic radiation or only by microreactor. Copyright © 2016 Elsevier B.V. All rights reserved.

Fluorescence enhancement by Au nanostructures: nanoshells and nanorods.

PubMed

Bardhan, Rizia; Grady, Nathaniel K; Cole, Joseph R; Joshi, Amit; Halas, Naomi J

2009-03-24

Metallic nanoparticles influence the quantum yield and lifetime of adjacent fluorophores in a manner dependent on the properties of the nanostructure. Here we directly compare the fluorescence enhancement of the near-infrared fluorophore IR800 by Au nanoshells (NSs) and Au nanorods (NRs), where human serum albumin (HSA) serves as a spacer layer between the nanoparticle and the fluorophore. Our measurements reveal that the quantum yield of IR800 is enhanced from approximately 7% as an isolated fluorophore to 86% in a NSs-HSA-IR800 complex and 74% in a NRs-HSA-IR800 complex. This dramatic increase in fluorescence shows tremendous potential for contrast enhancement in fluorescence-based bioimaging.

Degradation Mechanisms in Blue Phosphorescent Organic Light-Emitting Devices by Exciton-Polaron Interactions: Loss in Quantum Yield versus Loss in Charge Balance.

PubMed

Zhang, Yingjie; Aziz, Hany

2017-01-11

We study the relative importance of deterioration of material quantum yield and charge balance to the electroluminescence stability of PHOLEDs, with a special emphasis on blue devices. Investigations show that the quantum yields of both host and emitter in the emission layer degrade due to exciton-polaron interactions and that the deterioration in material quantum yield plays the primary role in device degradation under operation. On the other hand, the results show that the charge balance factor is also affected by exciton-polaron interactions but only plays a secondary role in determining device stability. Finally, we show that the degradation mechanisms in blue PHOLEDs are fundamentally the same as those in green PHOLEDs. The limited stability of the blue devices is a result of faster deterioration in the quantum yield of the emitter.

Quantum plasmonic sensing

DOE PAGES

Fan, Wenjiang; Lawrie, Benjamin J.; Pooser, Raphael C.

2015-11-04

Surface plasmon resonance (SPR) sensors can reach the quantum noise limit of the optical readout field in various configurations. We demonstrate that two-mode intensity squeezed states produce a further enhancement in sensitivity compared with a classical optical readout when the quantum noise is used to transduce an SPR sensor signal in the Kretschmann configuration. The quantum noise reduction between the twin beams when incident at an angle away from the plasmonic resonance, combined with quantum noise resulting from quantum anticorrelations when on resonance, results in an effective SPR-mediated modulation that yields a measured sensitivity 5 dB better than that withmore » a classical optical readout in this configuration. Furthermore, the theoretical potential of this technique points to resolving particle concentrations with more accuracy than is possible via classical approaches to optical transduction.« less

Fluorescence Quantum Yield Measurements of Fluorescent Proteins: A Laboratory Experiment for a Biochemistry or Molecular Biophysics Laboratory Course

ERIC Educational Resources Information Center

Wall, Kathryn P.; Dillon, Rebecca; Knowles, Michelle K.

2015-01-01

Fluorescent proteins are commonly used in cell biology to assess where proteins are within a cell as a function of time and provide insight into intracellular protein function. However, the usefulness of a fluorescent protein depends directly on the quantum yield. The quantum yield relates the efficiency at which a fluorescent molecule converts…

Spectroscopy characterization and quantum yield determination of quantum dots

NASA Astrophysics Data System (ADS)

Contreras Ortiz, S. N.; Mejía Ospino, E.; Cabanzo, R.

2016-02-01

In this paper we show the characterization of two kinds of quantum dots: hydrophilic and hydrophobic, with core and core/shell respectively, using spectroscopy techniques such as UV-Vis, fluorescence and Raman. We determined the quantum yield in the quantum dots using the quinine sulphate as standard. This salt is commonly used because of its quantum yield (56%) and stability. For the CdTe excitation, we used a wavelength of 549nm and for the CdSe/ZnS excitation a wavelength of 527nm. The results show that CdSe/ZnS (49%) has better fluorescence, better quantum dots, and confirm the fluorescence result. The quantum dots have shown a good fluorescence performance, so this property will be used to replace dyes, with the advantage that quantum dots are less toxic than some dyes like the rhodamine. In addition, in this work we show different techniques to find the quantum dots emission: fluorescence spectrum, synchronous spectrum and Raman spectrum.

Optical and Photophysical Investigation of (2E)-1-(2,5-Dimethylfuran-3-Yl)-3-(9-Ethyl-9H-Carbazol-3-Yl)Prop-2-en-1-One (DEPO) by Spectrofluorometer in Organized Medium.

PubMed

Asiri, Abdullah M; Al-Dies, Al-Anood M; Khan, Salman A

2017-07-01

(2E)-1-(2,5-dimethylfuran-3-yl)-3-(9-ethyl-9H-carbazol-3-yl)prop-2-en-1-one (DEPO) was prepared by the reaction of 9-ethyl-9H-carbazole-3-carbaldehyde with 1-(2,5-dimethylfuran-3-yl)ethanone under microwave irradiation. The structure of DEPO was established experimentally by EI-MS, FT-IR, 1 H and 13 C NMR spectral studies. Electronic absorption and emission spectra of DEPO were studied in different solvents on the basis of polarities, and the obtain data were used to determine the solvatochromic properties such as extinction coefficient, oscillator strength, transition dipole moment, stokes shift, fluorescence quantum yield and photochemical quantum yield. Photochemical quantum yield (Φ c ) of DEPO dye was determined in different solvent. The dye comparatively photostable in DMSO but undergoes photodecomposition in chloro methane solvents. The DEPO dye may be use as probe or quencher to determine critical micelle concentration (CMC) of cetyltri methyl ammonium bromide (CTAB) and sodium dodecyl sulfate (SDS).

In vivo characterization of hair and skin derived carbon quantum dots with high quantum yield as long-term bioprobes in zebrafish

PubMed Central

Zhang, Jing-Hui; Niu, Aping; Li, Jing; Fu, Jian-Wei; Xu, Qun; Pei, De-Sheng

2016-01-01

Carbon quantum dots (CDs) were widely investigated because of their tunable fluorescence properties and low toxicity. However, so far there have been no reports on in vivo functional studies of hair and skin derived CDs. Here, hair derived CDs (HCDs) and skin derived CDs (SCDs) were produced by using human hair and pig skin as precursors. The quantum yields (QYs) of HCDs and SCDs were quite high, compared to citric acid derived CDs (CCDs). HCDs and SCDs possess optimal photostability, hypotoxicity and biocompatibility in zebrafish, indicating that HCDs and SCDs possess the capacity of being used as fluorescence probes for in vivo biological imaging. The long-time observation for fluorescence alternation of CDs in zebrafish and the quenching assay of CDs by ATP, NADH and Fe3+ ions demonstrated that the decaying process of CDs in vivo might be induced by the synergistic effect of the metabolism process. All results indicated that large batches and high QYs of CDs can be acquired by employing natural and nontoxic hair and skin as precursors. To our knowledge, this is the first time to report SCDs, in vivo comparative studies of HCDs, SCDs and CCDs as bioprobes, and explore their mechanism of photostability in zebrafish. PMID:27886267

In vivo characterization of hair and skin derived carbon quantum dots with high quantum yield as long-term bioprobes in zebrafish.

PubMed

Zhang, Jing-Hui; Niu, Aping; Li, Jing; Fu, Jian-Wei; Xu, Qun; Pei, De-Sheng

2016-11-25

Carbon quantum dots (CDs) were widely investigated because of their tunable fluorescence properties and low toxicity. However, so far there have been no reports on in vivo functional studies of hair and skin derived CDs. Here, hair derived CDs (HCDs) and skin derived CDs (SCDs) were produced by using human hair and pig skin as precursors. The quantum yields (QYs) of HCDs and SCDs were quite high, compared to citric acid derived CDs (CCDs). HCDs and SCDs possess optimal photostability, hypotoxicity and biocompatibility in zebrafish, indicating that HCDs and SCDs possess the capacity of being used as fluorescence probes for in vivo biological imaging. The long-time observation for fluorescence alternation of CDs in zebrafish and the quenching assay of CDs by ATP, NADH and Fe 3+ ions demonstrated that the decaying process of CDs in vivo might be induced by the synergistic effect of the metabolism process. All results indicated that large batches and high QYs of CDs can be acquired by employing natural and nontoxic hair and skin as precursors. To our knowledge, this is the first time to report SCDs, in vivo comparative studies of HCDs, SCDs and CCDs as bioprobes, and explore their mechanism of photostability in zebrafish.

In vivo characterization of hair and skin derived carbon quantum dots with high quantum yield as long-term bioprobes in zebrafish

NASA Astrophysics Data System (ADS)

Zhang, Jing-Hui; Niu, Aping; Li, Jing; Fu, Jian-Wei; Xu, Qun; Pei, De-Sheng

2016-11-01

Carbon quantum dots (CDs) were widely investigated because of their tunable fluorescence properties and low toxicity. However, so far there have been no reports on in vivo functional studies of hair and skin derived CDs. Here, hair derived CDs (HCDs) and skin derived CDs (SCDs) were produced by using human hair and pig skin as precursors. The quantum yields (QYs) of HCDs and SCDs were quite high, compared to citric acid derived CDs (CCDs). HCDs and SCDs possess optimal photostability, hypotoxicity and biocompatibility in zebrafish, indicating that HCDs and SCDs possess the capacity of being used as fluorescence probes for in vivo biological imaging. The long-time observation for fluorescence alternation of CDs in zebrafish and the quenching assay of CDs by ATP, NADH and Fe3+ ions demonstrated that the decaying process of CDs in vivo might be induced by the synergistic effect of the metabolism process. All results indicated that large batches and high QYs of CDs can be acquired by employing natural and nontoxic hair and skin as precursors. To our knowledge, this is the first time to report SCDs, in vivo comparative studies of HCDs, SCDs and CCDs as bioprobes, and explore their mechanism of photostability in zebrafish.

Tuning Optoelectronic Properties of the Graphene-Based Quantum Dots C16- xSi xH10 Family.

PubMed

Ramadan, F-Z; Ouarrad, H; Drissi, L B

2018-06-07

The electronic and optical properties of graphene-based quantum dots (QDs) are investigated using DFT and many-body perturbation theory. Formation energy, hardeness and electrophilicity show that all structures, from pyrene to silicene QD passing through 15 CSi QD configurations, are energetically and chemically stable. It is also found that they are reactive which implies their favorable character for the possible electronic transport and conductivity. The electronic and optical properties are very sensitive to the number and position of the substituted silicon atoms as well as the directions of the light polarization. Moreover, quantum confinement effects make the exciton binding energy of CSi quantum dots larger than those of their higher dimensional allotropes such as silicene, graphene, and SiC sheet and nanotube. It is also higher those of other shapes of quantum dots like hexagonal graphene QDs and can be tailored from the ultraviolet region to the visible one. The values of the singlet-triplet splitting determined for the X- and Y-light polarized indicate that all configurations have a high fluorescence quantum yield compared to the yield of typical semiconductors, which makes them very promising for various applications such as the light-emitting diode material and nanomedicine.

Can we Predict Quantum Yields Using Excited State Density Functional Theory for New Families of Fluorescent Dyes?

NASA Astrophysics Data System (ADS)

Kohn, Alexander W.; Lin, Zhou; Shepherd, James J.; Van Voorhis, Troy

2016-06-01

For a fluorescent dye, the quantum yield characterizes the efficiency of energy transfer from the absorbed light to the emitted fluorescence. In the screening among potential families of dyes, those with higher quantum yields are expected to have more advantages. From the perspective of theoreticians, an efficient prediction of the quantum yield using a universal excited state electronic structure theory is in demand but still challenging. The most representative examples for such excited state theory include time-dependent density functional theory (TDDFT) and restricted open-shell Kohn-Sham (ROKS). In the present study, we explore the possibility of predicting the quantum yields for conventional and new families of organic dyes using a combination of TDDFT and ROKS. We focus on radiative (kr) and nonradiative (knr) rates for the decay of the first singlet excited state (S_1) into the ground state (S_0) in accordance with Kasha's rule. M. Kasha, Discuss. Faraday Soc., 9, 14 (1950). For each dye compound, kr is calculated with the S_1-S_0 energy gap and transition dipole moment obtained using ROKS and TDDFT respectively at the relaxed S_1 geometry. Our predicted kr agrees well with the experimental value, so long as the order of energy levels is correctly predicted. Evaluation of knr is less straightforward as multiple processes are involved. Our study focuses on the S_1-T_1 intersystem crossing (ISC) and the S_1-S_0 internal conversion (IC): we investigate the properties that allow us to model the knr value using a Marcus-like expression, such as the Stokes shift, the reorganization energy, and the S_1-T_1 and S_1-S_0 energy gaps. Taking these factors into consideration, we compare our results with those obtained using the actual Marcus theory and provide explanation for discrepancy. T. Kowalczyk, T. Tsuchimochi, L. Top, P.-T. Chen, and T. Van Voorhis, J. Chem. Phys., 138, 164101 (2013). M. Kasha, Discuss. Faraday Soc., 9, 14 (1950).

Quantum Yields of Soluble and Particulate Material in the Ocean

DTIC Science & Technology

1999-09-30

and prospects. IEEE Transactions, 46(5): 825-829 In Press Moisan, T.A. & B.G. Mitchell UV Absorption by Mycosporine - like Amino Acids in Phaeocystis...were grown to evaluate the spectral quantum yield of in vivo chlorophyll a fluorescence. We determined that mycosporine amino acids with UV absorption...evaluate the role of photoprotective pigments, including mycosporine amino acids and the xanthophyll pigments in Phaeocystis, on the spectral quantum yield

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

Chen, Haixia; Zhang, Jing

We propose a scheme for continuous-variable quantum cloning of coherent states with phase-conjugate input modes using linear optics. The quantum cloning machine yields M identical optimal clones from N replicas of a coherent state and N replicas of its phase conjugate. This scheme can be straightforwardly implemented with the setups accessible at present since its optical implementation only employs simple linear optical elements and homodyne detection. Compared with the original scheme for continuous-variable quantum cloning with phase-conjugate input modes proposed by Cerf and Iblisdir [Phys. Rev. Lett. 87, 247903 (2001)], which utilized a nondegenerate optical parametric amplifier, our scheme losesmore » the output of phase-conjugate clones and is regarded as irreversible quantum cloning.« less

[Fluorescence spectra and quantum yield of TiO2 nanocrystals synthesized by alcohothermal method].

PubMed

Song, Cui-Hong; Li, Yan-Ting; Li, Jing; Wei, Yong-Ju; Hu, Yu-Zhu; Wei, Yu

2008-01-01

Fluorescence spectra and fluorescence quantum yield of TiO2 nanocrystals were studied. Using tetra n-butyl titanate as a starting material, a facile alcohothermal technique was used to synthesize TiO2 nanocrystals. As can be seen from the transmittance electron microscopy (TEM) image, TiO2 nanocrystals with a relatively uniform particle size distribution of < 10 nm are present in the transparent sol. The transparent sol presents a strong stable fluorescence emission with a maximum at 450 nm, which is greatly dependent on the size quantization effects, defect energy level and the surface state of TiO2 nanocrystals. The quantum yield (gamma) of TiO2 was determined by the relative comparison procedure, using freshly prepared analytical purity quinine sulfate in 0.05 mol x L(-1) H2SO4 as a relative quantum yield standard. The emission quantum yield of TiO2 nanocrystals prepared in alcoholic media was calculated to be about 0.20 at wavelengths ranging from 330 to 370 nm, which was much higher than the values reported in previous works. So, it is supposed that nano-TiO2 will be applied as a potential quantum dots fluorescence probe in biological analysis.

Surface Stabilized InP/GaP/ZnS Quantum Dots with Mg Ions for WLED Application.

PubMed

Park, Joong Pill; Kim, Sang-Wook

2016-05-01

One of the most highlighted cadmium-free quantum dots (QDs), InP-based QDs, have improved their optical properties. However, InP-based QDs have some practical drawbacks, for example, stability, compared with CdSe-based QDs. Poor stability of InP-based QDs yields critical problems, such as agglomeration and photoluminescence quenching in light emitting diode (LED). It has to be solved for applications and most research has focused on thick outer shells as an effective solution. We introduced magnesium cations for improving stability of InP-based QDs. We applied very small amounts of Mg cations as surface stabilizers, as a result, stability of QDs is clearly improved. Then, QD based LED chips also yield improved values including RA of 84.4, CCT of 3799 K, and luminous efficiency of 129.57 Im/W, which are highly improved data compared with our previous results.

Ensemble brightening and enhanced quantum yield in size-purified silicon nanocrystals

DOE PAGES

Miller, Joseph B.; Van Sickle, Austin R.; Anthony, Rebecca J.; ...

2012-07-18

Here, we report on the quantum yield, photoluminescence (PL) lifetime and ensemble photoluminescent stability of highly monodisperse plasma-synthesized silicon nanocrystals (SiNCs) prepared though density-gradient ultracentrifugation in mixed organic solvents. Improved size uniformity leads to a reduction in PL line width and the emergence of entropic order in dry nanocrystal films. We find excellent agreement with the anticipated trends of quantum confinement in nanocrystalline silicon, with a solution quantum yield that is independent of nanocrystal size for the larger fractions but decreases dramatically with size for the smaller fractions. We also find a significant PL enhancement in films assembled from themore » fractions, and we use a combination of measurement, simulation and modeling to link this ‘brightening’ to a temporally enhanced quantum yield arising from SiNC interactions in ordered ensembles of monodisperse nanocrystals. Using an appropriate excitation scheme, we exploit this enhancement to achieve photostable emission.« less

Aeronomical determinations of the quantum yields of O (1S) and O (1D) from dissociative recombination of O2(+)

NASA Technical Reports Server (NTRS)

Yee, Jeng-Hwa; Abreu, Vincent J.; Colwell, William B.

1989-01-01

Data from the visible-airglow experiment on the Atmosphere Explorer-E satellite have been used to determine the quantum yields of O (1S) and O (1D) from the dissociative recombination of O2(+) based on a constant total recombination rate from each vibrational level. A range of values between 0.05 and 0.18 has been obtained for the quantum yield of O (1S) and shows a positive correlation with the extent of the vibrational excitation of O2(+). The quantum yield of O (1D) has been measured to be 0.9 + or - 0.2, with no apparent dependence on the vibrational distribution of O2(+).

Tuning Single Quantum Dot Emission with a Micromirror.

PubMed

Yuan, Gangcheng; Gómez, Daniel; Kirkwood, Nicholas; Mulvaney, Paul

2018-02-14

The photoluminescence of single quantum dots fluctuates between bright (on) and dark (off) states, also termed fluorescence intermittency or blinking. This blinking limits the performance of quantum dot-based devices such as light-emitting diodes and solar cells. However, the origins of the blinking remain unresolved. Here, we use a movable gold micromirror to determine both the quantum yield of the bright state and the orientation of the excited state dipole of single quantum dots. We observe that the quantum yield of the bright state is close to unity for these single QDs. Furthermore, we also study the effect of a micromirror on blinking, and then evaluate excitation efficiency, biexciton quantum yield, and detection efficiency. The mirror does not modify the off-time statistics, but it does change the density of optical states available to the quantum dot and hence the on times. The duration of the on times can be lengthened due to an increase in the radiative recombination rate.

Solvent Dependency in the Quantum Efficiency of 4-[(4-Aminophenyl)-(4-imino-1-cyclohexa-2, 5- dienylidene) methyl] Aniline Hydrochloride.

PubMed

Pathrose, Bini; Nampoori, V P N; Radhakrishnan, P; Sahira, H; Mujeeb, A

2015-05-01

In the present work dual beam thermal lens technique is used for studying the solvent dependency on the quantum efficiency of a novel dye used for biomedical applications. The role of solvent in the absolute fluorescence quantum yield of 4-[(4-Aminophenyl)-(4-imino-1-cyclohexa-2, 5- dienylidene) methyl] aniline hydrochloride is studied using thermal lens technique. It is observed that the variation in solvents and its concentration results considerable variations in the fluorescence quantum yield. These variations are due to the non-radiative relaxation of the absorbed energy and because of the different solvent properties. The highest quantum yield of the dye is observed in the polar protic solvent-water.

In Search of the Perfect Photocage: Structure-Reactivity Relationships in meso-Methyl BODIPY Photoremovable Protecting Groups.

PubMed

Slanina, Tomáš; Shrestha, Pradeep; Palao, Eduardo; Kand, Dnyaneshwar; Peterson, Julie A; Dutton, Andrew S; Rubinstein, Naama; Weinstain, Roy; Winter, Arthur H; Klán, Petr

2017-10-25

A detailed investigation of the photophysical parameters and photochemical reactivity of meso-methyl BODIPY photoremovable protecting groups was accomplished through systematic variation of the leaving group (LG) and core substituents as well as substitutions at boron. Efficiencies of the LG release were evaluated using both steady-state and transient absorption spectroscopies as well as computational analyses to identify the optimal structural features. We find that the quantum yields for photorelease with this photocage are highly sensitive to substituent effects. In particular, we find that the quantum yields of photorelease are improved with derivatives with higher intersystem crossing quantum yields, which can be promoted by core heavy atoms. Moreover, release quantum yields are dramatically improved by boron alkylation, whereas alkylation in the meso-methyl position has no effect. Better LGs are released considerably more efficiently than poorer LGs. We find that these substituent effects are additive, for example, a 2,6-diiodo-B-dimethyl BODIPY photocage features quantum yields of 28% for the mediocre LG acetate and a 95% quantum yield of release for chloride. The high chemical and quantum yields combined with the outstanding absorption properties of BODIPY dyes lead to photocages with uncaging cross sections over 10 000 M -1 cm -1 , values that surpass cross sections of related photocages absorbing visible light. These new photocages, which absorb strongly near the second harmonic of an Nd:YAG laser (532 nm), hold promise for manipulating and interrogating biological and material systems with the high spatiotemporal control provided by pulsed laser irradiation, while avoiding the phototoxicity problems encountered with many UV-absorbing photocages. More generally, the insights gained from this structure-reactivity relationship may aid in the development of new highly efficient photoreactions.

Quantum yield measurements of light-induced H₂ generation in a photosystem I-[FeFe]-H₂ase nanoconstruct.

PubMed

Applegate, Amanda M; Lubner, Carolyn E; Knörzer, Philipp; Happe, Thomas; Golbeck, John H

2016-01-01

The quantum yield for light-induced H2 generation was measured for a previously optimized bio-hybrid cytochrome c 6-crosslinked PSI(C13G)-1,8-octanedithiol-[FeFe]-H2ase(C97G) (PSI-H2ase) nanoconstruct. The theoretical quantum yield for the PSI-H2ase nanoconstruct is 0.50 molecules of H2 per photon absorbed, which equates to a requirement of two photons per H2 generated. Illumination of the PSI-H2ase nanoconstruct with visible light between 400 and 700 nm resulted in an average quantum yield of 0.10-0.15 molecules of H2 per photon absorbed, which equates to a requirement of 6.7-10 photons per H2 generated. A possible reason for the difference between the theoretical and experimental quantum yield is the occurrence of non-productive PSI(C13G)-1,8-octanedithiol-PSIC13G (PSI-PSI) conjugates, which would absorb light without generating H2. Assuming the thiol-Fe coupling is equally efficient at producing PSI-PSI conjugates as well as in producing PSI-H2ase nanoconstructs, the theoretical quantum yield would decrease to 0.167 molecules of H2 per photon absorbed, which equates to 6 photons per H2 generated. This value is close to the range of measured values in the current study. A strategy that purifies the PSI-H2ase nanoconstructs from the unproductive PSI-PSI conjugates or that incorporates different chemistries on the PSI and [FeFe]-H2ase enzyme sites could potentially allow the PSI-H2ase nanoconstruct to approach the expected theoretical quantum yield for light-induced H2 generation.

Quantum Yield Heterogeneity among Single Nonblinking Quantum Dots Revealed by Atomic Structure-Quantum Optics Correlation

DOE PAGES

Orfield, Noah J.; McBride, James R.; Wang, Feng; ...

2016-02-05

Physical variations in colloidal nanostructures give rise to heterogeneity in expressed optical behavior. This correlation between nanoscale structure and function demands interrogation of both atomic structure and photophysics at the level of single nanostructures to be fully understood. In this paper, by conducting detailed analyses of fine atomic structure, chemical composition, and time-resolved single-photon photoluminescence data for the same individual nanocrystals, we reveal inhomogeneity in the quantum yields of single nonblinking “giant” CdSe/CdS core/shell quantum dots (g-QDs). We find that each g-QD possesses distinctive single exciton and biexciton quantum yields that result mainly from variations in the degree of charging,more » rather than from volume or structure inhomogeneity. We further establish that there is a very limited nonemissive “dark” fraction (<2%) among the studied g-QDs and present direct evidence that the g-QD core must lack inorganic passivation for the g-QD to be “dark”. Finally and therefore, in contrast to conventional QDs, ensemble photoluminescence quantum yield is principally defined by charging processes rather than the existence of dark g-QDs.« less

High-Fidelity Single-Shot Toffoli Gate via Quantum Control.

PubMed

Zahedinejad, Ehsan; Ghosh, Joydip; Sanders, Barry C

2015-05-22

A single-shot Toffoli, or controlled-controlled-not, gate is desirable for classical and quantum information processing. The Toffoli gate alone is universal for reversible computing and, accompanied by the Hadamard gate, forms a universal gate set for quantum computing. The Toffoli gate is also a key ingredient for (nontopological) quantum error correction. Currently Toffoli gates are achieved by decomposing into sequentially implemented single- and two-qubit gates, which require much longer times and yields lower overall fidelities compared to a single-shot implementation. We develop a quantum-control procedure to construct a single-shot Toffoli gate for three nearest-neighbor-coupled superconducting transmon systems such that the fidelity is 99.9% and is as fast as an entangling two-qubit gate under the same realistic conditions. The gate is achieved by a nongreedy quantum control procedure using our enhanced version of the differential evolution algorithm.

Influence of Bridgehead Substitution and Ring Annelation on the Photophysical Properties of Polycyclic DBO-Type Azoalkanes.

PubMed

Adam, Waldemar; Nikolaus, Achim; Sauer, Jürgen

1999-05-14

The photophysical data for the polycyclic, bridgehead-substituted derivatives 1-10 of the photoreluctant diazabicyclo[2.2.2]oct-2-ene (DBO) are presented. Substitution on the bridgehead positions with radical-stabilizing substituents enhances the photoreactivity (Phi(r)) and decreases the fluorescence quantum yields (Phi(f)) and lifetimes (tau) compared to the parent DBO. The annelated rings have no influence on the photoreactivity, except when steric interactions with an alpha substituent hinder the optimal radical-stabilizing conformation. The fused rings and some of the bridgehead substituents reduce the solvent-induced quenching of the singlet-excited azo chromophore by steric shielding of the azo group and, thus, increase the fluorescence quantum yields and lifetimes.

Carrier Multiplication in Quantum Dots within the Framework of Two Competing Energy Relaxation Mechanisms.

PubMed

Stewart, John T; Padilha, Lazaro A; Bae, Wan Ki; Koh, Weon-Kyu; Pietryga, Jeffrey M; Klimov, Victor I

2013-06-20

The realization of high-yield, low-threshold carrier multiplication (CM) in semiconductor quantum dots (QDs) is a promising step toward third-generation photovoltaics (PV). Recent studies of QD solar cells have shown that CM can indeed produce greater-than-unity quantum efficiencies in photon-to-charge-carrier conversion, establishing the relevance of this process to practical PV technologies. While being appreciable, the reported CM yields are still not high enough for a significant increase in the power conversion efficiency over traditional bulk materials. At present, the design of nanomaterials with improved CM is hindered by a poor understanding of the mechanism underlying this process. Here, we present a possible solution to this problem by introducing a model that treats CM as a competition between impact-ionization-like scattering and non-CM energy losses. Importantly, it allows for evaluation of expected CM yields from fairly straightforward measurements of Auger recombination (inverse of CM) and near-band-edge carrier cooling. The validation of this model via a comparative CM study of PbTe, PbSe, and PbS QDs suggests that it indeed represents a predictive capability, which might help in the development of nanomaterials with improved CM performance.

Ultrafast and Efficient Transport of Hot Plasmonic Electrons by Graphene for Pt Free, Highly Efficient Visible-Light Responsive Photocatalyst.

PubMed

Kumar, Dinesh; Lee, Ahreum; Lee, Taegon; Lim, Manho; Lim, Dong-Kwon

2016-03-09

We report that reduced graphene-coated gold nanoparticles (r-GO-AuNPs) are excellent visible-light-responsive photocatalysts for the photoconversion of CO2 into formic acid (HCOOH). The wavelength-dependent quantum and chemical yields of HCOOH shows a significant contribution of plasmon-induced hot electrons for CO2 photoconversion. Furthermore, the presence and reduced state of the graphene layers are critical parameters for the efficient CO2 photoconversion because of the electron mobility of graphene. With an excellent selectivity toward HCOOH (>90%), the quantum yield of HCOOH using r-GO-AuNPs is 1.52%, superior to that of Pt-coated AuNPs (quantum yield: 1.14%). This indicates that r-GO is a viable alternative to platinum metal. The excellent colloidal stability and photocatalytic stability of r-GO-AuNPs enables CO2 photoconversion under more desirable reaction conditions. These results highlight the role of reduced graphene layers as highly efficient electron acceptors and transporters to facilitate the use of hot electrons for plasmonic photocatalysts. The femtosecond transient spectroscopic analysis also shows 8.7 times higher transport efficiency of hot plasmonic electrons in r-GO-AuNPs compared with AuNPs.

Photophysics and catalysis of porphyrinoids

NASA Astrophysics Data System (ADS)

Aggarwal, Amit

Organic nanoparticles (ONP) of metalloporphyrins can be versatile catalysts for the selective oxidation of alkenes and other hydrocarbons. Herein, we report the catalytic activity of ONP of 5,10,15,20-tetrakis-[4-(1'H,1'H,2'H,2'H-heptadecafluorodecane-1-thiol)-2,3,5,6-tetrafluorophenyl] porphyrinato iron(III), Fe(III)TPPF84, and 5,10,15,20-tetakis-(2,3,4,5,6-pentafluorophenyl) porphyrinato manganese(III), Mn(III)TPPF20, for cyclohexene oxidation using molecular oxygen as an oxidant in water under ambient conditions. Sequential dipping of indium-tin-oxide electrodes into solutions of tetra cationic porphyrins and tetra anionic polyoxometalates results in the controlled formation of nm thick films. The potential applications of these robust films on electrodes range from catalysts to sensors. This chapter focuses on the electrochemistry of the multilayered films where it is found that the oxidation and reduction potentials of each species remain largely the same as found in solution. Photophysical properties of Porphyrinoids bearing four rigid hydrogen bonding motifs on the meso positions, self-assembled into a cofacial cage with four complementary bis(decyl)melamine units in dry solvents are presented here. Self-assembly was investigated by NMR spectroscopy, dynamic light scattering, and atomic force microscopy. The phototphysical properties of the cage formation involve the measurement of their absorption and emission spectra and the fluorescence life time in dry THF. The hydrocarbon chains on the bis(decyl)melamine mediate the formation of nanofilms on surfaces as the solvent slowly evaporates. A systematic study of the photophysical properties of a series of porphyrinoids is presented. The role of the location of a heavy atom in shunting the excited state from the singlet to the triplet manifolds is compared for three cases. It is well known that Pt(II) metalloporphyrins do not fluoresce. For meso pyridyl porphyrins, the fluorescence quantum yield decreases as the number of coordinatively attached Pt(II) complexes increase from 0-4, but the tetracoordinated species retains about 30% of the fluorescence. Covalently attaching a heavy metal complex e.g. Pt(II) complex to the macrocycle by an organometalic bond at the peripheral meso position causes greater than a 20-fold decrease in fluorescence quantum yield and may enhance some internal conversion to the ground state. For comparison, the fluorescence quantum yield decreases somewhat as the number of pyridyl groups on the meso positions increase 0-4. We also evaluate the photophysical properties of a series of porphyrins with nitro groups on the beta pyrrole position and on the meso phenyl group, which also quenches the fluorescence. These studies bear on the use of metal ions to enhance the photophysical properties of these dyes as photodynamic therapeutics and for supramolecular systems, while the nitrated macrocycles have potential application in non linear optics. The photophysical properties of non-hydrolysable tetra- thioglycosylated conjugates of chlorin (CGlc4), isobacteriochlorin (IGlc4) and bacteriochlorin (BGlc4) and core F20 platforms are reported here. These studies involve the measurement of absorption and emission spectra, fluorescence quantum yield, singlet oxygen quantum yield, and singlet state life time in three different solvents: phosphate buffer saline (PBS), ethanol, and ethylacetate. Compared to the porphyrin in PBS, CGlc4 has a markedly greater absorbance of red light near 650 nm and a 6-fold increase in fluorescence quantum yield; whereas IGlc4 has broad Q bands and a 12-fold increase in fluorescence quantum yield. Since IGlc4 CGlc4 very slowly bleach, these properties may enable their use as fluorescent tags to track biological processes. BGlc4 has a similar fluorescence quantum yield to PGlc4, (<10%), but the lowest energy absorption/emission peaks of BGlc4 are considerably red shifted to near 730 nm with a nearly 50-fold greater absorbance, which may allow this conjugate to be an effective PDT agent. (Abstract shortened by UMI.)

The Broken Ring: Reduced Aromaticity in Lys-Trp Cations and High pH Tautomer Correlates with Lower Quantum Yield and Shorter Lifetimes

PubMed Central

2015-01-01

Several nonradiative processes compete with tryptophan fluorescence emission. The difficulty in spectral interpretation lies in associating specific molecular environmental features with these processes and thereby utilizing the fluorescence spectral data to identify the local environment of tryptophan. Here, spectroscopic and molecular modeling study of Lys-Trp dipeptide charged species shows that backbone-ring interactions are undistinguished. Instead, quantum mechanical ground state isosurfaces reveal variations in indole π electron distribution and density that parallel charge (as a function of pK1, pK2, and pKR) on the backbone and residues. A pattern of aromaticity-associated quantum yield and fluorescence lifetime changes emerges. Where quantum yield is high, isosurfaces have a charge distribution similar to the highest occupied molecular orbital (HOMO) of indole, which is the dominant fluorescent ground state of the 1La transition dipole moment. Where quantum yield is low, isosurface charge distribution over the ring is uneven, diminished, and even found off ring. At pH 13, the indole amine is deprotonated, and Lys-Trp quantum yield is extremely low due to tautomer structure that concentrates charge on the indole amine; the isosurface charge distribution bears scant resemblance to the indole HOMO. Such greatly diminished fluorescence has been observed for proteins where the indole nitrogen is hydrogen bonded, lending credence to the association of aromaticity changes with diminished quantum yield in proteins as well. Thus tryptophan ground state isosurfaces are an indicator of indole aromaticity, signaling the partition of excitation energy between radiative and nonradiative processes. PMID:24882092

Comparison of femtosecond laser and continuous wave UV sources for protein-nucleic acid crosslinking.

PubMed

Fecko, Christopher J; Munson, Katherine M; Saunders, Abbie; Sun, Guangxing; Begley, Tadhg P; Lis, John T; Webb, Watt W

2007-01-01

Crosslinking proteins to the nucleic acids they bind affords stable access to otherwise transient regulatory interactions. Photochemical crosslinking provides an attractive alternative to formaldehyde-based protocols, but irradiation with conventional UV sources typically yields inadequate product amounts. Crosslinking with pulsed UV lasers has been heralded as a revolutionary technique to increase photochemical yield, but this method had only been tested on a few protein-nucleic acid complexes. To test the generality of the yield enhancement, we have investigated the benefits of using approximately 150 fs UV pulses to crosslink TATA-binding protein, glucocorticoid receptor and heat shock factor to oligonucleotides in vitro. For these proteins, we find that the quantum yields (and saturating yields) for forming crosslinks using the high-peak intensity femtosecond laser do not improve on those obtained with low-intensity continuous wave (CW) UV sources. The photodamage to the oligonucleotides and proteins also has comparable quantum yields. Measurements of the photochemical reaction yields of several small molecules selected to model the crosslinking reactions also exhibit nearly linear dependences on UV intensity instead of the previously predicted quadratic dependence. Unfortunately, these results disprove earlier assertions that femtosecond pulsed laser sources provide significant advantages over CW radiation for protein-nucleic acid crosslinking.

Primary quantum yields of NO2 photodissociation

NASA Technical Reports Server (NTRS)

Gardner, Edward P.; Sperry, Paul D.; Calvert, Jack G.

1987-01-01

The quantum yields of formation of NO, O2, and NO2 loss are measured for NO2 vapor at low pressures (0.13-0.30 torr) irradiated at 334-405 nm wavelengths and temperature in the range 273-370 K in order to study the primary quantum efficiencies of NO2 photodecomposition. The temperature and wavelength dependences of the primary quantum efficiencies are examined. It is observed that the primary quantum efficiencies increase rapidly from near zero at 424 nm to near unity for excitation at wavelengths less than 394 nm. The theory of Pitts et al. (1964) that the energy deficiency for photodissociation of NO2 excited at wavelengths greater than 397.9 nm is due to the rotational and vibrational energy of the NO2 molecules is confirmed by the data. Values for the primary quantum yields of NO2 photodecomposition as a function of wavelength are presented.

On the Ising character of the quantum-phase transition in LiHoF4

NASA Astrophysics Data System (ADS)

Skomski, R.

2016-05-01

It is investigated how a transverse magnetic field affects the quantum-mechanical character of LiHoF4, a system generally considered as a textbook example for an Ising-like quantum-phase transition. In small magnetic fields, the low-temperature behavior of the ions is Ising-like, involving the nearly degenerate low-lying Jz = ± 8 doublet. However, as the transverse field increases, there is a substantial admixture of states having |Jz| < 8. Near the quantum-phase-transition field, the system is distinctively non-Ising like, and all Jz eigenstates yield ground-state contributions of comparable magnitude. A classical analog to this mechanism is the micromagnetic single point in magnets with uniaxial anisotropy. Since Ho3+ has J = 8, the ion's behavior is reminiscent of the classical limit (J = ∞), but quantum corrections remain clearly visible.

First-principles calculations of Ti and O NMR chemical shift tensors in ferroelectric perovskites

NASA Astrophysics Data System (ADS)

Pechkis, Daniel; Walter, Eric; Krakauer, Henry

2011-03-01

Complementary chemical shift calculations were carried out with embedded clusters, using quantum chemistry methods, and with periodic boundary conditions, using the GIPAW approach within the Quantum Espresso package. Compared to oxygen chemical shifts, δ̂ (O), cluster calculations for δ̂ (Ti) were found to be more sensitive to size effects, termination, and choice of gaussian-type atomic basis set, while GIPAW results were found to be more sensitive to the pseudopotential construction. The two approaches complemented each other in optimizing these factors. We show that the two approaches yield comparable chemical shifts for suitably converged simulations, and results are compared with available experimental measurements. Supported by ONR.

Noncommuting observables in quantum detection and estimation theory

NASA Technical Reports Server (NTRS)

Helstrom, C. W.

1972-01-01

Basing decisions and estimates on simultaneous approximate measurements of noncommuting observables in a quantum receiver is shown to be equivalent to measuring commuting projection operators on a larger Hilbert space than that of the receiver itself. The quantum-mechanical Cramer-Rao inequalities derived from right logarithmic derivatives and symmetrized logarithmic derivatives of the density operator are compared, and it is shown that the latter give superior lower bounds on the error variances of individual unbiased estimates of arrival time and carrier frequency of a coherent signal. For a suitably weighted sum of the error variances of simultaneous estimates of these, the former yield the superior lower bound under some conditions.

A versatile method for the determination of photochemical quantum yields via online UV-Vis spectroscopy.

PubMed

Stadler, Eduard; Eibel, Anna; Fast, David; Freißmuth, Hilde; Holly, Christian; Wiech, Mathias; Moszner, Norbert; Gescheidt, Georg

2018-05-16

We have developed a simple method for determining the quantum yields of photo-induced reactions. Our setup features a fibre coupled UV-Vis spectrometer, LED irradiation sources, and a calibrated spectrophotometer for precise measurements of the LED photon flux. The initial slope in time-resolved absorbance profiles provides the quantum yield. We show the feasibility of our methodology for the kinetic analysis of photochemical reactions and quantum yield determination. The typical chemical actinometers, ferrioxalate and ortho-nitrobenzaldehyde, as well as riboflavin, a spiro-compound, phosphorus- and germanium-based photoinitiators for radical polymerizations and the frequently utilized photo-switch azobenzene serve as paradigms. The excellent agreement of our results with published data demonstrates the high potential of the proposed method as a convenient alternative to the time-consuming chemical actinometry.

Fluorescence quantum yield measurements of fluorescent proteins: a laboratory experiment for a biochemistry or molecular biophysics laboratory course.

PubMed

Wall, Kathryn P; Dillon, Rebecca; Knowles, Michelle K

2015-01-01

Fluorescent proteins are commonly used in cell biology to assess where proteins are within a cell as a function of time and provide insight into intracellular protein function. However, the usefulness of a fluorescent protein depends directly on the quantum yield. The quantum yield relates the efficiency at which a fluorescent molecule converts absorbed photons into emitted photons and it is necessary to know for assessing what fluorescent protein is the most appropriate for a particular application. In this work, we have designed an upper-level, biochemistry laboratory experiment where students measure the fluorescence quantum yields of fluorescent proteins relative to a standard organic dye. Four fluorescent protein variants, enhanced cyan fluorescent protein (ECFP), enhanced green fluorescent protein (EGFP), mCitrine, and mCherry, were used, however the methods described are useful for the characterization of any fluorescent protein or could be expanded to fluorescent quantum yield measurements of organic dye molecules. The laboratory is designed as a guided inquiry project and takes two, 4 hr laboratory periods. During the first day students design the experiment by selecting the excitation wavelength, choosing the standard, and determining the concentration needed for the quantum yield experiment that takes place in the second laboratory period. Overall, this laboratory provides students with a guided inquiry learning experience and introduces concepts of fluorescence biophysics into a biochemistry laboratory curriculum. © 2014 The International Union of Biochemistry and Molecular Biology.

Photochemical redox reactions of copper(II)-alanine complexes in aqueous solutions.

PubMed

Lin, Chen-Jui; Hsu, Chao-Sheng; Wang, Po-Yen; Lin, Yi-Liang; Lo, Yu-Shiu; Wu, Chien-Hou

2014-05-19

The photochemical redox reactions of Cu(II)/alanine complexes have been studied in deaerated solutions over an extensive range of pH, Cu(II) concentration, and alanine concentration. Under irradiation, the ligand-to-metal charge transfer results in the reduction of Cu(II) to Cu(I) and the concomitant oxidation of alanine, which produces ammonia and acetaldehyde. Molar absorptivities and quantum yields of photoproducts for Cu(II)/alanine complexes at 313 nm are characterized mainly with the equilibrium Cu(II) speciation where the presence of simultaneously existing Cu(II) species is taken into account. By applying regression analysis, individual Cu(I) quantum yields are determined to be 0.094 ± 0.014 for the 1:1 complex (CuL) and 0.064 ± 0.012 for the 1:2 complex (CuL2). Individual quantum yields of ammonia are 0.055 ± 0.007 for CuL and 0.036 ± 0.005 for CuL2. Individual quantum yields of acetaldehyde are 0.030 ± 0.007 for CuL and 0.024 ± 0.007 for CuL2. CuL always has larger quantum yields than CuL2, which can be attributed to the Cu(II) stabilizing effect of the second ligand. For both CuL and CuL2, the individual quantum yields of Cu(I), ammonia, and acetaldehyde are in the ratio of 1.8:1:0.7. A reaction mechanism for the formation of the observed photoproducts is proposed.

Cl2O photochemistry: ultraviolet/vis absorption spectrum temperature dependence and O(3P) quantum yield at 193 and 248 nm.

PubMed

Papanastasiou, Dimitrios K; Feierabend, Karl J; Burkholder, James B

2011-05-28

The photochemistry of Cl(2)O (dichlorine monoxide) was studied using measurements of its UV/vis absorption spectrum temperature dependence and the O((3)P) atom quantum yield, Φ(Cl(2)O)(O)(λ), in its photolysis at 193 and 248 nm. The Cl(2)O UV/vis absorption spectrum was measured over the temperature range 201-296 K between 200 and 500 nm using diode array spectroscopy. Cl(2)O absorption cross sections, σ(Cl(2)O)(λ,T), at temperatures <296 K were determined relative to its well established room temperature values. A wavelength and temperature dependent parameterization of the Cl(2)O spectrum using the sum of six Gaussian functions, which empirically represent transitions from the ground (1)A(1) electronic state to excited states, is presented. The Gaussian functions are found to correlate well with published theoretically calculated vertical excitation energies. O((3)P) quantum yields in the photolysis of Cl(2)O at 193 and 248 nm were measured using pulsed laser photolysis combined with atomic resonance fluorescence detection of O((3)P) atoms. O((3)P) quantum yields were measured to be 0.85 ± 0.15 for 193 nm photolysis at 296 K and 0.20 ± 0.03 at 248 nm, which was also found to be independent of temperature (220-352 K) and pressure (17 and 28 Torr, N(2)). The quoted uncertainties are at the 2σ (95% confidence) level and include estimated systematic errors. ClO radical temporal profiles obtained following the photolysis of Cl(2)O at 248 nm, as reported previously in Feierabend et al. [J. Phys. Chem. A 114, 12052, (2010)], were interpreted to establish a <5% upper-limit for the O + Cl(2) photodissociation channel, which indicates that O((3)P) is primarily formed in the three-body, O + 2Cl, photodissociation channel at 248 nm. The analysis also indirectly provided a Cl atom quantum yield of 1.2 ± 0.1 at 248 nm. The results from this work are compared with previous studies where possible. © 2011 American Institute of Physics

Quantum anonymous voting with unweighted continuous-variable graph states

NASA Astrophysics Data System (ADS)

Guo, Ying; Feng, Yanyan; Zeng, Guihua

2016-08-01

Motivated by the revealing topological structures of continuous-variable graph state (CVGS), we investigate the design of quantum voting scheme, which has serious advantages over the conventional ones in terms of efficiency and graphicness. Three phases are included, i.e., the preparing phase, the voting phase and the counting phase, together with three parties, i.e., the voters, the tallyman and the ballot agency. Two major voting operations are performed on the yielded CVGS in the voting process, namely the local rotation transformation and the displacement operation. The voting information is carried by the CVGS established before hand, whose persistent entanglement is deployed to keep the privacy of votes and the anonymity of legal voters. For practical applications, two CVGS-based quantum ballots, i.e., comparative ballot and anonymous survey, are specially designed, followed by the extended ballot schemes for the binary-valued and multi-valued ballots under some constraints for the voting design. Security is ensured by entanglement of the CVGS, the voting operations and the laws of quantum mechanics. The proposed schemes can be implemented using the standard off-the-shelf components when compared to discrete-variable quantum voting schemes attributing to the characteristics of the CV-based quantum cryptography.

Light propagation and fluorescence quantum yields in liquid scintillators

NASA Astrophysics Data System (ADS)

Buck, C.; Gramlich, B.; Wagner, S.

2015-09-01

For the simulation of the scintillation and Cherenkov light propagation in large liquid scintillator detectors a detailed knowledge about the absorption and emission spectra of the scintillator molecules is mandatory. Furthermore reemission probabilities and quantum yields of the scintillator components influence the light propagation inside the liquid. Absorption and emission properties are presented for liquid scintillators using 2,5-Diphenyloxazole (PPO) and 4-bis-(2-Methylstyryl)benzene (bis-MSB) as primary and secondary wavelength shifter. New measurements of the quantum yields for various aromatic molecules are shown.

The source of stratospheric NO and N2O

NASA Technical Reports Server (NTRS)

Slanger, T. G.

1984-01-01

The photodissociation of O3 was investigated as a possible sources of N2O production in the stratosphere. Photolysis was conducted at 1576 A to generate the excited O2 states that react with N2 to form N2O. At this wavelength, there is a quantum yield of two for prompt production of oygen atoms, which is a consequence of the existence of two photodissociative channels giving comparable yields. One of these channels gives O(D1) and O2(b1sigma(+)subg), with a quantum yield of 0.6, whereas the other results in fragmentation of the O3, with production of three ground state oxygen atoms. The O2(b) is generated with vibrational excitation, and there are comparable populations in levels O to 3. These observations are the first to show O2(b) production from any photodissociative process, and were made under conditions in which the kinetics of vibrationally excited O2(b) can be studied. It appears that O3 photodissociation at 1576 A is not a good system for generating the higher electronic states of O2; it is likely that better results will be obtained at 1930 A.

Chromophore-Based Luminescent Metal–Organic Frameworks as Lighting Phosphors

DOE PAGES

Lustig, William P.; Wang, Fangming; Teat, Simon J.; ...

2016-05-31

Here, energy-efficient solid-state-lighting (SSL) technologies are rapidly developing, but the lack of stable, high-performance rare-earth free phosphors may impede the growth of the SSL market. One possible alternative is organic phosphor materials, but these can suffer from lower quantum yields and thermal instability compared to rare-earth phosphors. However, if luminescent organic chromophores can be built into a rigid metal-organic framework, their quantum yields and thermal stability can be greatly improved. This Forum Article discusses the design of a group of such chromophore-based luminescent metal-organic frameworks with exceptionally high performance and rational control of the important parameters that influence their emissionmore » properties, including electronic structures of chromophore, coligands, metal ions, and guest molecule s.« less

Quantum mechanics: The Bayesian theory generalized to the space of Hermitian matrices

NASA Astrophysics Data System (ADS)

Benavoli, Alessio; Facchini, Alessandro; Zaffalon, Marco

2016-10-01

We consider the problem of gambling on a quantum experiment and enforce rational behavior by a few rules. These rules yield, in the classical case, the Bayesian theory of probability via duality theorems. In our quantum setting, they yield the Bayesian theory generalized to the space of Hermitian matrices. This very theory is quantum mechanics: in fact, we derive all its four postulates from the generalized Bayesian theory. This implies that quantum mechanics is self-consistent. It also leads us to reinterpret the main operations in quantum mechanics as probability rules: Bayes' rule (measurement), marginalization (partial tracing), independence (tensor product). To say it with a slogan, we obtain that quantum mechanics is the Bayesian theory in the complex numbers.

Intermediate quantum maps for quantum computation

NASA Astrophysics Data System (ADS)

Giraud, O.; Georgeot, B.

2005-10-01

We study quantum maps displaying spectral statistics intermediate between Poisson and Wigner-Dyson. It is shown that they can be simulated on a quantum computer with a small number of gates, and efficiently yield information about fidelity decay or spectral statistics. We study their matrix elements and entanglement production and show that they converge with time to distributions which differ from random matrix predictions. A randomized version of these maps can be implemented even more economically and yields pseudorandom operators with original properties, enabling, for example, one to produce fractal random vectors. These algorithms are within reach of present-day quantum computers.

Practical characterization of quantum devices without tomography

NASA Astrophysics Data System (ADS)

Landon-Cardinal, Olivier; Flammia, Steven; Silva, Marcus; Liu, Yi-Kai; Poulin, David

2012-02-01

Quantum tomography is the main method used to assess the quality of quantum information processing devices, but its complexity presents a major obstacle for the characterization of even moderately large systems. Part of the reason for this complexity is that tomography generates much more information than is usually sought. Taking a more targeted approach, we develop schemes that enable (i) estimating the ?delity of an experiment to a theoretical ideal description, (ii) learning which description within a reduced subset best matches the experimental data. Both these approaches yield a signi?cant reduction in resources compared to tomography. In particular, we show how to estimate the ?delity between a predicted pure state and an arbitrary experimental state using only a constant number of Pauli expectation values selected at random according to an importance-weighting rule. In addition, we propose methods for certifying quantum circuits and learning continuous-time quantum dynamics that are described by local Hamiltonians or Lindbladians.

Combined atomic force microscopy and photoluminescence imaging to select single InAs/GaAs quantum dots for quantum photonic devices.

PubMed

Sapienza, Luca; Liu, Jin; Song, Jin Dong; Fält, Stefan; Wegscheider, Werner; Badolato, Antonio; Srinivasan, Kartik

2017-07-24

We report on a combined photoluminescence imaging and atomic force microscopy study of single, isolated self-assembled InAs quantum dots. The motivation of this work is to determine an approach that allows to assess single quantum dots as candidates for quantum nanophotonic devices. By combining optical and scanning probe characterization techniques, we find that single quantum dots often appear in the vicinity of comparatively large topographic features. Despite this, the quantum dots generally do not exhibit significant differences in their non-resonantly pumped emission spectra in comparison to quantum dots appearing in defect-free regions, and this behavior is observed across multiple wafers produced in different growth chambers. Such large surface features are nevertheless a detriment to applications in which single quantum dots are embedded within nanofabricated photonic devices: they are likely to cause large spectral shifts in the wavelength of cavity modes designed to resonantly enhance the quantum dot emission, thereby resulting in a nominally perfectly-fabricated single quantum dot device failing to behave in accordance with design. We anticipate that the approach of screening quantum dots not only based on their optical properties, but also their surrounding surface topographies, will be necessary to improve the yield of single quantum dot nanophotonic devices.

Unusually high fluorescence quantum yield of a homopolyfluorenylazomethine--towards a universal fluorophore.

PubMed

Mallet, Charlotte; Bolduc, Andréanne; Bishop, Sophie; Gautier, Yohan; Skene, W G

2014-11-28

The absolute fluorescence quantum yield (Φfl) of a polyfluorenyl azomethine homopolymer was measured as a function of solvent polarity. The solvent induced and temperature dependent fluorescence of the homopolymer were also investigated and they were compared to the corresponding monomer and copolymer. The Φfl of the homopolymer was consistent (45-70%), regardless of solvent polarity with Stokes shifts up to 7460 cm(-1) in ethanol. In contrast, the Φfl of its corresponding monomer decreased from 60% in ethanol to 1% in toluene, whereas a Φfl < 5% for its analogous copolymer was measured. Moderate fluorescence yields (Φfl ≈ 25%) were also possible in thin film when co-depositing the homopolymer with PMMA. Cryofluorescence was used to probe the excited state deactivation modes. Deactivation by internal conversion was found to compete with fluorescence. The fluorescence deactivation pathways of the homopolymer and its corresponding monomer could be suppressed at 77 K, resulting in fluorescence turn-on. Both fluorophores were found to detect nitroaromatics.

Poly(vinylpyrrolidone) supported copper nanoclusters: glutathione enhanced blue photoluminescence for application in phosphor converted light emitting devices

NASA Astrophysics Data System (ADS)

Wang, Zhenguang; Susha, Andrei S.; Chen, Bingkun; Reckmeier, Claas; Tomanec, Ondrej; Zboril, Radek; Zhong, Haizheng; Rogach, Andrey L.

2016-03-01

Poly(vinylpyrrolidone) supported Cu nanoclusters were synthesized by reduction of Cu(ii) ions with ascorbic acid in water, and initially showed blue photoluminescence with a quantum yield of 8%. An enhancement of the emission quantum yield has been achieved by treatment of Cu clusters with different electron-rich ligands, with the most pronounced effect (photoluminescence quantum yield of 27%) achieved with glutathione. The bright blue emission of glutathione treated Cu NCs is fully preserved in the solid state powder, which has been combined with commercial green and red phosphors to fabricate down-conversion white light emitting diodes with a high colour rendering index of 92.Poly(vinylpyrrolidone) supported Cu nanoclusters were synthesized by reduction of Cu(ii) ions with ascorbic acid in water, and initially showed blue photoluminescence with a quantum yield of 8%. An enhancement of the emission quantum yield has been achieved by treatment of Cu clusters with different electron-rich ligands, with the most pronounced effect (photoluminescence quantum yield of 27%) achieved with glutathione. The bright blue emission of glutathione treated Cu NCs is fully preserved in the solid state powder, which has been combined with commercial green and red phosphors to fabricate down-conversion white light emitting diodes with a high colour rendering index of 92. Electronic supplementary information (ESI) available: The optical spectra of control experiments for Cu NC synthesis, optimization of the reaction conditions, and spectra for LEDs chips and blue LEDs. See DOI: 10.1039/c6nr00806b

Single-particle tracking of quantum dot-conjugated prion proteins inside yeast cells

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

Tsuji, Toshikazu; Kawai-Noma, Shigeko; Pack, Chan-Gi

2011-02-25

Research highlights: {yields} We develop a method to track a quantum dot-conjugated protein in yeast cells. {yields} We incorporate the conjugated quantum dot proteins into yeast spheroplasts. {yields} We track the motions by conventional or 3D tracking microscopy. -- Abstract: Yeast is a model eukaryote with a variety of biological resources. Here we developed a method to track a quantum dot (QD)-conjugated protein in the budding yeast Saccharomyces cerevisiae. We chemically conjugated QDs with the yeast prion Sup35, incorporated them into yeast spheroplasts, and tracked the motions by conventional two-dimensional or three-dimensional tracking microscopy. The method paves the way towardmore » the individual tracking of proteins of interest inside living yeast cells.« less

Analytic continuation of quantum Monte Carlo data by stochastic analytical inference.

PubMed

Fuchs, Sebastian; Pruschke, Thomas; Jarrell, Mark

2010-05-01

We present an algorithm for the analytic continuation of imaginary-time quantum Monte Carlo data which is strictly based on principles of Bayesian statistical inference. Within this framework we are able to obtain an explicit expression for the calculation of a weighted average over possible energy spectra, which can be evaluated by standard Monte Carlo simulations, yielding as by-product also the distribution function as function of the regularization parameter. Our algorithm thus avoids the usual ad hoc assumptions introduced in similar algorithms to fix the regularization parameter. We apply the algorithm to imaginary-time quantum Monte Carlo data and compare the resulting energy spectra with those from a standard maximum-entropy calculation.

High-fidelity gates in quantum dot spin qubits

PubMed Central

Koh, Teck Seng; Coppersmith, S. N.; Friesen, Mark

2013-01-01

Several logical qubits and quantum gates have been proposed for semiconductor quantum dots controlled by voltages applied to top gates. The different schemes can be difficult to compare meaningfully. Here we develop a theoretical framework to evaluate disparate qubit-gating schemes on an equal footing. We apply the procedure to two types of double-dot qubits: the singlet–triplet and the semiconducting quantum dot hybrid qubit. We investigate three quantum gates that flip the qubit state: a DC pulsed gate, an AC gate based on logical qubit resonance, and a gate-like process known as stimulated Raman adiabatic passage. These gates are all mediated by an exchange interaction that is controlled experimentally using the interdot tunnel coupling g and the detuning ϵ, which sets the energy difference between the dots. Our procedure has two steps. First, we optimize the gate fidelity (f) for fixed g as a function of the other control parameters; this yields an that is universal for different types of gates. Next, we identify physical constraints on the control parameters; this yields an upper bound that is specific to the qubit-gate combination. We show that similar gate fidelities should be attainable for singlet-triplet qubits in isotopically purified Si, and for hybrid qubits in natural Si. Considerably lower fidelities are obtained for GaAs devices, due to the fluctuating magnetic fields ΔB produced by nuclear spins. PMID:24255105

Efficient Generation of Chemiluminescence during the reduction of manganese(IV) ions with lactic acid

NASA Astrophysics Data System (ADS)

Tsaplev, Yu. B.

2016-12-01

The kinetics and mechanism of chemiluminescence during the reduction of manganese(IV) ions with lactic acid in an H2SO4-AcOH medium are studied. Kinetic spectrophotometric measurements are used to determine the profiles of change in the concentrations of Mn(IV) and Mn(III) ions during the reaction. The results from kinetic spectrophotometric measurements are compared to the light yield kinetics. The quantum chemiluminescence and chemiexcitation yields reach record values.

Photoelectric Effect: Back to Basics.

ERIC Educational Resources Information Center

Powell, R. A.

1978-01-01

Presents a simplified theoretical analysis of the variation of quantum yield with photon energy in the photoelectric experiment. Describes a way to amplify the experiment and make it more instructive to advanced students through the measurement of quantum yield of a photo cell. (GA)

DETERMINATION OF APPARENT QUANTUM YIELD SPECTRA FOR THE FORMATION OF BIOLOGICALLY LABILE PHOTOPRODUCTS

EPA Science Inventory

Quantum yield spectra for the photochemical formation of biologically labile photoproducts from dissolved organic matter (DOM) have not been available previously, although they would greatly facilitate attempts to model photoproduct formation rates across latitudinal, seasonal, a...

Terahertz cascades from nanoparticles

NASA Astrophysics Data System (ADS)

Arnardottir, K. B.; Liew, T. C. H.

2018-05-01

In this article we propose a system capable of terahertz (THz) radiation with quantum yield above unity. The system consists of nanoparticles where the material composition varies along the radial direction of each nanoparticle in such a way that a ladder of equidistant energy levels emerges. By then exciting the highest level of this ladder we produce multiple photons of the same frequency in the THz range. We demonstrate how we can calculate a continuous material composition profile that achieves a high quantum yield and then show that a more experimentally friendly design of a multishell nanoparticle can still result in a high quantum yield.

Photo-kinetics of photoinduced transformation reaction of methylene green with titanium trichloride in different solvents

NASA Astrophysics Data System (ADS)

Nadeem, Syed Muhammad Saqib; Saeed, Rehana

2017-08-01

The photo-kinetics of photoinduced transformation reaction of methylene green and titanium trichloride was investigated in water and different aqueous-alcoholic solvents. The reaction is pseudo-first order, dependent only on the concentration of titanium trichloride at fixed concentration of methylene green. The effect of water and aqueous-alcoholic solvents was studied in the acidic range from 4 to 7. It was observed that the quantum yield (φ) of reaction increased with increase in polarity of the solvent. The quantum yield (φ) was high in acidic condition and decreased with further increase in acidity. The quantum yield (φ) increased sharply with increase in concentration of titanium trichloride while it almost remained unaffected by change in concentration of methylene green. The addition of ions increased the quantum yield (φ) of reaction. The increase in temperature decreased the rate and quantum yield (φ) of reaction. An electron transfer mechanism for the reaction has been proposed in accordance with the kinetics of reaction. The absence of any reaction intermediate was confirmed by spectroscopic investigations. Activation energy ( E a) was calculated by Arrhenius relation. Thermodynamic parameters such as activation energy ( E a), enthalpy change (Δ H), free energy change (Δ G) and entropy change (Δ S) were also evaluated.

Fluorescence quantum yield of carbon dioxide for quantitative UV laser-induced fluorescence in high-pressure flames

NASA Astrophysics Data System (ADS)

Lee, T.; Bessler, W. G.; Yoo, J.; Schulz, C.; Jeffries, J. B.; Hanson, R. K.

2008-11-01

The fluorescence quantum yield for ultraviolet laser-induced fluorescence of CO2 is determined for selected excitation wavelengths in the range 215-250 nm. Wavelength-resolved laser-induced fluorescence (LIF) spectra of CO2, NO, and O2 are measured in the burned gases of a laminar CH4/air flame ( φ=0.9 and 1.1) at 20 bar with additional NO seeded into the flow. The fluorescence spectra are fit to determine the relative contribution of the three species to infer an estimate of fluorescence quantum yield for CO2 that ranges from 2-8×10-6 depending on temperature and excitation wavelength with an estimated uncertainty of ±0.5×10-6. The CO2 fluorescence signal increases linearly with gas pressure for flames with constant CO2 mole fraction for the 10 to 60 bar range, indicating that collisional quenching is not an important contributor to the CO2 fluorescence quantum yield. Spectral simulation calculations are used to choose two wavelengths for excitation of CO2, 239.34 and 242.14 nm, which minimize interference from LIF of NO and O2. Quantitative LIF images of CO2 are demonstrated using these two excitation wavelengths and the measured fluorescence quantum yield.

Control of the external photoluminescent quantum yield of emitters coupled to nanoantenna phased arrays

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

Guo, Ke; Verschuuren, Marc A.; Lozano, Gabriel

2015-08-21

Optical losses in metals represent the largest limitation to the external quantum yield of emitters coupled to plasmonic antennas. These losses can be at the emission wavelength, but they can be more important at shorter wavelengths, i.e., at the excitation wavelength of the emitters, where the conductivity of metals is usually lower. We present accurate measurements of the absolute external photoluminescent quantum yield of a thin layer of emitting material deposited over a periodic nanoantenna phased array. Emission and absorptance measurements of the sample are performed using a custom-made setup including an integrating sphere and variable angle excitation. The measurementsmore » reveal a strong dependence of the external quantum yield on the angle at which the optical field excites the sample. Such behavior is attributed to the coupling between far-field illumination and near-field excitation mediated by the collective resonances supported by the array. Numerical simulations confirm that the inherent losses associated with the metal can be greatly reduced by selecting an optimum angle of illumination, which boosts the light conversion efficiency in the emitting layer. This combined experimental and numerical characterization of the emission from plasmonic arrays reveals the need to carefully design the illumination to achieve the maximum external quantum yield.« less

Efficient Carrier Multiplication in Colloidal Silicon Nanorods

DOE PAGES

Stolle, Carl Jackson; Lu, Xiaotang; Yu, Yixuan; ...

2017-08-01

In this study, auger recombination lifetimes, absorption cross sections, and the quantum yields of carrier multiplication (CM), or multiexciton generation (MEG), were determined for solvent-dispersed silicon (Si) nanorods using transient absorption spectroscopy (TAS). Nanorods with an average diameter of 7.5 nm and aspect ratios of 6.1, 19.3, and 33.2 were examined. Colloidal Si nanocrystals of similar diameters were also studied for comparison. The nanocrystals and nanorods were passivated with organic ligands by hydrosilylation to prevent surface oxidation and limit the effects of surface trapping of photoexcited carriers. All samples used in the study exhibited relatively efficient photoluminescence. The Auger lifetimesmore » increased with nanorod length, and the nanorods exhibited higher CM quantum yield and efficiency than the nanocrystals with a similar band gap energy E g. Beyond a critical length, the CM quantum yield decreases. Finally, nanorods with the aspect ratio of 19.3 had the highest CM quantum yield of 1.6 ± 0.2 at 2.9E g, which corresponded to a multiexciton yield that was twice as high as observed for the spherical nanocrystals.« less

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

Stolle, Carl Jackson; Lu, Xiaotang; Yu, Yixuan

In this study, auger recombination lifetimes, absorption cross sections, and the quantum yields of carrier multiplication (CM), or multiexciton generation (MEG), were determined for solvent-dispersed silicon (Si) nanorods using transient absorption spectroscopy (TAS). Nanorods with an average diameter of 7.5 nm and aspect ratios of 6.1, 19.3, and 33.2 were examined. Colloidal Si nanocrystals of similar diameters were also studied for comparison. The nanocrystals and nanorods were passivated with organic ligands by hydrosilylation to prevent surface oxidation and limit the effects of surface trapping of photoexcited carriers. All samples used in the study exhibited relatively efficient photoluminescence. The Auger lifetimesmore » increased with nanorod length, and the nanorods exhibited higher CM quantum yield and efficiency than the nanocrystals with a similar band gap energy E g. Beyond a critical length, the CM quantum yield decreases. Finally, nanorods with the aspect ratio of 19.3 had the highest CM quantum yield of 1.6 ± 0.2 at 2.9E g, which corresponded to a multiexciton yield that was twice as high as observed for the spherical nanocrystals.« less

In situ intercalation strategies for device-quality hybrid inorganic-organic self-assembled quantum wells

NASA Astrophysics Data System (ADS)

Pradeesh, K.; Baumberg, J. J.; Prakash, G. Vijaya

2009-07-01

Thin films of self-organized quantum wells of inorganic-organic hybrid perovskites of (C6H9C2H4NH3)2PbI4 are formed from a simple intercalation strategy to yield well-ordered uniform films over centimeter-size scales. These films compare favorably with traditional solution-chemistry-synthesized thin films. The hybrid films show strong room-temperature exciton-related absorption and photoluminescence, which shift with fabrication protocol. We demonstrate the potential of this method for electronic and photonic device applications.

Optical characterization of Nd (3+):AgBr.

PubMed

Bunimovich, D; Nagli, L; Katzir, A

1997-10-20

The luminescence of silver bromide crystals, doped with neodymium, was investigated over the visible and near-infrared spectral ranges. The emission, excitation, and absorption spectra were measured over a broad temperature range. The absolute luminescence quantum yield was estimated by comparing the luminescence with that of a neodymium-doped phosphate glass, for which the manufacturer gives a value of 0.4. The Judd-Ofelt analysis was applied to both materials, and transition rates, branching ratios, and quantum efficiencies were calculated for all the observed bands. Good agreement was obtained between theory and experiment.

Effects of Bleaching by Nitrogen Deficiency on the Quantum Yield of Photosystem II in Synechocystis sp. PCC 6803 Revealed by Chl Fluorescence Measurements.

PubMed

Ogawa, Takako; Sonoike, Kintake

2016-03-01

Estimation of photosynthesis by Chl fluorescence measurement of cyanobacteria is always problematic due to the interference from respiratory electron transfer and from phycocyanin fluorescence. The interference from respiratory electron transfer could be avoided by the use of DCMU or background illumination by blue light, which oxidizes the plastoquinone pool that tends to be reduced by respiration. On the other hand, the precise estimation of photosynthesis in cells with a different phycobilisome content by Chl fluorescence measurement is difficult. By subtracting the basal fluorescence due to the phycobilisome and PSI, it becomes possible to estimate the precise maximum quantum yield of PSII in cyanobacteria. Estimated basal fluorescence accounted for 60% of the minimum fluorescence, resulting in a large difference between the 'apparent' yield and 'true' yield under high phycocyanin conditions. The calculated value of the 'true' maximum quantum yield of PSII was around 0.8, which was similar to the value observed in land plants. The results suggest that the cause of the apparent low yield reported in cyanobacteria is mainly ascribed to the interference from phycocyanin fluorescence. We also found that the 'true' maximum quantum yield of PSII decreased under nitrogen-deficient conditions, suggesting the impairment of the PSII reaction center, while the 'apparent' maximum quantum yield showed a marginal change under the same conditions. Due to the high contribution of phycocyanin fluorescence in cyanobacteria, it is essential to eliminate the influence of the change in phycocyanin content on Chl fluorescence measurement and to evaluate the 'true' photosynthetic condition. © The Author 2016. Published by Oxford University Press on behalf of Japanese Society of Plant Physiologists. All rights reserved. For permissions, please email: journals.permissions@oup.com.

Improved photoluminescence quantum yield and stability of CdSe-TOP, CdSe-ODA-TOPO, CdSe/CdS and CdSe/EP nanocomposites

NASA Astrophysics Data System (ADS)

Wei, Shutian; Zhu, Zhilin; Wang, Zhixiao; Wei, Gugangfen; Wang, Pingjian; Li, Hai; Hua, Zhen; Lin, Zhonghai

2016-07-01

Size-controllable monodisperse CdSe nanocrystals with different organic capping were prepared based on the hot-injection method. The effective separation of nucleation and growth was achieved by rapidly mixing two highly reactive precursors. As a contrast, we prepared CdSe/CdS nanocrystals (NCs) successfully based on the selective ion layer adsorption and reaction (SILAR) technique. This inorganic capping obtained higher photoluminescence quantum yield (PLQY) of 59.3% compared with organic capping of 40.8%. Furthermore, the CdSe-epoxy resin (EP) composites were prepared by adopting a flexible ex situ method, and showed excellent stability in the ambient environment for one year. So the composites with both high PLQY of nanocrystals and excellent stability are very promising to device application.

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

Galperin, Michael

The progress of experimental techniques at the nanoscale in the last decade made optical measurements in current-carrying nanojunctions a reality, thus indicating the emergence of a new field of research coined optoelectronics. Optical spectroscopy of open nonequilibrium systems is a natural meeting point for (at least) two research areas: nonlinear optical spectroscopy and quantum transport, each with its own theoretical toolbox. We review recent progress in the field comparing theoretical treatments of optical response in nanojunctions as is accepted in nonlinear spectroscopy and quantum transport communities. A unified theoretical description of spectroscopy in nanojunctions is presented. Here, we argue thatmore » theoretical approaches of the quantum transport community (and in particular, the Green function based considerations) yield a convenient tool for optoelectronics when the radiation field is treated classically, and that differences between the toolboxes may become critical when studying the quantum radiation field in junctions.« less

High quantum-yield phosphors via quantum splitting and upconversion

NASA Astrophysics Data System (ADS)

Jeong, Joayoung

The Gd3+ ion has been used to induce quantum splitting in luminescent materials by using cross-relaxation energy transfer (CRET). In Nd:LiGdF4, quantum splitting results from a two-step CRET between Gd3+ and Nd3+, first involving a transition 6G→6I on Gd3+ and an excitation within the 4f3 configuration of Nd3+ followed by a second CRET that brings Gd3+ to 6P7/2. The excited Nd3+ ion rapidly relaxes nonradiatively to the emitting 4F3/2. The excited Gd3+ ion then transfers its energy back to Nd3+, which gives rise to the second photon. The result is a quantum yield of 1.05 +/- 0.35 with emission in the NIR following excitation at 175 nm. GdF3:Pr3+, Eu 3+ also exhibits quantum splitting, but only at very low concentration of Pr3+ (0.3%) and Eu3+ (0.2%), resulting in a quantum yield of approximately 20% under 160-nm excitation. Host intrinsic emission via a self-trapped exciton (STE) was also examined as a means to sensitize Gd3+ emission. The material ScPO4:Gd 3+ exhibits a high absolute quantum yield of 0.9 +/- 0.2 under 170-nm excitation, demonstrating a potentially new and efficient pathway for exciting quantum splitting phosphors. Single crystals of the material GdZrF7 were grown, and its structure was established via single-crystal X-ray diffraction methods. Doped samples of GdZrF7:Yb3+, Er3+ exhibit bright up-conversion luminescence with light output that is up to twice that of a commercial material based on the host Gd2O2S. When doped with Eu3+, the fluoride also emits a nearly white color under vacuum ultraviolet excitation with an absolute quantum yield near 0.9. The new compound Gd4.67(SiO4)3S was synthesized and studied. The structure was established via single-crystal X-ray methods, and the luminescence of Tb3+ samples was investigated.

Photoactive High Explosives: Substituents Effects on Tetrazine Photochemistry and Photophysics

DOE PAGES

McGrane, Shawn David; Bolme, Cynthia Anne; Greenfield, Margo Torello; ...

2016-01-21

High explosives that are photoactive, i.e., can be initiated with light, offer significant advantages in reduced potential for accidental electrical initiation. In this study, we examined a series of structurally related tetrazine based photoactive high explosive materials to detail their photochemical and photophysical properties. Using photobleaching infrared absorption, we determined quantum yields of photochemistry for nanosecond pulsed excitation at 355 and 532 nm. Changes in mass spectrometry during laser irradiation in vacuum measured the evolution of gaseous products. Fluorescence spectra, quantum yields, and lifetimes were measured to observe radiative channels of energy decay that compete with photochemistry. For the 6more » materials studied, quantum yields of photochemistry ranged from <10 –5 to 0.03 and quantum yield of fluorescence ranged from <10 –3 to 0.33. In all cases, the photoexcitation nonradiatively relaxed primarily to heat, appropriate for supporting photothermal initiation processes. Lastly, the photochemistry observed was dominated by ring scission of the tetrazine, but there was evidence of more extensive multistep reactions as well.« less

Optomechanical Control of Quantum Yield in Trans-Cis Ultrafast Photoisomerization of a Retinal Chromophore Model.

PubMed

Valentini, Alessio; Rivero, Daniel; Zapata, Felipe; García-Iriepa, Cristina; Marazzi, Marco; Palmeiro, Raúl; Fdez Galván, Ignacio; Sampedro, Diego; Olivucci, Massimo; Frutos, Luis Manuel

2017-03-27

The quantum yield of a photochemical reaction is one of the most fundamental quantities in photochemistry, as it measures the efficiency of the transduction of light energy into chemical energy. Nature has evolved photoreceptors in which the reactivity of a chromophore is enhanced by its molecular environment to achieve high quantum yields. The retinal chromophore sterically constrained inside rhodopsin proteins represents an outstanding example of such a control. In a more general framework, mechanical forces acting on a molecular system can strongly modify its reactivity. Herein, we show that the exertion of tensile forces on a simplified retinal chromophore model provokes a substantial and regular increase in the trans-to-cis photoisomerization quantum yield in a counterintuitive way, as these extension forces facilitate the formation of the more compressed cis photoisomer. A rationale for the mechanochemical effect on this photoisomerization mechanism is also proposed. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Accuracy of quantum sensors measuring yield photon flux and photosynthetic photon flux

NASA Technical Reports Server (NTRS)

Barnes, C.; Tibbitts, T.; Sager, J.; Deitzer, G.; Bubenheim, D.; Koerner, G.; Bugbee, B.; Knott, W. M. (Principal Investigator)

1993-01-01

Photosynthesis is fundamentally driven by photon flux rather than energy flux, but not all absorbed photons yield equal amounts of photosynthesis. Thus, two measures of photosynthetically active radiation have emerged: photosynthetic photon flux (PPF), which values all photons from 400 to 700 nm equally, and yield photon flux (YPF), which weights photons in the range from 360 to 760 nm according to plant photosynthetic response. We selected seven common radiation sources and measured YPF and PPF from each source with a spectroradiometer. We then compared these measurements with measurements from three quantum sensors designed to measure YPF, and from six quantum sensors designed to measure PPF. There were few differences among sensors within a group (usually <5%), but YPF values from sensors were consistently lower (3% to 20%) than YPF values calculated from spectroradiometric measurements. Quantum sensor measurements of PPF also were consistently lower than PPF values calculated from spectroradiometric measurements, but the differences were <7% for all sources, except red-light-emitting diodes. The sensors were most accurate for broad-band sources and least accurate for narrow-band sources. According to spectroradiometric measurements, YPF sensors were significantly less accurate (>9% difference) than PPF sensors under metal halide, high-pressure sodium, and low-pressure sodium lamps. Both sensor types were inaccurate (>18% error) under red-light-emitting diodes. Because both YPF and PPF sensors are imperfect integrators, and because spectroradiometers can measure photosynthetically active radiation much more accurately, researchers should consider developing calibration factors from spectroradiometric data for some specific radiation sources to improve the accuracy of integrating sensors.

Comment on "Comparative study of ab initio nonradiative recombination rate calculations under different formalisms"

NASA Astrophysics Data System (ADS)

Wickramaratne, Darshana; Shen, Jimmy-Xuan; Alkauskas, Audrius; Van de Walle, Chris G.

2018-02-01

In a recent article [Phys. Rev. B 91, 205315 (2015), 10.1103/PhysRevB.91.205315] Shi, Xu, and Wang presented a comparison of several formalisms to calculate nonradiative recombination rates and concluded the "one-dimensional (1D) quantum formula" that was used by Alkauskas et al. [Phys. Rev. B 90, 075202 (2014), 10.1103/PhysRevB.90.075202] is insufficient to accurately describe nonradiative capture rates. Our analysis of the results of Shi, Xu, and Wang indicates that their conclusions about the 1D quantum formula are unfounded and stem from an error in their calculations. Our own calculations demonstrate that the 1D quantum formula approach yields reliable and accurate results for nonradiative recombination rates.

Photosynthetic Physiological Response of Radix Isatidis (Isatis indigotica Fort.) Seedlings to Nicosulfuron

PubMed Central

Ning, Na; Wen, Yinyuan; Dong, Shuqi; Yin, Meiqiang; Guo, Meijun; Wang, Binqiang; Feng, Lei; Guo, Pingyi

2014-01-01

Radix Isatidis (Isatis indigotica Fort.) is one of the most important traditional Chinese medicine plants. However, there is no suitable herbicide used for weed control in Radix Isatidis field during postemergence stage. To explore the safety of sulfonylurea herbicide nicosulfuron on Radix Isatidis (Isatis indigotica Fort.) seedlings and the photosynthetic physiological response of the plant to the herbicide, biological mass, leaf area, photosynthetic pigment content, photosynthetic rate, chlorophyll fluorescence characteristics, and P700 parameters of Radix Isatidis seedlings were analyzed 10 d after nicosulfuron treatment at 5th leaf stage in this greenhouse research. The results showed that biological mass, total chlorophyll, chlorophyll a, and carotenoids content, photosynthetic rate, stomatal conductance, PS II maximum quantum yield, PS II effective quantum yield, PS II electron transport rate, photochemical quenching, maximal P700 change, photochemical quantum yield of PS I, and PS I electron transport rate decreased with increasing herbicide concentrations, whereas initial fluorescence, quantum yield of non-regulated energy dissipation in PS II and quantum yield of non-photochemical energy dissipation due to acceptor side limitation in PS I increased. It suggests that nicosulfuron ≥1 mg L−1 causes the damage of chloroplast, PS II and PS I structure. Electron transport limitations in PS I receptor side, and blocked dark reaction process may be the main cause of the significantly inhibited growth and decreased photosynthetic rate of Radix Isatidis seedlings. PMID:25165819

Silicon Nanoparticles with Surface Nitrogen: 90% Quantum Yield with Narrow Luminescence Bandwidth and the Ligand Structure Based Energy Law.

PubMed

Li, Qi; Luo, Tian-Yi; Zhou, Meng; Abroshan, Hadi; Huang, Jingchun; Kim, Hyung J; Rosi, Nathaniel L; Shao, Zhengzhong; Jin, Rongchao

2016-09-27

Silicon nanoparticles (NPs) have been widely accepted as an alternative material for typical quantum dots and commercial organic dyes in light-emitting and bioimaging applications owing to silicon's intrinsic merits of least toxicity, low cost, and high abundance. However, to date, how to improve Si nanoparticle photoluminescence (PL) performance (such as ultrahigh quantum yield, sharp emission peak, high stability) is still a major issue. Herein, we report surface nitrogen-capped Si NPs with PL quantum yield up to 90% and narrow PL bandwidth (full width at half-maximum (fwhm) ≈ 40 nm), which can compete with commercial dyes and typical quantum dots. Comprehensive studies have been conducted to unveil the influence of particle size, structure, and amount of surface ligand on the PL of Si NPs. Especially, a general ligand-structure-based PL energy law for surface nitrogen-capped Si NPs is identified in both experimental and theoretical analyses, and the underlying PL mechanisms are further discussed.

Fluorescence Imaging Assisted Photodynamic Therapy Using Photosensitizer-Linked Gold Quantum Clusters.

PubMed

Nair, Lakshmi V; Nazeer, Shaiju S; Jayasree, Ramapurath S; Ajayaghosh, Ayyappanpillai

2015-06-23

Fluorescence imaging assisted photodynamic therapy (PDT) is a viable two-in-one clinical tool for cancer treatment and follow-up. While the surface plasmon effect of gold nanorods and nanoparticles has been effective for cancer therapy, their emission properties when compared to gold nanoclusters are weak for fluorescence imaging guided PDT. In order to address the above issues, we have synthesized a near-infrared-emitting gold quantum cluster capped with lipoic acid (L-AuC with (Au)18(L)14) based nanoplatform with excellent tumor reduction property by incorporating a tumor-targeting agent (folic acid) and a photosensitizer (protoporphyrin IX), for selective PDT. The synthesized quantum cluster based photosensitizer PFL-AuC showed 80% triplet quantum yield when compared to that of the photosensitizer alone (63%). PFL-AuC having 60 μg (0.136 mM) of protoporphyrin IX was sufficient to kill 50% of the tumor cell population. Effective destruction of tumor cells was evident from the histopathology and fluorescence imaging, which confirm the in vivo PDT efficacy of PFL-AuC.

Do the cations in clay and the polymer matrix affect quantum dot fluorescent properties?

PubMed

Wei, Wenjun; Liu, Cui; Liu, Jiyan; Liu, Xueqing; Zou, Linling; Cai, Shaojun; Shi, Hong; Cao, Yuan-Cheng

2016-06-01

This paper studied the effects of cations and polymer matrix on the fluorescent properties of quantum dots (QDs). The results indicated that temperature has a greater impact on fluorescence intensity than clay cations (mainly K(+) and Na(+) ). Combined fluorescence lifetime and steady-state spectrometer tests showed that QD lifetimes all decreased when the cation concentration was increased, but the quantum yields were steady at various cation concentrations of 0, 0.05, 0.5 and 1 M. Poly(ethylene oxide) (PEO), poly(vinyl alcohol) (PVA) and diepoxy resin were used to study the effects of polymers on QD lifetime and quantum yield. The results showed that the lifetime for QDs 550 nm in PEO and PVA was 17.33 and 17.12 ns, respectively; for the epoxy resin, the lifetime was 0.74 ns, a sharp decrease from 24.47 ns. The quantum yield for QDs 550 nm changed from 34.22% to 7.45% and 7.81% in PEO and PVA, respectively; for the epoxy resin the quantum yield was 2.25%. QDs 580 nm and 620 nm showed the same results as QDs 550 nm. This study provides useful information on the design, synthesis and application of QDs-polymer luminescent materials. Copyright © 2015 John Wiley & Sons, Ltd. Copyright © 2015 John Wiley & Sons, Ltd.

Action spectra of photosystems II and I and quantum yield of photosynthesis in leaves in State 1.

PubMed

Laisk, Agu; Oja, Vello; Eichelmann, Hillar; Dall'Osto, Luca

2014-02-01

The spectral global quantum yield (YII, electrons/photons absorbed) of photosystem II (PSII) was measured in sunflower leaves in State 1 using monochromatic light. The global quantum yield of PSI (YI) was measured using low-intensity monochromatic light flashes and the associated transmittance change at 810nm. The 810-nm signal change was calibrated based on the number of electrons generated by PSII during the flash (4·O2 evolution) which arrived at the PSI donor side after a delay of 2ms. The intrinsic quantum yield of PSI (yI, electrons per photon absorbed by PSI) was measured at 712nm, where photon absorption by PSII was small. The results were used to resolve the individual spectra of the excitation partitioning coefficients between PSI (aI) and PSII (aII) in leaves. For comparison, pigment-protein complexes for PSII and PSI were isolated, separated by sucrose density ultracentrifugation, and their optical density was measured. A good correlation was obtained for the spectral excitation partitioning coefficients measured by these different methods. The intrinsic yield of PSI was high (yI=0.88), but it absorbed only about 1/3 of quanta; consequently, about 2/3 of quanta were absorbed by PSII, but processed with the low intrinsic yield yII=0.63. In PSII, the quantum yield of charge separation was 0.89 as detected by variable fluorescence Fv/Fm, but 29% of separated charges recombined (Laisk A, Eichelmann H and Oja V, Photosynth. Res. 113, 145-155). At wavelengths less than 580nm about 30% of excitation is absorbed by pigments poorly connected to either photosystem, most likely carotenoids bound in pigment-protein complexes. Copyright © 2013 Elsevier B.V. All rights reserved.

ABSORBANCE, ABSORPTION COEFFICIENT, AND APPARENT QUANTUM YIELD: A COMMENT ON AMBIGUITY IN THE USE OF THESE OPTICAL CONCEPTS

EPA Science Inventory

Several important optical terms such as "absorbance" and "absorption coefficient" are frequently used ambiguously in the current peer-reviewed literature. Since they are important terms that are required to derive other quantities such as the "apparent quantum yield" of photoprod...

High-fidelity gates in quantum dot spin qubits.

PubMed

Koh, Teck Seng; Coppersmith, S N; Friesen, Mark

2013-12-03

Several logical qubits and quantum gates have been proposed for semiconductor quantum dots controlled by voltages applied to top gates. The different schemes can be difficult to compare meaningfully. Here we develop a theoretical framework to evaluate disparate qubit-gating schemes on an equal footing. We apply the procedure to two types of double-dot qubits: the singlet-triplet and the semiconducting quantum dot hybrid qubit. We investigate three quantum gates that flip the qubit state: a DC pulsed gate, an AC gate based on logical qubit resonance, and a gate-like process known as stimulated Raman adiabatic passage. These gates are all mediated by an exchange interaction that is controlled experimentally using the interdot tunnel coupling g and the detuning [Symbol: see text], which sets the energy difference between the dots. Our procedure has two steps. First, we optimize the gate fidelity (f) for fixed g as a function of the other control parameters; this yields an f(opt)(g) that is universal for different types of gates. Next, we identify physical constraints on the control parameters; this yields an upper bound f(max) that is specific to the qubit-gate combination. We show that similar gate fidelities (~99:5%) should be attainable for singlet-triplet qubits in isotopically purified Si, and for hybrid qubits in natural Si. Considerably lower fidelities are obtained for GaAs devices, due to the fluctuating magnetic fields ΔB produced by nuclear spins.

Analogues of uracil nucleosides with intrinsic fluorescence (NIF-analogues): synthesis and photophysical properties.

PubMed

Segal, Meirav; Fischer, Bilha

2012-02-28

Uridine cannot be utilized as fluorescent probe due to its extremely low quantum yield. For improving the uracil fluorescence characteristics we extended the natural chromophore at the C5 position by coupling substituted aromatic rings directly or via an alkenyl or alkynyl linker to create fluorophores. Extension of the uracil base was achieved by treating 5-I-uridine with the appropriate boronic acid under the Suzuki coupling conditions. Analogues containing an alkynyl linker were obtained from 5-I-uridine and the suitable boronic acid in a Sonogashira coupling reaction. The uracil fluorescent analogues proposed here were designed to satisfy the following requirements: a minimal chemical modification at a position not involved in base-pairing, resulting in relatively long absorption and emission wavelengths and high quantum yield. 5-((4-Methoxy-phenyl)-trans-vinyl)-2'-deoxy-uridine, 6b, was found to be a promising fluorescent probe. Probe 6b exhibits a quantum yield that is 3000-fold larger than that of the natural chromophore (Φ 0.12), maximum emission (478 nm) which is 170 nm red shifted as compared to uridine, and a Stokes shift of 143 nm. In addition, since probe 6b adopts the anti conformation and S sugar puckering favored by B-DNA, it makes a promising nucleoside analogue to be incorporated in an oligonucleotide probe for detection of genetic material.

Pilot-Wave Hydrodynamics

NASA Astrophysics Data System (ADS)

Bush, John W. M.

2015-01-01

Yves Couder, Emmanuel Fort, and coworkers recently discovered that a millimetric droplet sustained on the surface of a vibrating fluid bath may self-propel through a resonant interaction with its own wave field. This article reviews experimental evidence indicating that the walking droplets exhibit certain features previously thought to be exclusive to the microscopic, quantum realm. It then reviews theoretical descriptions of this hydrodynamic pilot-wave system that yield insight into the origins of its quantum-like behavior. Quantization arises from the dynamic constraint imposed on the droplet by its pilot-wave field, and multimodal statistics appear to be a feature of chaotic pilot-wave dynamics. I attempt to assess the potential and limitations of this hydrodynamic system as a quantum analog. This fluid system is compared to quantum pilot-wave theories, shown to be markedly different from Bohmian mechanics and more closely related to de Broglie's original conception of quantum dynamics, his double-solution theory, and its relatively recent extensions through researchers in stochastic electrodynamics.

Photonics and spectroscopy in nanojunctions: a theoretical insight

DOE PAGES

Galperin, Michael

2017-04-11

The progress of experimental techniques at the nanoscale in the last decade made optical measurements in current-carrying nanojunctions a reality, thus indicating the emergence of a new field of research coined optoelectronics. Optical spectroscopy of open nonequilibrium systems is a natural meeting point for (at least) two research areas: nonlinear optical spectroscopy and quantum transport, each with its own theoretical toolbox. We review recent progress in the field comparing theoretical treatments of optical response in nanojunctions as is accepted in nonlinear spectroscopy and quantum transport communities. A unified theoretical description of spectroscopy in nanojunctions is presented. Here, we argue thatmore » theoretical approaches of the quantum transport community (and in particular, the Green function based considerations) yield a convenient tool for optoelectronics when the radiation field is treated classically, and that differences between the toolboxes may become critical when studying the quantum radiation field in junctions.« less

Long-distance measurement-device-independent quantum key distribution with coherent-state superpositions.

PubMed

Yin, H-L; Cao, W-F; Fu, Y; Tang, Y-L; Liu, Y; Chen, T-Y; Chen, Z-B

2014-09-15

Measurement-device-independent quantum key distribution (MDI-QKD) with decoy-state method is believed to be securely applied to defeat various hacking attacks in practical quantum key distribution systems. Recently, the coherent-state superpositions (CSS) have emerged as an alternative to single-photon qubits for quantum information processing and metrology. Here, in this Letter, CSS are exploited as the source in MDI-QKD. We present an analytical method that gives two tight formulas to estimate the lower bound of yield and the upper bound of bit error rate. We exploit the standard statistical analysis and Chernoff bound to perform the parameter estimation. Chernoff bound can provide good bounds in the long-distance MDI-QKD. Our results show that with CSS, both the security transmission distance and secure key rate are significantly improved compared with those of the weak coherent states in the finite-data case.

Infrared-induced conformational isomerization and vibrational relaxation dynamics in melatonin and 5-methoxy-N-acetyl tryptophan methyl amide

NASA Astrophysics Data System (ADS)

Dian, Brian C.; Florio, Gina M.; Clarkson, Jasper R.; Longarte, Asier; Zwier, Timothy S.

2004-05-01

The conformational isomerization dynamics of melatonin and 5-methoxy N-acetyltryptophan methyl amide (5-methoxy NATMA) have been studied using the methods of IR-UV hole-filling spectroscopy and IR-induced population transfer spectroscopy. Using these techniques, single conformers of melatonin were excited via a well-defined NH stretch fundamental with an IR pump laser. This excess energy was used to drive conformational isomerization. By carrying out the infrared excitation early in a supersonic expansion, the excited molecules were re-cooled into their zero-point levels, partially re-filling the hole created in the ground state population of the excited conformer, and creating gains in population of the other conformers. These changes in population were detected using laser-induced fluorescence downstream in the expansion via an UV probe laser. The isomerization quantum yields for melatonin show some conformation specificity but no hint of vibrational mode specificity. In 5-methoxy NATMA, no isomerization was observed out of the single conformational well populated in the expansion in the absence of the infrared excitation. In order to study the dependence of the isomerization on the cooling rate, the experimental arrangement was modified so that faster cooling conditions could be studied. In this arrangement, the pump and probe lasers were overlapped in space in the high density region of the expansion, and the time dependence of the zero-point level populations of the conformers was probed following selective excitation of a single conformation. The analysis needed to extract isomerization quantum yields from the timing scans was developed and applied to the melatonin timing scans. Comparison between the frequency and time domain isomerization quantum yields under identical experimental conditions produced similar results. Under fast cooling conditions, the product quantum yields were shifted from their values under standard conditions. The results for melatonin are compared with those for N-acetyl tryptophan methyl amide.

Quantum Criticality and Black Holes

ScienceCinema

Sachdev, Subir [Harvard University, Cambridge, Massachusetts, United States

2017-12-09

I will describe the behavior of a variety of condensed matter systems in the vicinity of zero temperature quantum phase transitions. There is a remarkable analogy between the hydrodynamics of such systems and the quantum theory of black holes. I will show how insights from this analogy have shed light on recent experiments on the cuprate high temperature superconductors. Studies of new materials and trapped ultracold atoms are yielding new quantum phases, with novel forms of quantum entanglement. Some materials are of technological importance: e.g. high temperature superconductors. Exact solutions via black hole mapping have yielded first exact results for transport coefficients in interacting many-body systems, and were valuable in determining general structure of hydrodynamics. Theory of VBS order and Nernst effect in cuprates. Tabletop 'laboratories for the entire universe': quantum mechanics of black holes, quark-gluon plasma, neutrons stars, and big-bang physics.

Brightly Luminescent and Color-Tunable Colloidal CH3NH3PbX3 (X = Br, I, Cl) Quantum Dots: Potential Alternatives for Display Technology.

PubMed

Zhang, Feng; Zhong, Haizheng; Chen, Cheng; Wu, Xian-gang; Hu, Xiangmin; Huang, Hailong; Han, Junbo; Zou, Bingsuo; Dong, Yuping

2015-04-28

Organometal halide perovskites are inexpensive materials with desirable characteristics of color-tunable and narrow-band emissions for lighting and display technology, but they suffer from low photoluminescence quantum yields at low excitation fluencies. Here we developed a ligand-assisted reprecipitation strategy to fabricate brightly luminescent and color-tunable colloidal CH3NH3PbX3 (X = Br, I, Cl) quantum dots with absolute quantum yield up to 70% at room temperature and low excitation fluencies. To illustrate the photoluminescence enhancements in these quantum dots, we conducted comprehensive composition and surface characterizations and determined the time- and temperature-dependent photoluminescence spectra. Comparisons between small-sized CH3NH3PbBr3 quantum dots (average diameter 3.3 nm) and corresponding micrometer-sized bulk particles (2-8 μm) suggest that the intense increased photoluminescence quantum yield originates from the increase of exciton binding energy due to size reduction as well as proper chemical passivations of the Br-rich surface. We further demonstrated wide-color gamut white-light-emitting diodes using green emissive CH3NH3PbBr3 quantum dots and red emissive K2SiF6:Mn(4+) as color converters, providing enhanced color quality for display technology. Moreover, colloidal CH3NH3PbX3 quantum dots are expected to exhibit interesting nanoscale excitonic properties and also have other potential applications in lasers, electroluminescence devices, and optical sensors.

Structural Basis for Near Unity Quantum Yield Core/Shell Nanostructures

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

McBride, James; Treadway, Joe; Pennycook, Stephen J

2006-01-01

Aberration-corrected Z-contrast scanning transmission electron microscopy of core/shell nanocrystals shows clear correlations between structure and quantum efficiency. Uniform shell coverage is obtained only for a graded CdS/ZnS shell material and is found to be critical to achieving near 100% quantum yield. The sublattice sensitivity of the images confirms that preferential growth takes place on the anion-terminated surfaces. This explains the three-dimensional "nanobullet" shape observed in the case of core/shell nanorods.

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

Chen Lin; Chen Yixin

We show that no universal quantum cloning machine exists that can broadcast an arbitrary mixed qubit with a constant fidelity. Based on this result, we investigate the dependent quantum cloner in the sense that some parameter of the input qubit {rho}{sub s}({theta},{omega},{lambda}) is regarded as constant in the fidelity. For the case of constant {omega}, we establish the 1{yields}2 optimal symmetric dependent cloner with a fidelity 1/2. It is also shown that the 1{yields}M optimal quantum cloning machine for pure qubits is also optimal for mixed qubits, when {lambda} is the unique parameter in the fidelity. For general N{yields}M broadcastingmore » of mixed qubits, the situation is very different.« less

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

Bisio, Alessandro; D'Ariano, Giacomo Mauro; Perinotti, Paolo

We analyze quantum algorithms for cloning of a quantum measurement. Our aim is to mimic two uses of a device performing an unknown von Neumann measurement with a single use of the device. When the unknown device has to be used before the bipartite state to be measured is available we talk about 1{yields}2 learning of the measurement, otherwise the task is called 1{yields}2 cloning of a measurement. We perform the optimization for both learning and cloning for arbitrary dimension d of the Hilbert space. For 1{yields}2 cloning we also propose a simple quantum network that achieves the optimal fidelity.more » The optimal fidelity for 1{yields}2 learning just slightly outperforms the estimate and prepare strategy in which one first estimates the unknown measurement and depending on the result suitably prepares the duplicate.« less

Transport properties of N2 gas at cryogenic temperatures. [computation of viscosity and thermal conductivity

NASA Technical Reports Server (NTRS)

Pearson, W. E.

1974-01-01

The viscosity and thermal conductivity of nitrogen gas for the temperature range 5 K - 135 K have been computed from the second Chapman-Enskog approximation. Quantum effects, which become appreciable at the lower temperatures, are included by utilizing collision integrals based on quantum theory. A Lennard-Jones (12-6) potential was assumed. The computations yield viscosities about 20 percent lower than those predicted for the high end of this temperature range by the method of corresponding states, but the agreement is excellent when the computed values are compared with existing experimental data.

Triazatruxene: A Rigid Central Donor Unit for a D-A3 Thermally Activated Delayed Fluorescence Material Exhibiting Sub-Microsecond Reverse Intersystem Crossing and Unity Quantum Yield via Multiple Singlet-Triplet State Pairs.

PubMed

Dos Santos, Paloma L; Ward, Jonathan S; Congrave, Daniel G; Batsanov, Andrei S; Eng, Julien; Stacey, Jessica E; Penfold, Thomas J; Monkman, Andrew P; Bryce, Martin R

2018-06-01

By inverting the common structural motif of thermally activated delayed fluorescence materials to a rigid donor core and multiple peripheral acceptors, reverse intersystem crossing (rISC) rates are demonstrated in an organic material that enables utilization of triplet excited states at faster rates than Ir-based phosphorescent materials. A combination of the inverted structure and multiple donor-acceptor interactions yields up to 30 vibronically coupled singlet and triplet states within 0.2 eV that are involved in rISC. This gives a significant enhancement to the rISC rate, leading to delayed fluorescence decay times as low as 103.9 ns. This new material also has an emission quantum yield ≈1 and a very small singlet-triplet gap. This work shows that it is possible to achieve both high photoluminescence quantum yield and fast rISC in the same molecule. Green organic light-emitting diode devices with external quantum efficiency >30% are demonstrated at 76 cd m -2 .

The Effect of Correlated Energetic Disorder on Charge Transport in Organic Semiconductors

NASA Astrophysics Data System (ADS)

Allen, Jonathan; Röding, Sebastian; Cherqui, Charles; Dunlap, David

2012-10-01

In their 1995 paper describing a Monte Carlo simulation for dissociation of an electron-hole pair in the presence of Gaussian energetic disorder, Albrect and Bäassler reported a surprising result. They found that increasing the width σ of the energetic disorder increases the quantum yield φ. They attributed this behavior to the tendency for energy fluctuations to compete against the Coulombic pair attraction, driving the electron-hole pair apart at short distances where, without disorder, recombination would be almost certain. We have expanded upon this notion, and introduced spatial correlation into the energetic disorder. By correlating the energetic disorder, we have demonstrated even larger quantum yields in simulation, attributable to the tendency of correlation to drive the charges further apart spatially than merely random disorder. Our results generally support the findings of Greenham et al. in that a larger correlation radius gives a larger quantum yield. In addition to larger quantum yield, we believe that correlated disorder could be used to create pathways for charge transport within a material, allowing the charge carrier behavior to be tuned.

A Quick and Parallel Analytical Method Based on Quantum Dots Labeling for ToRCH-Related Antibodies

NASA Astrophysics Data System (ADS)

Yang, Hao; Guo, Qing; He, Rong; Li, Ding; Zhang, Xueqing; Bao, Chenchen; Hu, Hengyao; Cui, Daxiang

2009-12-01

Quantum dot is a special kind of nanomaterial composed of periodic groups of II-VI, III-V or IV-VI materials. Their high quantum yield, broad absorption with narrow photoluminescence spectra and high resistance to photobleaching, make them become a promising labeling substance in biological analysis. Here, we report a quick and parallel analytical method based on quantum dots for ToRCH-related antibodies including Toxoplasma gondii, Rubella virus, Cytomegalovirus and Herpes simplex virus type 1 (HSV1) and 2 (HSV2). Firstly, we fabricated the microarrays with the five kinds of ToRCH-related antigens and used CdTe quantum dots to label secondary antibody and then analyzed 100 specimens of randomly selected clinical sera from obstetric outpatients. The currently prevalent enzyme-linked immunosorbent assay (ELISA) kits were considered as “golden standard” for comparison. The results show that the quantum dots labeling-based ToRCH microarrays have comparable sensitivity and specificity with ELISA. Besides, the microarrays hold distinct advantages over ELISA test format in detection time, cost, operation and signal stability. Validated by the clinical assay, our quantum dots-based ToRCH microarrays have great potential in the detection of ToRCH-related pathogens.

Triplet and ground state potential energy surfaces of 1,4-diphenyl-1,3-butadiene: theory and experiment.

PubMed

Saltiel, J; Dmitrenko, O; Pillai, Z S; Klima, R; Wang, S; Wharton, T; Huang, Z-N; van de Burgt, L J; Arranz, J

2008-05-01

Relative energies of the ground state isomers of 1,4-diphenyl-1,3-butadiene (DPB) are determined from the temperature dependence of equilibrium isomer compositions obtained with the use of diphenyl diselenide as catalyst. Temperature and concentration effects on photostationary states and isomerization quantum yields with biacetyl or fluorenone as triplet sensitizers with or without the presence of O(2), lead to significant modification of the proposed DPB triplet potential energy surface. Quantum yields for ct-DPB formation from tt-DPB increase with [tt-DPB] revealing a quantum chain process in the tt --> ct direction, as had been observed for the ct --> tt direction, and suggesting an energy minimum at the (3)ct* geometry. They confirm the presence of planar and twisted isomeric triplets in equilibrium (K), with energy transfer from planar or quasi-planar geometries (quantum chain events from tt and ct triplets) and unimolecular decay (k(d)) from twisted geometries. Starting from cc-DPB, varphi(cc-->tt) increases with increasing [cc-DPB] whereas varphi(cc-->ct) is relatively insensitive to concentration changes. The concentration and temperature dependencies of the decay rate constants of DPB triplets in cyclohexane are consistent with the mechanism deduced from the photoisomerization quantum yields. The experimental DeltaH between (3)tt-DPB* and (3)tp-DPB*, 2.7 kcal mol(-1), is compared with the calculated energy difference [DFT with B3LYP/6-31+G(d,p) basis set]. Use of the calculated DeltaS = 4.04 eu between the two triplets gives k(d) = (2.4-6.4) x 10(7) s(-1), close to 1.70 x 10(7) s(-1), the value for twisted stilbene triplet decay. Experimental and calculated relative energies of DPB isomers on the ground and triplet state surfaces agree and theory is relied upon to deduce structural characteristics of the equilibrated conformers in the DPB triplet state.

One-pot synthesis of polythiol ligand for highly bright and stable hydrophilic quantum dots toward bioconjugate formation

NASA Astrophysics Data System (ADS)

Dezhurov, Sergey V.; Krylsky, Dmitry V.; Rybakova, Anastasia V.; Ibragimova, Sagila A.; Gladyshev, Pavel P.; Vasiliev, Alexey A.; Morenkov, Oleg S.

2018-03-01

A fast and efficient one-pot synthesis of thiol-terminated poly(vinylpirrolidone-co-maleic anhydride-co-ethylene glycol dimethacrylate) based heterobifunctional polymer (PTVP) has been developed. The polymer was used for the modification of quantum dots (QDs) to prepare water soluble and stable QDs with emission quantum yield as high as 80%. Using carbodiimide method, PTVP-capped red light-emitting QDs were conjugated to model monoclonal antibodies specific to glycoprotein B (gB) of Aujeszky’s disease virus (ADV) and successfully used in the lateral flow assay (LFA) for the detection of ADV gB in biological fluids. A comparative analysis of the sensitivity of the method was carried out using three types of QDs emitting in the red and far-red region.

Room-temperature processing of CdSe quantum dots with tunable sizes

NASA Astrophysics Data System (ADS)

Joo, So-Yeong; Jeong, Da-Woon; Lee, Chan-Gi; Kim, Bum-Sung; Park, Hyun-Su; Kim, Woo-Byoung

2017-06-01

In this work, CdSe quantum dots (QDs) with tunable sizes have been fabricated via photo-induced chemical etching at room temperature, and the related reaction mechanism was investigated. The surface of QDs was oxidized by the holes generated through photon irradiation of oxygen species, and the obtained oxide layer was dissolved in an aqueous solution of 3-amino-1-propanol (APOL) with an APOL:H2O volume ratio of 5:1. The generated electrons promoted QD surface interactions with amino groups, which ultimately passivated surface defects. The absorption and photoluminescence emission peaks of the produced QDs were clearly blue-shifted about 26 nm with increasing time, and the resulting quantum yield for an 8 h etched sample was increased from 20% to 26%, as compared to the initial sample.

Quantum-chemical investigations of spectroscopic properties of a fluorescence probe

NASA Astrophysics Data System (ADS)

Titova, T. Yu.; Morozova, Yu. P.; Zharkova, O. M.; Artyukhov, V. Ya.; Korolev, B. V.

2012-09-01

The prodan molecule (6-propionyl-2-dimethylamino naphthalene) - fluorescence probe - is investigated by quantum-chemical methods of intermediate neglect of differential overlap (INDO) and molecular electrostatic potential (MEP). The dipole moments of the ground and excited states, the nature and position of energy levels, the centers of specific solvation, the rate constants of photoprocesses, and the fluorescence quantum yield are estimated. To elucidate the role of the dimethylamino group in the formation of bands and spectral characteristics, the molecule only with the propionyl group (pron) is investigated. The long-wavelength absorption bands of prodan and pron molecules are interpreted. The results obtained for the prodan molecule by the INDO method with original spectroscopic parameterization are compared with the literature data obtained by the DFT/CIS, ZINDO/S, and AM1/CISD methods.

Direct impact of the sustained decline in the photosystem II efficiency upon plant productivity at different developmental stages.

PubMed

Tian, Yonglan; Ungerer, Petra; Zhang, Huayong; Ruban, Alexander V

2017-05-01

The impact of chronic photoinhibition of photosystem II (PSII) on the productivity of plants remains unknown. The present study investigated the influences of persistent decline in the PSII yield on morphology and productivity of Arabidopsis plants that were exposed to lincomycin at two different developmental stages (seedling and rosette stage). The results indicated that, although retarded, the lincomycin treated plants were able to accomplish the entire growth period with only 50% of the maximum quantum yield of primary photochemistry (Fv/Fm) of the control plants. The decline in quantum yield limited the electron transport rate (ETR). The impact of lincomycin on NPQ was not significant in seedlings, but was pronounced in mature plants. The treated plants produced an above ground biomass of 50% compared to control plants. Moreover, a linear relationship was found between the above ground biomass and total rosette leaf area, and the slope was decreased due to photoinhibition. The starch accumulation was highly inhibited by lincomycin treatment. Lincomycin induced a significant decrease in seed yield with plants treated from the rosette state showing higher yield than those treated from the seedling stage. Our data suggest that the sustained decline of PSII efficiency decreases plant productivity by constraining the ETR, leaf development and starch production. Copyright © 2017 Elsevier GmbH. All rights reserved.

Cryogenic on-chip multiplexer for the study of quantum transport in 256 split-gate devices

NASA Astrophysics Data System (ADS)

Al-Taie, H.; Smith, L. W.; Xu, B.; See, P.; Griffiths, J. P.; Beere, H. E.; Jones, G. A. C.; Ritchie, D. A.; Kelly, M. J.; Smith, C. G.

2013-06-01

We present a multiplexing scheme for the measurement of large numbers of mesoscopic devices in cryogenic systems. The multiplexer is used to contact an array of 256 split gates on a GaAs/AlGaAs heterostructure, in which each split gate can be measured individually. The low-temperature conductance of split-gate devices is governed by quantum mechanics, leading to the appearance of conductance plateaux at intervals of 2e2/h. A fabrication-limited yield of 94% is achieved for the array, and a "quantum yield" is also defined, to account for disorder affecting the quantum behaviour of the devices. The quantum yield rose from 55% to 86% after illuminating the sample, explained by the corresponding increase in carrier density and mobility of the two-dimensional electron gas. The multiplexer is a scalable architecture, and can be extended to other forms of mesoscopic devices. It overcomes previous limits on the number of devices that can be fabricated on a single chip due to the number of electrical contacts available, without the need to alter existing experimental set ups.

Adaptation to high CO2 concentration in an optimal environment: radiation capture, canopy quantum yield and carbon use efficiency

NASA Technical Reports Server (NTRS)

Monje, O.; Bugbee, B.

1998-01-01

The effect of elevated [CO2] on wheat (Triticum aestivum L. Veery 10) productivity was examined by analysing radiation capture, canopy quantum yield, canopy carbon use efficiency, harvest index and daily C gain. Canopies were grown at either 330 or 1200 micromoles mol-1 [CO2] in controlled environments, where root and shoot C fluxes were monitored continuously from emergence to harvest. A rapidly circulating hydroponic solution supplied nutrients, water and root zone oxygen. At harvest, dry mass predicted from gas exchange data was 102.8 +/- 4.7% of the observed dry mass in six trials. Neither radiation capture efficiency nor carbon use efficiency were affected by elevated [CO2], but yield increased by 13% due to a sustained increase in canopy quantum yield. CO2 enrichment increased root mass, tiller number and seed mass. Harvest index and chlorophyll concentration were unchanged, but CO2 enrichment increased average life cycle net photosynthesis (13%, P < 0.05) and root respiration (24%, P < 0.05). These data indicate that plant communities adapt to CO2 enrichment through changes in C allocation. Elevated [CO2] increases sink strength in optimal environments, resulting in sustained increases in photosynthetic capacity, canopy quantum yield and daily C gain throughout the life cycle.

Rigidifying fluorescent linkers by metal-organic framework formation for fluorescence blue shift and quantum yield enhancement.

PubMed

Wei, Zhangwen; Gu, Zhi-Yuan; Arvapally, Ravi K; Chen, Ying-Pin; McDougald, Roy N; Ivy, Joshua F; Yakovenko, Andrey A; Feng, Dawei; Omary, Mohammad A; Zhou, Hong-Cai

2014-06-11

We demonstrate that rigidifying the structure of fluorescent linkers by structurally constraining them in metal-organic frameworks (MOFs) to control their conformation effectively tunes the fluorescence energy and enhances the quantum yield. Thus, a new tetraphenylethylene-based zirconium MOF exhibits a deep-blue fluorescent emission at 470 nm with a unity quantum yield (99.9 ± 0.5%) under Ar, representing ca. 3600 cm(-1) blue shift and doubled radiative decay efficiency vs the linker precursor. An anomalous increase in the fluorescence lifetime and relative intensity takes place upon heating the solid MOF from cryogenic to ambient temperatures. The origin of these unusual photoluminescence properties is attributed to twisted linker conformation, intramolecular hindrance, and framework rigidity.

The reaction of NH2 with NO2

NASA Technical Reports Server (NTRS)

Jayanty, R. K. M.; Simonaitis, R.; Heicklen, J.

1976-01-01

Ammonia (NH3) was photolyzed at 213.9 nm in the presence of NO2 at 25 C in order to study the reactions of NH2 with NO2. The products included NO, with a quantum yield of 1.0. The other measured products of the reaction were N2 and N2O with respective quantum yields of 0.94 plus or minus 0.10 and 0.3 in the presence of small amounts of He and 0.65 plus or minus 0.15 and 0.13 in the presence of a large excess of He. The quantum yield for NO2 consumption was 6.0 plus or minus 2.0 in the absence of He. These results are explained in terms of various reactions.

AgCl-doped CdSe quantum dots with near-IR photoluminescence.

PubMed

Kotin, Pavel Aleksandrovich; Bubenov, Sergey Sergeevich; Mordvinova, Natalia Evgenievna; Dorofeev, Sergey Gennadievich

2017-01-01

We report the synthesis of colloidal CdSe quantum dots doped with a novel Ag precursor: AgCl. The addition of AgCl causes dramatic changes in the morphology of synthesized nanocrystals from spherical nanoparticles to tetrapods and finally to large ellipsoidal nanoparticles. Ellipsoidal nanoparticles possess an intensive near-IR photoluminescence ranging up to 0.9 eV (ca. 1400 nm). In this article, we explain the reasons for the formation of the ellipsoidal nanoparticles as well as the peculiarities of the process. The structure, Ag content, and optical properties of quantum dots are also investigated. The optimal conditions for maximizing both the reaction yield and IR photoluminescence quantum yield are found.

Production of graphene quantum dots by ultrasound-assisted exfoliation in supercritical CO2/H2O medium.

PubMed

Gao, Hanyang; Xue, Chen; Hu, Guoxin; Zhu, Kunxu

2017-07-01

In this research, three kinds of graphene quantum dots (GQDs)-pristine graphene quantum dots (PGQDs), expanded graphene quantum dots (EGQDs) and graphene oxide quantum dots (GOQDs)-were produced from natural graphite, expanded graphite, and oxide graphite respectively in an ultrasound-assisted supercritical CO 2 (scCO 2 )/H 2 O system. The effects of aqueous solution content ratio, system pressure, and ultrasonic power on the yields of different kinds of GQDs were investigated. According to these experiment results, the combination of the intense knocking force generated from high-pressure acoustic cavitation in a scCO 2 /H 2 O system and the superior penetration ability of scCO 2 was considered to be the key to the successful exfoliation of such tiny pieces from bulk graphite. An interesting result was found that, contrary to common experience, the yield of PGQDs from natural graphite was much higher than that of GOQDs from graphite oxide. Based on the experimental analysis, the larger interlayer resistance of natural graphite, which hindered the insertion of scCO 2 molecules, and the hydrophobic property of natural graphite surface, which made the planar more susceptible to the attack of ultrasonic collapsing bubbles, were deduced to be the two main reasons for this result. The differences in characteristics among the three kinds of GQDs were also studied and compared in this research. In our opinion, this low-cost and time-saving method may provide an alternative green route for the production of various kinds of GQDs, especially PGQDs. Copyright © 2017 Elsevier B.V. All rights reserved.

Effect of the Semiconductor Quantum Dot Shell Structure on Fluorescence Quenching by Acridine Ligand

NASA Astrophysics Data System (ADS)

Linkov, P. A.; Vokhmintcev, K. V.; Samokhvalov, P. S.; Laronze-Cochard, M.; Sapi, J.; Nabiev, I. R.

2018-02-01

The main line of research in cancer treatment is the development of methods for early diagnosis and targeted drug delivery to cancer cells. Fluorescent semiconductor core/shell nanocrystals of quantum dots (e.g., CdSe/ZnS) conjugated with an anticancer drug, e.g., an acridine derivative, allow real-time tracking and control of the process of the drug delivery to tumors. However, linking of acridine derivatives to a quantum dot can be accompanied by quantum dot fluorescence quenching caused by electron transfer from the quantum dot to the organic molecule. In this work, it has been shown that the structure of the shell of the quantum dot plays the decisive role in the process of photoinduced charge transfer from the quantum dot to the acridine ligand, which is responsible for fluorescence quenching. It has been shown that multicomponent ZnS/CdS/ZnS shells of CdSe cores of quantum dots, which have a relatively small thickness, make it possible to significantly suppress a decrease in the quantum yield of fluorescence of quantum dots as compared to both the classical ZnS thin shell and superthick shells of the same composition. Thus, core/multicomponent shell CdSe/ZnS/CdS/ZnS quantum dots can be used as optimal fluorescent probes for the development of systems for diagnosis and treatment of cancer with the use of anticancer compounds based on acridine derivatives.

Bright conjugated polymer nanoparticles containing a biodegradable shell produced at high yields and with tuneable optical properties by a scalable microfluidic device.

PubMed

Abelha, T F; Phillips, T W; Bannock, J H; Nightingale, A M; Dreiss, C A; Kemal, E; Urbano, L; deMello, J C; Green, M; Dailey, L A

2017-02-02

This study compares the performance of a microfluidic technique and a conventional bulk method to manufacture conjugated polymer nanoparticles (CPNs) embedded within a biodegradable poly(ethylene glycol) methyl ether-block-poly(lactide-co-glycolide) (PEG 5K -PLGA 55K ) matrix. The influence of PEG 5K -PLGA 55K and conjugated polymers cyano-substituted poly(p-phenylene vinylene) (CN-PPV) and poly(9,9-dioctylfluorene-2,1,3-benzothiadiazole) (F8BT) on the physicochemical properties of the CPNs was also evaluated. Both techniques enabled CPN production with high end product yields (∼70-95%). However, while the bulk technique (solvent displacement) under optimal conditions generated small nanoparticles (∼70-100 nm) with similar optical properties (quantum yields ∼35%), the microfluidic approach produced larger CPNs (140-260 nm) with significantly superior quantum yields (49-55%) and tailored emission spectra. CPNs containing CN-PPV showed smaller size distributions and tuneable emission spectra compared to F8BT systems prepared under the same conditions. The presence of PEG 5K -PLGA 55K did not affect the size or optical properties of the CPNs and provided a neutral net electric charge as is often required for biomedical applications. The microfluidics flow-based device was successfully used for the continuous preparation of CPNs over a 24 hour period. On the basis of the results presented here, it can be concluded that the microfluidic device used in this study can be used to optimize the production of bright CPNs with tailored properties with good reproducibility.

Seasonal and spatial variabilities in the water chemistry of prairie pothole wetlands influence the photoproduction of reactive intermediates.

PubMed

McCabe, Andrew J; Arnold, William A

2016-07-01

The hydrology and water chemistry of prairie pothole wetlands vary spatially and temporally, on annual and decadal timescales. Pesticide contamination of wetlands arising from agricultural activities is a foremost concern. Photochemical reactions are important in the natural attenuation of pesticides and may be important in limiting ecological and human exposure. Little is known, however, about the variable influence of wetland water chemistry on indirect photochemistry. In this study, seasonal water samples were collected from seven sites throughout the prairie pothole region over three years to understand the spatiotemporal dynamics of reactive intermediate photoproduction. Samples were classified by the season in which they were collected (spring, summer, or fall) and the typical hydroperiod of the wetland surface water (temporary or semi-permanent). Under photostable conditions, steady-state concentrations and apparent quantum yields or quantum yield coefficients were measured for triplet excited states of dissolved organic matter, singlet oxygen, hydroxyl radical, and carbonate radical under simulated sunlight. Steady-state concentrations and quantum yields increased on average by 15% and 40% from spring to fall, respectively. Temporary wetlands had 40% higher steady-state concentrations of reactive intermediates than semi-permanent wetlands, but 50% lower quantum yields. Computed quantum yields for reactive intermediate formation were used to predict the indirect photochemical half-lives of seven pesticides in average temporary and semi-permanent prairie pothole wetlands. As a first approximation, the predictions agree to within two orders of magnitude of previously reported half-lives. Copyright © 2016 Elsevier Ltd. All rights reserved.

Generalized Weyl-Wigner map and Vey quantum mechanics

NASA Astrophysics Data System (ADS)

Dias, Nuno Costa; Prata, João Nuno

2001-12-01

The Weyl-Wigner map yields the entire structure of Moyal quantum mechanics directly from the standard operator formulation. The covariant generalization of Moyal theory, also known as Vey quantum mechanics, was presented in the literature many years ago. However, a derivation of the formalism directly from standard operator quantum mechanics, clarifying the relation between the two formulations, is still missing. In this article we present a covariant generalization of the Weyl order prescription and of the Weyl-Wigner map and use them to derive Vey quantum mechanics directly from the standard operator formulation. The procedure displays some interesting features: it yields all the key ingredients and provides a more straightforward interpretation of the Vey theory including a direct implementation of unitary operator transformations as phase space coordinate transformations in the Vey idiom. These features are illustrated through a simple example.

Nanophotonic photon echo memory based on rare-earth-doped crystals

NASA Astrophysics Data System (ADS)

Zhong, Tian; Kindem, Jonathan; Miyazono, Evan; Faraon, Andrei; Caltech nano quantum optics Team

2015-03-01

Rare earth ions (REIs) are promising candidates for implementing solid-state quantum memories and quantum repeater devices. Their high spectral stability and long coherence times make REIs a good choice for integration in an on-chip quantum nano-photonic platform. We report the coupling of the 883 nm transition of Neodymium (Nd) to a Yttrium orthosilicate (YSO) photonic crystal nano-beam resonator, achieving Purcell enhanced spontaneous emission by 21 times and increased optical absorption. Photon echoes were observed in nano-beams of different doping concentrations, yielding optical coherence times T2 up to 80 μs that are comparable to unprocessed bulk samples. This indicates the remarkable coherence properties of Nd are preserved during nanofabrication, therefore opening the possibility of efficient on-chip optical quantum memories. The nano-resonator with mode volume of 1 . 6(λ / n) 3 was fabricated using focused ion beam, and a quality factor of 3200 was measured. Purcell enhanced absorption of 80% by an ensemble of ~ 1 × 106 ions in the resonator was measured, which fulfills the cavity impedance matching condition that is necessary to achieve quantum storage of photons with unity efficiency.

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

Wang, Peng; State Key Laboratory of Superhard Materials, College of Physics, Jilin University, Changchun 130012; Bai, Xue, E-mail: baix@jlu.edu.cn, E-mail: yuzhang@jlu.edu.cn

High quantum yield, narrow full width at half-maximum and tunable emission color of perovskite quantum dots (QDs) make this kind of material good prospects for light-emitting diodes (LEDs). However, the relatively poor stability under high temperature and air condition limits the device performance. To overcome this issue, the liquid-type packaging structure in combination with blue LED chip was employed to fabricate the fluorescent perovskite quantum dot-based LEDs. A variety of monochromatic LEDs with green, yellow, reddish-orange, and red emission were fabricated by utilizing the inorganic cesium lead halide perovskite quantum dots as the color-conversion layer, which exhibited the narrow fullmore » width at half-maximum (<35 nm), the relatively high luminous efficiency (reaching 75.5 lm/W), and the relatively high external quantum efficiency (14.6%), making it the best-performing perovskite LEDs so far. Compared to the solid state LED device, the liquid-type LED devices exhibited excellent color stability against the various working currents. Furthermore, we demonstrated the potential prospects of all-inorganic perovskite QDs for the liquid-type warm white LEDs.« less

Peculiarities of the photoinitiator-free photopolymerization of pentabrominated and pentafluorinated aromatic acrylates and methacrylates.

PubMed

Daikos, Olesya; Naumov, Sergej; Knolle, Wolfgang; Heymann, Katja; Scherzer, Tom

2016-11-30

Pentabrominated and fluorinated aromatic (meth)acrylates as well as their non-halogenated counterparts have been studied with the aim to avoid conventional photoinitiators and to overcome some negative consequences related to their use. Therefore, RTIR spectroscopy, laser flash photolysis and GC/MS were utilized. Even low concentrations (1 to 5 wt%) of brominated (meth)acrylates in the model varnish lead to initiation of a photopolymerization reaction under exposure to UV light with λ > 300 nm. This is due to the fact that excitation of the aryl moiety leads to the homolysis of bromine-phenyl bonds with a high quantum yield of ∼0.15-0.3. Both, bromine radicals released from either ortho, meta or para position as well as the corresponding tetrabromoaryl radicals, may initiate the polymerization of brominated aromatic (meth)acrylates. In contrast, fluorinated aromatic (meth)acrylates undergo α-cleavage of the carboxyl group (as in the case of non-halogenated aromatic (meth)acrylates), if excitation of the acrylic double bonds is done with UV-C light (λ < 280 nm). Radical formation occurs with a comparable quantum yield of 0.1-0.22 (fluorinated) and 0.16-0.36 (non-halogenated compounds), despite the different pathway of fragmentation. Thus, in all cases the efficiency of initiation is comparable to conventional photoinitiators. Quantum chemical calculations of orbitals involved and of the Gibbs free energy of transients and products support the suggested reaction pathway.

Purcell-enhanced quantum yield from carbon nanotube excitons coupled to plasmonic nanocavities

DOE PAGES

Luo, Yue; Ahmadi, Ehsaneh D.; Shayan, Kamran; ...

2017-11-10

Single-walled carbon nanotubes (SWCNTs) are promising absorbers and emitters to enable novel photonic applications and devices but are also known to suffer from low optical quantum yields. Here we demonstrate SWCNT excitons coupled to plasmonic nanocavity arrays reaching deeply into the Purcell regime with Purcell factors (F P) up to F P = 180 (average F P = 57), Purcell-enhanced quantum yields of 62% (average 42%), and a photon emission rate of 15 MHz into the first lens. The cavity coupling is quasi-deterministic since the photophysical properties of every SWCNT are enhanced by at least one order of magnitude. Furthermore,more » the measured ultra-narrow exciton linewidth (18 ueV) reaches the radiative lifetime limit, which is promising towards generation of transform-limited single photons. Furthermore, to demonstrate utility beyond quantum light sources we show that nanocavity-coupled SWCNTs perform as single-molecule thermometers detecting plasmonically induced heat at cryogenic temperatures in a unique interplay of excitons, phonons, and plasmons at the nanoscale.« less

Quantum yield and rate constant of the singlet 1Δ g oxygen luminescence in an aqueous medium in the presence of nanoscale inhomogeneities

NASA Astrophysics Data System (ADS)

Jarnikova, E. S.; Parkhats, M. V.; Stasheuski, A. S.; Lepeshkevich, S. V.; Dzhagarov, B. M.

2017-04-01

The quantum yields and lifetimes of photosensitized luminescence of the 1Δ g state of singlet oxygen in an aquatic media with a controlled concentration of dielectric anisotropy centers (polyethylene glycol) have been measured using the methods of laser fluorometry. It is established that the quantum yield and the rate constant ( k r ) of the a 1Δ g → X 3Σ g - luminescence of 1O2 increase as the polymer concentration increases. The effect is analyzed within a general approach involving a relationship between kr and dielectric properties of the medium and is explained by the increased density of photon states and the local field factor in the space around O2( a 1Δ g ).

Accurate quantum yields by laser gain vs absorption spectroscopy - Investigation of Br/Br(asterisk) channels in photofragmentation of Br2 and IBr

NASA Technical Reports Server (NTRS)

Haugen, H. K.; Weitz, E.; Leone, S. R.

1985-01-01

Various techniques have been used to study photodissociation dynamics of the halogens and interhalogens. The quantum yields obtained by these techniques differ widely. The present investigation is concerned with a qualitatively new approach for obtaining highly accurate quantum yields for electronically excited states. This approach makes it possible to obtain an accuracy of 1 percent to 3 percent. It is shown that measurement of the initial transient gain/absorption vs the final absorption in a single time-resolved signal is a very accurate technique in the study of absolute branching fractions in photodissociation. The new technique is found to be insensitive to pulse and probe laser characteristics, molecular absorption cross sections, and absolute precursor density.

Cross sections and quantum yields of the 3 micron emission for Er(3+) and Ho(3+) dopants in crystalsls

NASA Astrophysics Data System (ADS)

Payne, Stephen A.; Smith, Larry K.; Krupke, William F.

1995-05-01

The lifetime, quantum yields, and branching ratios for the 2.8 micron emissions of several Er-and Ho-doped fluorides and oxides were measured. Among the fluoride crystals examined, which included LiYF4, BaY2F8, LaF3, and KY3F10, only the Ho:LiFY4 systems showed any proof of nonradiative decay. Conversely, all the oxide crystals were affected by nonradiative processes, resulting in measured quantum yields ranging from 3.6% for Er:Y3Al5O12 to 62% for Er in Gd3Sc2Ga3O12. In addition, plots of the 2.8 micron emission cross sections for seven Er- and Ho-doped crystals were presented.

Sample-averaged biexciton quantum yield measured by solution-phase photon correlation.

PubMed

Beyler, Andrew P; Bischof, Thomas S; Cui, Jian; Coropceanu, Igor; Harris, Daniel K; Bawendi, Moungi G

2014-12-10

The brightness of nanoscale optical materials such as semiconductor nanocrystals is currently limited in high excitation flux applications by inefficient multiexciton fluorescence. We have devised a solution-phase photon correlation measurement that can conveniently and reliably measure the average biexciton-to-exciton quantum yield ratio of an entire sample without user selection bias. This technique can be used to investigate the multiexciton recombination dynamics of a broad scope of synthetically underdeveloped materials, including those with low exciton quantum yields and poor fluorescence stability. Here, we have applied this method to measure weak biexciton fluorescence in samples of visible-emitting InP/ZnS and InAs/ZnS core/shell nanocrystals, and to demonstrate that a rapid CdS shell growth procedure can markedly increase the biexciton fluorescence of CdSe nanocrystals.

Femtosecond two-photon photoassociation of hot magnesium atoms: A quantum dynamical study using thermal random phase wavefunctions

NASA Astrophysics Data System (ADS)

Amaran, Saieswari; Kosloff, Ronnie; Tomza, Michał; Skomorowski, Wojciech; Pawłowski, Filip; Moszynski, Robert; Rybak, Leonid; Levin, Liat; Amitay, Zohar; Berglund, J. Martin; Reich, Daniel M.; Koch, Christiane P.

2013-10-01

Two-photon photoassociation of hot magnesium atoms by femtosecond laser pulses, creating electronically excited magnesium dimer molecules, is studied from first principles, combining ab initio quantum chemistry and molecular quantum dynamics. This theoretical framework allows for rationalizing the generation of molecular rovibrational coherence from thermally hot atoms [L. Rybak, S. Amaran, L. Levin, M. Tomza, R. Moszynski, R. Kosloff, C. P. Koch, and Z. Amitay, Phys. Rev. Lett. 107, 273001 (2011)]. Random phase thermal wavefunctions are employed to model the thermal ensemble of hot colliding atoms. Comparing two different choices of basis functions, random phase wavefunctions built from eigenstates are found to have the fastest convergence for the photoassociation yield. The interaction of the colliding atoms with a femtosecond laser pulse is modeled non-perturbatively to account for strong-field effects.

Quantum optimization for training support vector machines.

PubMed

Anguita, Davide; Ridella, Sandro; Rivieccio, Fabio; Zunino, Rodolfo

2003-01-01

Refined concepts, such as Rademacher estimates of model complexity and nonlinear criteria for weighting empirical classification errors, represent recent and promising approaches to characterize the generalization ability of Support Vector Machines (SVMs). The advantages of those techniques lie in both improving the SVM representation ability and yielding tighter generalization bounds. On the other hand, they often make Quadratic-Programming algorithms no longer applicable, and SVM training cannot benefit from efficient, specialized optimization techniques. The paper considers the application of Quantum Computing to solve the problem of effective SVM training, especially in the case of digital implementations. The presented research compares the behavioral aspects of conventional and enhanced SVMs; experiments in both a synthetic and real-world problems support the theoretical analysis. At the same time, the related differences between Quadratic-Programming and Quantum-based optimization techniques are considered.

Magneto-transport of an electron bilayer system in an undoped Si/SiGe double-quantum-well heterostructure

DOE PAGES

Laroche, Dominique; Huang, ShiHsien; Nielsen, Erik; ...

2015-04-08

We report the design, the fabrication, and the magneto-transport study of an electron bilayer system embedded in an undoped Si/SiGe double-quantum-well heterostructure. Additionally, the combined Hall densities (n Hall ) ranging from 2.6 × 10 10 cm -2 to 2.7 × 10 11 cm -2 were achieved, yielding a maximal combined Hall mobility (μ Hall ) of 7.7 × 10 5 cm 2/(V • s) at the highest density. Simultaneous electron population of both quantum wells is clearly observed through a Hall mobility drop as the Hall density is increased to n Hall > 3.3 × 10 10 cm -2,more » consistent with Schrödinger-Poisson simulations. Furthermore, the integer and fractional quantum Hall effects are observed in the device, and single-layer behavior is observed when both layers have comparable densities, either due to spontaneous interlayer coherence or to the symmetric-antisymmetric gap.« less

Rotations of a logical qubit using the quantum Zeno effect extended to a manifold

NASA Astrophysics Data System (ADS)

Touzard, S.; Grimm, A.; Leghtas, Z.; Mundhada, S. O.; Reinhold, P.; Heeres, R.; Axline, C.; Reagor, M.; Chou, K.; Blumoff, J.; Sliwa, K. M.; Shankar, S.; Frunzio, L.; Schoelkopf, R. J.; Mirrahimi, M.; Devoret, M. H.

Encoding Quantum Information in the large Hilbert space of a harmonic oscillator has proven to have advantages over encoding in a register of physical qubits, but has also provided new challenges. While recent experiments have demonstrated quantum error correction using such an encoding based on superpositions of coherent states, these codes are still susceptible to non-corrected errors and lack controllability: compared to physical qubits it is hard to make arbitrary states and to perform operations on them. Our approach is to engineer the dynamics and the dissipation of a microwave cavity to implement a continuous dissipative measurement yielding two degenerate outcomes. This extends the quantum Zeno effect to a manifold, which in our case is spanned by two coherent states of opposite phases. In this second talk we present the result and analysis of an experiment that performs rotations on a logical qubit encoded in this protected manifold. Work supported by: ARO, ONR, AFOSR and YINQE.

Rotations of a logical qubit using the quantum Zeno effect extended to a manifold - Part 1

NASA Astrophysics Data System (ADS)

Grimm, A.; Touzard, S.; Leghtas, Z.; Mundhada, S. O.; Reinhold, P.; Heeres, R.; Axline, C.; Reagor, M.; Chou, K.; Blumoff, J.; Sliwa, K. M.; Shankar, S.; Frunzio, L.; Schoelkopf, R. J.; Mirrahimi, M.; Devoret, M. H.

Encoding Quantum Information in the large Hilbert space of a harmonic oscillator has proven to have advantages over encoding in a register of physical qubits, but has also provided new challenges. While recent experiments have demonstrated quantum error correction using such an encoding based on superpositions of coherent states, these codes are still susceptible to non-corrected errors and lack controllability: compared to physical qubits it is hard to make arbitrary states and to perform operations on them. Our approach is to engineer the dynamics and the dissipation of a microwave cavity to implement a continuous dissipative measurement yielding two degenerate outcomes. This extends the quantum Zeno effect to a manifold, which in our case is spanned by two coherent states of opposite phases. In this first talk we present the concept and architecture of an experiment that performs rotations on a logical qubit encoded in this protected manifold. Work supported by: ARO, ONR, AFOSR and YINQE.

Emerging technologies for high performance infrared detectors

NASA Astrophysics Data System (ADS)

Tan, Chee Leong; Mohseni, Hooman

2018-01-01

Infrared photodetectors (IRPDs) have become important devices in various applications such as night vision, military missile tracking, medical imaging, industry defect imaging, environmental sensing, and exoplanet exploration. Mature semiconductor technologies such as mercury cadmium telluride and III-V material-based photodetectors have been dominating the industry. However, in the last few decades, significant funding and research has been focused to improve the performance of IRPDs such as lowering the fabrication cost, simplifying the fabrication processes, increasing the production yield, and increasing the operating temperature by making use of advances in nanofabrication and nanotechnology. We will first review the nanomaterial with suitable electronic and mechanical properties, such as two-dimensional material, graphene, transition metal dichalcogenides, and metal oxides. We compare these with more traditional low-dimensional material such as quantum well, quantum dot, quantum dot in well, semiconductor superlattice, nanowires, nanotube, and colloid quantum dot. We will also review the nanostructures used for enhanced light-matter interaction to boost the IRPD sensitivity. These include nanostructured antireflection coatings, optical antennas, plasmonic, and metamaterials.

Water relation, leaf gas exchange and chlorophyll a fluorescence imaging of soybean leaves infected with Colletotrichum truncatum.

PubMed

Dias, Carla Silva; Araujo, Leonardo; Alves Chaves, Joicy Aparecida; DaMatta, Fábio M; Rodrigues, Fabrício A

2018-06-01

Considering the potential of anthracnose to decrease soybean yield and the need to gain more information regarding its effect on soybean physiology, the present study performed an in-depth analysis of the photosynthetic performance of soybean leaflets challenged with Colletotrichum truncatum by combining chlorophyll a fluorescence images with gas-exchange measurements and photosynthetic pigment pools. There were no significant differences between non-inoculated and inoculated plants in leaf water potential, apparent hydraulic conductance, net CO 2 assimilation rate, stomatal conductance to water vapor and transpiration rate. For internal CO 2 concentration, significant difference between non-inoculated and inoculated plants occurred only at 36 h after inoculation. Reductions in the values of the chlorophyll a fluorescence parameters [initial fluorescence (F 0 ), maximal fluorescence (F m ), maximal photosystem II quantum yield (F v /F m ), quantum yield of regulated energy dissipation (Y(NPQ))] and increases in effective PS II quantum yield (Y(II)), quantum yield of non-regulated energy dissipation Y(NO) and photochemical quenching coefficient (q P ) were noticed on the necrotic vein tissue in contrast to the surrounding leaf tissue. It appears that the impact of the infection by C. truncatum on the photosynthetic performance of the leaflets was minimal considering the preference of the fungus to colonize the veins. Copyright © 2018 Elsevier Masson SAS. All rights reserved.

Violet-to-Blue Gain and Lasing from Colloidal CdS Nanoplatelets: Low-Threshold Stimulated Emission Despite Low Photoluminescence Quantum Yield

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

Diroll, Benjamin T.; Talapin, Dmitri V.; Schaller, Richard D.

Amplified spontaneous emission (ASE) and lasing from solution-processed materials are demonstrated in the challenging violet-to-blue (430–490 nm) spectral region for colloidal nanoplatelets of CdS and newly synthesized core/shell CdS/ZnS nanoplatelets. Despite modest band-edge photoluminescence quantum yields of 2% or less for single excitons, which we show results from hole trapping, the samples exhibit low ASE thresholds. Furthermore, four-monolayer CdS samples show ASE at shorter wavelengths than any reported film of colloidal quantum-confined material. This work underlines that low quantum yields for single excitons do not necessarily lead to a poor gain medium. The low ASE thresholds originate from negligible dispersionmore » in thickness, large absorption cross sections of 2.8 × 10–14 cm–2, and rather slow (150 to 300 ps) biexciton recombination. We show that under higher-fluence excitation, ASE can kinetically outcompete hole trapping. Using nanoplatelets as the gain medium, lasing is observed in a linear optical cavity. This work confirms the fundamental advantages of colloidal quantum well structures as gain media, even in the absence of high photoluminescence efficiency.« less

Inkjet printed fluorescent nanorod layers exhibit superior optical performance over quantum dots

NASA Astrophysics Data System (ADS)

Halivni, Shira; Shemesh, Shay; Waiskopf, Nir; Vinetsky, Yelena; Magdassi, Shlomo; Banin, Uri

2015-11-01

Semiconductor nanocrystals exhibit unique fluorescence properties which are tunable in size, shape and composition. The high quantum yield and enhanced stability have led to their use in biomedical imaging and flat panel displays. Here, semiconductor nanorod based inkjet inks are presented, overcoming limitations of the commonly reported quantum dots in printing applications. Fluorescent seeded nanorods were found to be outstanding candidates for fluorescent inks, due to their low particle-particle interactions and negligible self-absorption. This is manifested by insignificant emission shifts upon printing, even in highly concentrated printed layers and by maintenance of a high fluorescence quantum yield, unlike quantum dots which exhibit fluorescence wavelength shifts and quenching effects. This behavior results from the reduced absorption/emission overlap, accompanied by low energy transfer efficiencies between the nanorods as supported by steady state and time resolved fluorescence measurements. The new seeded nanorod inks enable patterning of thin fluorescent layers, for demanding light emission applications such as signage and displays.Semiconductor nanocrystals exhibit unique fluorescence properties which are tunable in size, shape and composition. The high quantum yield and enhanced stability have led to their use in biomedical imaging and flat panel displays. Here, semiconductor nanorod based inkjet inks are presented, overcoming limitations of the commonly reported quantum dots in printing applications. Fluorescent seeded nanorods were found to be outstanding candidates for fluorescent inks, due to their low particle-particle interactions and negligible self-absorption. This is manifested by insignificant emission shifts upon printing, even in highly concentrated printed layers and by maintenance of a high fluorescence quantum yield, unlike quantum dots which exhibit fluorescence wavelength shifts and quenching effects. This behavior results from the reduced absorption/emission overlap, accompanied by low energy transfer efficiencies between the nanorods as supported by steady state and time resolved fluorescence measurements. The new seeded nanorod inks enable patterning of thin fluorescent layers, for demanding light emission applications such as signage and displays. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06248a

LASER APPLICATIONS AND OTHER TOPICS IN QUANTUM ELECTRONICS: Kinetics and quantum yield of photoluminescence of EuFOD3 doped into a nanoporous glass with the help of supercritical CO2

NASA Astrophysics Data System (ADS)

Bagratashvili, V. N.; Gerasimova, V. I.; Gordienko, V. M.; Tsypina, S. I.; Chutko, E. A.

2008-08-01

The kinetics of photoluminescence of a EuFOD3 metalloorganic compound doped into a nanoporous Vycor glass by the method of supercritical fluid impregnation is studied. The lifetime of luminescence of EuFOD3 molecules in pores excited by an excimer XeCl laser was 40 μs, which is considerably smaller than this lifetime (150—890 μs) in solutions. The quantum yield of luminescence of EuFOD3 was estimate as ≈4×10-4.

Separation of photoactive conformers based on hindered diarylethenes: efficient modulation in photocyclization quantum yields.

PubMed

Li, Wenlong; Jiao, Changhong; Li, Xin; Xie, Yongshu; Nakatani, Keitaro; Tian, He; Zhu, Weihong

2014-04-25

Endowing both solvent independency and excellent thermal bistability, the benzobis(thiadiazole)-bridged diarylethene system provides an efficient approach to realize extremely high photocyclization quantum yields (Φo-c , up to 90.6 %) by both separating completely pure anti-parallel conformer and suppressing intramolecular charge transfer (ICT). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Heterodiazocines: Synthesis and Photochromic Properties, Trans to Cis Switching within the Bio-optical Window.

PubMed

Hammerich, Melanie; Schütt, Christian; Stähler, Cosima; Lentes, Pascal; Röhricht, Fynn; Höppner, Ronja; Herges, Rainer

2016-10-04

Diazocines, bridged azobenzenes, exhibit superior photophysical properties compared to parent azobenzenes such as high switching efficiencies, quantum yields, and particularly switching wavelengths in the visible range. Synthesis, however, proceeds with low yields, and derivatives are difficult to prepare. We now present two heterodiazocines which are easier to synthesize, and the general procedures should also provide facile access to derivatives. Moreover, both compounds can be switched with light in the far-red (650 nm). Accessibility and photophysical properties make them ideal candidates for applications such as photoswitchable drugs and functional materials.

Spectrum sensitivity, energy yield, and revenue prediction of PV and CPV modules

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

Kinsey, Geoffrey S., E-mail: Geoffrey.kinsey@ee.doe.gov

2015-09-28

Impact on module performance of spectral irradiance variation has been determined for III-V multijunctions compared against the four most common flat-plate module types (cadmium telluride, multicrystalline silicon, copper indium gallium selenide, and monocrystalline silicon. Hour-by-hour representative spectra were generated using atmospheric variables for Albuquerque, New Mexico, USA. Convolution with published values for external quantum efficiency gave the predicted current output. When combined with specifications of commercial PV modules, energy yield and revenue were predicted. This approach provides a means for optimizing PV module design based on various site-specific temporal variables.

Spectrum sensitivity, energy yield, and revenue prediction of PV and CPV modules

NASA Astrophysics Data System (ADS)

Kinsey, Geoffrey S.

2015-09-01

Impact on module performance of spectral irradiance variation has been determined for III-V multijunctions compared against the four most common flat-plate module types (cadmium telluride, multicrystalline silicon, copper indium gallium selenide, and monocrystalline silicon. Hour-by-hour representative spectra were generated using atmospheric variables for Albuquerque, New Mexico, USA. Convolution with published values for external quantum efficiency gave the predicted current output. When combined with specifications of commercial PV modules, energy yield and revenue were predicted. This approach provides a means for optimizing PV module design based on various site-specific temporal variables.

Substituent effect on photophysical properties of bi-1,3,4-oxadiazole derivatives in solution

NASA Astrophysics Data System (ADS)

Chen, Fangyi; Tian, Taiji; Zhao, Chengxiao; Bai, Binglian; Li, Min; Wang, Haitao

2016-04-01

A series of phenyl substituted bi-1,3,4-oxadiazole derivatives were designed and synthesized; the effect of substituent on the photophysical properties and molecular electronic structures was fully studied by the combination of experimental techniques and theoretical calculations. Compared to parent compound without any substituent (BOXD), fluoro-substituent shows little effect on the absorption and emission spectra, whilst a little larger spectral red-shift could be observed for methoxy-, nitro-substituted derivatives and thienyl-substituted bi-1,3,4-oxadiazole (TBOXD). These spectral changes can be well explained by theoretically calculated HOMO and LUMO energy level changes. All these molecules show high fluorescence quantum yield except for nitro-substituted derivative in dilute solutions. The quantum yield of BOXD changes with the concentration and exhibits a high value at the concentrated solution. This work revealed the influence of substituent on the photophysical properties of bi-1,3,4-oxadizaole derivatives in dilute solutions and provided guidance for designing molecules with potential application.

Photophysical properties of fluorescently-labeled peptoids.

PubMed

Rudat, Birgit; Birtalan, Esther; Vollrath, Sidonie B L; Fritz, Daniel; Kölmel, Dominik K; Nieger, Martin; Schepers, Ute; Müllen, Klaus; Eisler, Hans-Jürgen; Lemmer, Uli; Bräse, Stefan

2011-09-01

Fluorescently-labeled biomolecules are often utilized in biochemical or cellular experiments without further detailed spectroscopical characterization. This report is intended to narrow this gap and therefore presents the photophysical investigation of a library of 17 fluorescently-labeled molecules, namely peptoid transporters. First, one peptoid structure is labeled with seven different fluorophores and the spectroscopical properties are examined. Absorption and fluorescence maxima are almost identical for free dyes and conjugated dyes, suggesting free choice of a spectrally suitable fluorophore for different applications. Otherwise, extinction coefficients and quantum yields, and therefore the brightness of all seven dyes are strongly influenced. For the fluorophores, e.g. rhodamine B, the extent of this influence depends on the peptoid itself. This is shown by comparing different structures in the second part of this report. Especially the side chain functionalities influence the brightness. And finally, peptoids having two identical fluorescent labels are presented, which show decreased quantum yields. Possible reasons for the observed photophysical properties are discussed. Copyright © 2011 Elsevier Masson SAS. All rights reserved.

Energy-Conversion Properties of Vapor-Liquid-Solid-Grown Silicon Wire-Array Photocathodes

NASA Astrophysics Data System (ADS)

Boettcher, Shannon W.; Spurgeon, Joshua M.; Putnam, Morgan C.; Warren, Emily L.; Turner-Evans, Daniel B.; Kelzenberg, Michael D.; Maiolo, James R.; Atwater, Harry A.; Lewis, Nathan S.

2010-01-01

Silicon wire arrays, though attractive materials for use in photovoltaics and as photocathodes for hydrogen generation, have to date exhibited poor performance. Using a copper-catalyzed, vapor-liquid-solid-growth process, SiCl4 and BCl3 were used to grow ordered arrays of crystalline p-type silicon (p-Si) microwires on p+-Si(111) substrates. When these wire arrays were used as photocathodes in contact with an aqueous methyl viologen2+/+ electrolyte, energy-conversion efficiencies of up to 3% were observed for monochromatic 808-nanometer light at fluxes comparable to solar illumination, despite an external quantum yield at short circuit of only 0.2. Internal quantum yields were at least 0.7, demonstrating that the measured photocurrents were limited by light absorption in the wire arrays, which filled only 4% of the incident optical plane in our test devices. The inherent performance of these wires thus conceptually allows the development of efficient photovoltaic and photoelectrochemical energy-conversion devices based on a radial junction platform.

Energy-conversion properties of vapor-liquid-solid-grown silicon wire-array photocathodes.

PubMed

Boettcher, Shannon W; Spurgeon, Joshua M; Putnam, Morgan C; Warren, Emily L; Turner-Evans, Daniel B; Kelzenberg, Michael D; Maiolo, James R; Atwater, Harry A; Lewis, Nathan S

2010-01-08

Silicon wire arrays, though attractive materials for use in photovoltaics and as photocathodes for hydrogen generation, have to date exhibited poor performance. Using a copper-catalyzed, vapor-liquid-solid-growth process, SiCl4 and BCl3 were used to grow ordered arrays of crystalline p-type silicon (p-Si) microwires on p+-Si(111) substrates. When these wire arrays were used as photocathodes in contact with an aqueous methyl viologen(2+/+) electrolyte, energy-conversion efficiencies of up to 3% were observed for monochromatic 808-nanometer light at fluxes comparable to solar illumination, despite an external quantum yield at short circuit of only 0.2. Internal quantum yields were at least 0.7, demonstrating that the measured photocurrents were limited by light absorption in the wire arrays, which filled only 4% of the incident optical plane in our test devices. The inherent performance of these wires thus conceptually allows the development of efficient photovoltaic and photoelectrochemical energy-conversion devices based on a radial junction platform.

Arene-Inserted Extended Germa[n]pericyclynes: Synthesis, Structure, and Phosphorescence Properties.

PubMed

Tanimoto, Hiroki; Mori, Junta; Ito, Shunichiro; Nishiyama, Yasuhiro; Morimoto, Tsumoru; Tanaka, Kazuo; Chujo, Yoshiki; Kakiuchi, Kiyomi

2017-07-26

This report describes the synthesis and characterization of arene-inserted extended (ArEx) germa[n]pericyclynes composed of germanium and 1,4-diethynylbenzene units. These novel cyclic germanium-π unit materials were synthesized with diethynylbenzene and germanium dichloride. X-ray crystallographic analysis revealed their structures, and the planar conformation of ArEx germa[4]pericyclyne along with the regular aromatic rings. UV/Vis absorption spectra and fluorescence emission spectra showed considerably unique and highly improved character compared to previously reported germa[n]pericyclynes. Even in the absence of transition metal components, phosphorescence emissions were observed, and the emission lifetimes were dramatically improved. ArEx germa[n]pericyclynes showed high photoluminescence quantum yields, whereas low photoluminescence quantum yields were observed for acyclic compounds. Density functional theory calculations show delocalized orbitals between skipped alkyne units through a germanium tether, and an increase in the HOMO energy level, leading to a small HOMO-LUMO energy gap. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A highly efficient silole-containing dithienylethene with excellent thermal stability and fatigue resistance: a promising candidate for optical memory storage materials.

PubMed

Chan, Jacky Chi-Hung; Lam, Wai Han; Yam, Vivian Wing-Wah

2014-12-10

Diarylethene compounds are potential candidates for applications in optical memory storage systems and photoswitchable molecular devices; however, they usually show low photocycloreversion quantum yields, which result in ineffective erasure processes. Here, we present the first highly efficient photochromic silole-containing dithienylethene with excellent thermal stability and fatigue resistance. The photochemical quantum yields for photocyclization and photocycloreversion of the compound are found to be high and comparable to each other; the latter of which is rarely found in diarylethene compounds. These would give rise to highly efficient photoswitchable material with effective writing and erasure processes. Incorporation of the silole moiety as a photochromic dithienylethene backbone also was demonstrated to enhance the thermal stability of the closed form, in which the thermal backward reaction to the open form was found to be negligible even at 100 °C, which leads to a promising candidate for use as photoswitchable materials and optical memory storage.

Chemiluminescence reactions with cationic, neutral, and anionic ruthenium(II) complexes containing 2,2'-bipyridine and bathophenanthroline disulfonate ligands.

PubMed

Francis, Paul S; Papettas, Dimitra; Zammit, Elizabeth M; Barnett, Neil W

2010-07-15

Ruthenium complexes containing 4,7-diphenyl-1,10-phenanthroline disulfonate (bathophenanthroline disulfonate; BPS) ligands, Ru(BPS)(3)(4-), Ru(BPS)(2)(bipy)(2-) and Ru(BPS)(bipy)(2), were compared to tris(2,2'-bipyridine)ruthenium(II) (Ru(bipy)(3)(2+)), including examination of the wavelengths of maximum absorption and corrected emission intensity, photoluminescence quantum yield, stability of their oxidised ruthenium(III) form, and relative chemiluminescence intensities and signal-to-blank ratios with cerium(IV) sulfate and six analytes (codeine, morphine cocaine, potassium oxalate, furosemide and hydrochlorothiazide) in acidic aqueous solution. The presence of BPS ligands in the complex increased the photoluminescence quantum yield, but decreased the stability of the oxidised form of the reagent. In contrast to previous evidence showing much greater electrochemiluminescence intensities using Ru(BPS)(2)(bipy)(2-) and Ru(BPS)(bipy)(2), these complexes did not provide superior chemiluminescence signals than their homoleptic analogues. Copyright 2010 Elsevier B.V. All rights reserved.

Photodissociation of quantum state-selected diatomic molecules yields new insight into ultracold chemistry

NASA Astrophysics Data System (ADS)

McDonald, Mickey; McGuyer, Bart H.; Lee, Chih-Hsi; Apfelbeck, Florian; Zelevinsky, Tanya

2016-05-01

When a molecule is subjected to a sufficiently energetic photon it can break apart into fragments through a process called ``photodissociation''. For over 70 years this simple chemical reaction has served as a vital experimental tool for acquiring information about molecular structure, since the character of the photodissociative transition can be inferred by measuring the 3D photofragment angular distribution (PAD). While theoretical understanding of this process has gradually evolved from classical considerations to a fully quantum approach, experiments to date have not yet revealed the full quantum nature of this process. In my talk I will describe recent experiments involving the photodissociation of ultracold, optical lattice-trapped, and fully quantum state-resolved 88Sr2 molecules. Optical absorption images of the PADs produced in these experiments reveal features which are inherently quantum mechanical in nature, such as matter-wave interference between output channels, and are sensitive to the quantum statistics of the molecular wavefunctions. The results of these experiments cannot be predicted using quasiclassical methods. Instead, we describe our results with a fully quantum mechanical model yielding new intuition about ultracold chemistry.

Aqueous synthesis of high bright and tunable near-infrared AgInSe2-ZnSe quantum dots for bioimaging.

PubMed

Che, Dongchen; Zhu, Xiaoxu; Wang, Hongzhi; Duan, Yourong; Zhang, Qinghong; Li, Yaogang

2016-02-01

Efficient synthetic methods for near-infrared quantum dots with good biophysical properties as bioimaging agents are urgently required. In this work, a simple and fast synthesis of highly luminescent, near-infrared AgInSe2-ZnSe quantum dots (QDs) with tunable emissions in aqueous media is reported. This method avoids high temperature and pressure and organic solvents to directly generate water-dispersible AgInSe2-ZnSe QDs. The photoluminescence emission peak of the AgInSe2-ZnSe QDs ranged from 625 to 940nm, with quantum yields up to 31%. The AgInSe2-ZnSe QDs with high quantum yield, near-infrared and low cytotoxic could be used as good cell labels, showing great potential applications in bio-imaging. Copyright © 2015 Elsevier Inc. All rights reserved.

Quantum yield for carbon monoxide production in the 248 nm photodissociation of carbonyl sulfide (OCS)

NASA Technical Reports Server (NTRS)

Zhao, Z.; Stickel, R. E.; Wine, P. H.

1995-01-01

Tunable diode laser absorption spectroscopy has been coupled with excimer laser flash photolysis to measure the quantum yield for CO production from 248 nm photodissociation of carbonyl sulfide (OCS) relative to the well-known quantum yield for CO production from 248 nm photolysis of phosgene (Cl2CO2). The temporal resolution of the experiments was sufficient to distinguish CO formed directly by photodissociation from that formed by subsequent S((sup 3)P(sub J)) reaction with OCS. Under the experimental conditions employed, CO formation via the fast S((sup 1)D(sub 2)) + OCS reaction was minimal. Measurements at 297K and total pressures from 4 to 100 Torr N2 + N2O show the CO yield to be greater than 0.95 and most likely unity. This result suggests that the contribution of OCS as a precursor to the lower stratospheric sulfate aerosol layer is somewhat larger than previously thought.

Analysis of wavelength-dependent photoisomerization quantum yields in bilirubins by fitting two exciton absorption bands

NASA Astrophysics Data System (ADS)

Mazzoni, M.; Agati, G.; Troup, G. J.; Pratesi, R.

2003-09-01

The absorption spectra of bilirubins were deconvoluted by two Gaussian curves of equal width representing the exciton bands of the non-degenerate molecular system. The two bands were used to study the wavelength dependence of the (4Z, 15Z) rightarrow (4Z, 15E) configurational photoisomerization quantum yield of the bichromophoric bilirubin-IXalpha (BR-IX), the intrinsically asymmetric bile pigment associated with jaundice and the symmetrically substituted bilirubins (bilirubin-IIIalpha and mesobilirubin-XIIIalpha), when they are irradiated in aqueous solution bound to human serum albumin (HSA). The same study was performed for BR-IX in ammoniacal methanol solution (NH4OH/MeOH). The quantum yields of the configurational photoprocesses were fitted with a combination function of the two Gaussian bands normalized to the total absorption, using the proportionality coefficients and a scaling factor as parameters. The decrease of the (4Z, 15Z) rightarrow (4Z, 15E) quantum yield with increasing wavelength, which occurs for wavelengths longer than the most probable Franck-Condon transition of the molecule, did not result in a unique function of the exciton absorptions. In particular we found two ranges corresponding to different exciton interactions with different proportionality coefficients and scaling factors. The wavelength-dependent photoisomerization of bilirubins was described as an abrupt change in quantum yield as soon as the resulting excitation was strongly localized in each chromophore. The change was correlated to a variation of the interaction between the two chromophores when the short-wavelength exciton absorption became vanishingly small. With the help of the circular dichroism (CD) spectrum of BR-IX in HSA, a small band was resolved in the bilirubin absorption spectrum, delivering part of the energy required for the (4Z, 15Z) rightarrow (4Z, 15E) photoisomerization of the molecule.

Comparisons of Photosynthetic Responses of Xanthium strumarium and Helianthus annuus to Chronic and Acute Water Stress in Sun and Shade 1

PubMed Central

Ben, Gui-Ying; Osmond, C. Barry; Sharkey, Thomas D.

1987-01-01

We have examined the effects of mild, chronic water stress and acute water stress on two water stress sensitive plants, Xanthium strumarium and Helianthus annuus. Using a combination of the leaf disc O2 electrode to measure the light responses of photosynthesis and 77 K fluorescence to monitor damage to the primary photochemistry, we have found the following: (a) The CO2 saturated rate of photosynthesis at high light is the most water stress sensitive parameter measured. (b) The apparent quantum yield (moles O2 per mole photons) was slightly, if at all, affected by mild water stress (>−1.5 megapascals). (c) Severe water stress (<−1.5 megapascals) reduced the quantum yield of photosynthesis regardless of whether the stress was applied in sun or shade. The light independent reduction of quantum yield was not associated with a reduction in 77 K fluorescence (Fv/Fm) indicating that the quantum yield reduction was not the result of damage to primary photochemistry. (d) The diel fluctuation in 77 K fluorescence seen in sun-exposed control leaves was greatly exaggerated in water stressed leaves because of enhanced decline in 77 K fluorescence in the morning. The rate of recovery was similar in both control and water stressed leaves. Shaded leaves showed no change in 77 K fluorescence regardless of whether water stress was imposed or not. (e) The water stress sensitive plants used in these experiments did not recover from acute water stress severe enough to reduce the quantum yield or chronic water stress which lasted long enough that light dependent damage to primary photochemistry occurred. PMID:16665465

Comparisons of Photosynthetic Responses of Xanthium strumarium and Helianthus annuus to Chronic and Acute Water Stress in Sun and Shade.

PubMed

Ben, G Y; Osmond, C B; Sharkey, T D

1987-06-01

We have examined the effects of mild, chronic water stress and acute water stress on two water stress sensitive plants, Xanthium strumarium and Helianthus annuus. Using a combination of the leaf disc O(2) electrode to measure the light responses of photosynthesis and 77 K fluorescence to monitor damage to the primary photochemistry, we have found the following: (a) The CO(2) saturated rate of photosynthesis at high light is the most water stress sensitive parameter measured. (b) The apparent quantum yield (moles O(2) per mole photons) was slightly, if at all, affected by mild water stress (>-1.5 megapascals). (c) Severe water stress (<-1.5 megapascals) reduced the quantum yield of photosynthesis regardless of whether the stress was applied in sun or shade. The light independent reduction of quantum yield was not associated with a reduction in 77 K fluorescence (F(v)/F(m)) indicating that the quantum yield reduction was not the result of damage to primary photochemistry. (d) The diel fluctuation in 77 K fluorescence seen in sun-exposed control leaves was greatly exaggerated in water stressed leaves because of enhanced decline in 77 K fluorescence in the morning. The rate of recovery was similar in both control and water stressed leaves. Shaded leaves showed no change in 77 K fluorescence regardless of whether water stress was imposed or not. (e) The water stress sensitive plants used in these experiments did not recover from acute water stress severe enough to reduce the quantum yield or chronic water stress which lasted long enough that light dependent damage to primary photochemistry occurred.

Sample-Averaged Biexciton Quantum Yield Measured by Solution-Phase Photon Correlation

DOE PAGES

Beyler, Andrew P.; Bischof, Thomas S.; Cui, Jian; ...

2014-11-19

The brightness of nanoscale optical materials such as semiconductor nanocrystals is currently limited in high excitation flux applications by inefficient multiexciton fluorescence. We have devised a solution-phase photon correlation measurement that can conveniently and reliably measure the average biexciton-to-exciton quantum yield ratio of an entire sample without user selection bias. This technique can be used to investigate the multiexciton recombination dynamics of a broad scope of synthetically underdeveloped materials, including those with low exciton quantum yields and poor fluorescence stability. Here in this study, we have applied this method to measure weak biexciton fluorescence in samples of visible-emitting InP/ZnS andmore » InAs/ZnS core/shell nanocrystals, and to demonstrate that a rapid CdS shell growth procedure can markedly increase the biexciton fluorescence of CdSe nanocrystals.« less

Sample-Averaged Biexciton Quantum Yield Measured by Solution-Phase Photon Correlation

PubMed Central

Beyler, Andrew P.; Bischof, Thomas S.; Cui, Jian; Coropceanu, Igor; Harris, Daniel K.; Bawendi, Moungi G.

2015-01-01

The brightness of nanoscale optical materials such as semiconductor nanocrystals is currently limited in high excitation flux applications by inefficient multiexciton fluorescence. We have devised a solution-phase photon correlation measurement that can conveniently and reliably measure the average biexciton-to-exciton quantum yield ratio of an entire sample without user selection bias. This technique can be used to investigate the multiexciton recombination dynamics of a broad scope of synthetically underdeveloped materials, including those with low exciton quantum yields and poor fluorescence stability. Here, we have applied this method to measure weak biexciton fluorescence in samples of visible-emitting InP/ZnS and InAs/ZnS core/shell nanocrystals, and to demonstrate that a rapid CdS shell growth procedure can markedly increase the biexciton fluorescence of CdSe nanocrystals. PMID:25409496

Fabrication of highly fluorescent graphene quantum dots using L-glutamic acid for in vitro/in vivo imaging and sensing.

PubMed

Wu, Xu; Tian, Fei; Wang, Wenxue; Chen, Jiao; Wu, Min; Zhao, Julia Xiaojun

2013-08-21

A facile bottom-up method for the synthesis of highly fluorescent graphene quantum dots (GQDs) has been developed using a one-step pyrolysis of a natural amino acid, L-glutamic acid, with the assistance of a simple heating mantle device. The developed GQDs showed strong blue, green and red luminescence under the irradiation of ultra-violet, blue and green light, respectively. Moreover, the GQDs emitted near-infrared (NIR) fluorescence in the range of 800-850 nm with the excitation-dependent manner. This NIR fluorescence has a large Stokes shift of 455 nm, providing significant advantage for sensitive determination and imaging of biological targets. The fluorescence properties of the GQDs, such as quantum yields, fluorescence life time, and photostability, were measured and the fluorescence quantum yield was as high as 54.5 %. The morphology and composites of the GQDs were characterized using TEM, SEM, EDS, and FT-IR. The feasibility of using the GQDs as a fluorescent biomarker was investigated through in vitro and in vivo fluorescence imaging. The results showed that the GQDs could be a promising candidate for bioimaging. Most importantly, compared to the traditional quantum dots (QDs), the GQDs is chemically inert. Thus, the potential toxicity of the intrinsic heavy metal in the traditional QDs would not be a concern for GQDs. In addition, the GQDs possessed an intrinsic peroxidase-like catalytic activity that was similar to the graphene sheets and carbon nanotubes. Coupled with 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS), the GQDs can be used for the sensitive detection of hydrogen peroxide with a limit of detection of 20 μM.

Role of electron transfer in Ce{sup 3+} sensitized Yb{sup 3+} luminescence in borate glass

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

Sontakke, Atul D., E-mail: sontakke.atul.55a@st.kyoto-u.ac.jp; Katayama, Yumiko; Zhuang, Yixi

2015-01-07

In a Ce{sup 3+}-Yb{sup 3+} system, two mechanisms are proposed so far namely, the quantum cutting mechanism and the electron transfer mechanism explaining Yb{sup 3+} infrared luminescence under Ce{sup 3+} excitation. Among them, the quantum cutting mechanism, where one Ce{sup 3+} photon (ultraviolet/blue) gives rise to two Yb{sup 3+} photons (near infrared) is widely sought for because of its huge potential in enhancing the solar cell efficiency. In present study on Ce{sup 3+}-Yb{sup 3+} codoped borate glasses, Ce{sup 3+} sensitized Yb{sup 3+} luminescence at ∼1 μm have been observed on Ce{sup 3+} 5d state excitation. However, the intensity of sensitized Yb{supmore » 3+} luminescence is found to be very weak compared to the strong quenching occurred in Ce{sup 3+} luminescence in Yb{sup 3+} codoped glasses. Moreover, the absolute luminescence quantum yield also showed a decreasing trend with Yb{sup 3+} codoping in the glasses. The overall behavior of the luminescence properties and the quantum yield is strongly contradicting with the quantum cutting phenomenon. The results are attributed to the energetically favorable electron transfer interactions followed by Ce{sup 3+}-Yb{sup 3+} ⇌ Ce{sup 4+}-Yb{sup 2+} inter-valence charge transfer and successfully explained using the absolute electron binding energies of dopant ions in the studied borate glass. Finally, an attempt has been presented to generalize the electron transfer mechanism among opposite oxidation/reduction property dopant ions using the vacuum referred electron binding energy (VRBE) scheme for lanthanide series.« less

Fabrication of highly fluorescent graphene quantum dots using L-glutamic acid for in vitro/in vivo imaging and sensing

PubMed Central

Wu, Xu; Tian, Fei; Wang, Wenxue; Chen, Jiao; Wu, Min; Zhao, Julia Xiaojun

2013-01-01

A facile bottom-up method for the synthesis of highly fluorescent graphene quantum dots (GQDs) has been developed using a one-step pyrolysis of a natural amino acid, L-glutamic acid, with the assistance of a simple heating mantle device. The developed GQDs showed strong blue, green and red luminescence under the irradiation of ultra-violet, blue and green light, respectively. Moreover, the GQDs emitted near-infrared (NIR) fluorescence in the range of 800–850 nm with the excitation-dependent manner. This NIR fluorescence has a large Stokes shift of 455 nm, providing significant advantage for sensitive determination and imaging of biological targets. The fluorescence properties of the GQDs, such as quantum yields, fluorescence life time, and photostability, were measured and the fluorescence quantum yield was as high as 54.5 %. The morphology and composites of the GQDs were characterized using TEM, SEM, EDS, and FT-IR. The feasibility of using the GQDs as a fluorescent biomarker was investigated through in vitro and in vivo fluorescence imaging. The results showed that the GQDs could be a promising candidate for bioimaging. Most importantly, compared to the traditional quantum dots (QDs), the GQDs is chemically inert. Thus, the potential toxicity of the intrinsic heavy metal in the traditional QDs would not be a concern for GQDs. In addition, the GQDs possessed an intrinsic peroxidase-like catalytic activity that was similar to the graphene sheets and carbon nanotubes. Coupled with 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS), the GQDs can be used for the sensitive detection of hydrogen peroxide with a limit of detection of 20 μM. PMID:23997934

A Phosphine-Free Route to Size-Adjustable CdSe and CdSe/CdS Core-Shell Quantum Dots for White-Light-Emitting Diodes.

PubMed

Zhang, Yugang; Li, Guopeng; Zhang, Ting; Song, Zihang; Wang, Hui; Zhang, Zhongping; Jiang, Yang

2018-03-01

The selenium dioxide was used as the precursor to synthesize wide-size-ranged CdSe quantum dots (2.4-5.7 nm) via hot-injection route. The CdSe quantum dots are featured with high crystalline, monodisperse, zinc blende structure and wide emission region (530-635 nm). In order to improve the stability and quantum yield, a phosphine-free single-molecular precursor approach is used to obtain CdSe/CdS core/shell quantum dots. The CdSe/CdS quantum dots are highly fluorescent with quantum yield up to 65%, and persist the good monodispersity and high crystallinity. Moreover, the quantum dots white light-emitting-diodes are fabricated by using the resultant red emission core/shell quantum dots and Y3Al5O12:Ce3+ yellow phosphors as color-conversion layers on a blue InGaN chip. The prepared light-emitting-diodes show good performance with CIE-1931 coordinated of (0.3583, 0.3349), an Ra of 92.9, and a Tc of 4410 K at 20 mA, which indicate that the combination of red-emission QDs and yellow phophors as a promising approach to obtain warm WLEDs with good color rendering.

Excited-state properties of nucleic acid components

NASA Astrophysics Data System (ADS)

Salet, C.; Bensasson, R. V.; Becker, R. S.

1981-12-01

Measurements were made of the fluorescence and phosphorescence spectra and lifetimes, and also of the absorption spectra, lifetimes, extinction coefficients, and quantum yields of the T1 lower triplet states of thymine, uracil, their N, N'-dimethyl derivatives, thymidine, thymidine monophosphate, uridine, and uridine monophosphate in various solvents at 300 °K. The influence of the solvent on the quantum yield of the T1 state of nucleic acid components is discussed.

Laboratory Measurements of Photolytic Parameters for Formaldehyde.

DTIC Science & Technology

1980-11-01

dynamic dilution methods. Compressed air stored in steel cylinders, carefully selected to contain carbon monoxide and hydrogen at mixing ratios of...in air has been investi- gated in the laboratory at two temperatures: 300 and 220 K. Quantum yields for the formation of CO and H2 were determined at...procedures in the case of pure formaldehyde gave consistent results. (b) Quantum Yields Mixtures of formaldehyde in air were photolyzed in a

Towards efficient solar hydrogen production by intercalated carbon nitride photocatalyst.

PubMed

Gao, Honglin; Yan, Shicheng; Wang, Jiajia; Huang, Yu An; Wang, Peng; Li, Zhaosheng; Zou, Zhigang

2013-11-07

The development of efficient photocatalytic material for converting solar energy to hydrogen energy as viable alternatives to fossil-fuel technologies is expected to revolutionize energy shortage and environment issues. However, to date, the low quantum yield for solar hydrogen production over photocatalysts has hindered advances in the practical applications of photocatalysis. Here, we show that a carbon nitride intercalation compound (CNIC) synthesized by a simple molten salt route is an efficient polymer photocatalyst with a high quantum yield. We found that coordinating the alkali metals into the C-N plane of carbon nitride will induce the un-uniform spatial charge distribution. The electrons are confined in the intercalated region while the holes are in the far intercalated region, which promoted efficient separation of photogenerated carriers. The donor-type alkali metal ions coordinating into the nitrogen pots of carbon nitrides increase the free carrier concentration and lead to the formation of novel nonradiative paths. This should favor improved transport of the photogenerated electron and hole and decrease the electron-hole recombination rate. As a result, the CNIC exhibits a quantum yield as high as 21.2% under 420 nm light irradiation for solar hydrogen production. Such high quantum yield opens up new opportunities for using cheap semiconducting polymers as energy transducers.

Intense visible emission from ZnO/PAAX (X = H or Na) nanocomposite synthesized via a simple and scalable sol-gel method

NASA Astrophysics Data System (ADS)

Zhu, Y.; Apostoluk, A.; Gautier, P.; Valette, A.; Omar, L.; Cornier, T.; Bluet, J. M.; Masenelli-Varlot, K.; Daniele, S.; Masenelli, B.

2016-03-01

Intense visible nano-emitters are key objects for many technologies such as single photon source, bio-labels or energy convertors. Chalcogenide nanocrystals have ruled this domain for several decades. However, there is a demand for cheaper and less toxic materials. In this scheme, ZnO nanoparticles have appeared as potential candidates. At the nanoscale, they exhibit crystalline defects which can generate intense visible emission. However, even though photoluminescence quantum yields as high as 60% have been reported, it still remains to get quantum yield of that order of magnitude which remains stable over a long period. In this purpose, we present hybrid ZnO/polyacrylic acid (PAAH) nanocomposites, obtained from the hydrolysis of diethylzinc in presence of PAAH, exhibiting quantum yield systematically larger than 20%. By optimizing the nature and properties of the polymeric acid, the quantum yield is increased up to 70% and remains stable over months. This enhancement is explained by a model based on the hybrid type II heterostructure formed by ZnO/PAAH. The addition of PAAX (X = H or Na) during the hydrolysis of ZnEt2 represents a cost effective method to synthesize scalable amounts of highly luminescent ZnO/PAAX nanocomposites.

Faster search by lackadaisical quantum walk

NASA Astrophysics Data System (ADS)

Wong, Thomas G.

2018-03-01

In the typical model, a discrete-time coined quantum walk searching the 2D grid for a marked vertex achieves a success probability of O(1/log N) in O(√{N log N}) steps, which with amplitude amplification yields an overall runtime of O(√{N} log N). We show that making the quantum walk lackadaisical or lazy by adding a self-loop of weight 4 / N to each vertex speeds up the search, causing the success probability to reach a constant near 1 in O(√{N log N}) steps, thus yielding an O(√{log N}) improvement over the typical, loopless algorithm. This improved runtime matches the best known quantum algorithms for this search problem. Our results are based on numerical simulations since the algorithm is not an instance of the abstract search algorithm.

Biochemical and molecular changes in response to aluminium-stress in highbush blueberry (Vaccinium corymbosum L.).

PubMed

Inostroza-Blancheteau, Claudio; Reyes-Díaz, Marjorie; Aquea, Felipe; Nunes-Nesi, Adriano; Alberdi, Miren; Arce-Johnson, Patricio

2011-09-01

Aluminium (Al) stress is an important factor limiting crop yields in acid soils. Despite this, very little is known about the mechanisms of resistance to this stress in woody plants. To understand the mechanisms of Al-toxicity and response in blueberries, we compared the impact of Al-stress in Al-resistant and Al-sensitive genotypes using Vaccinium corymbosum L. (Ericaceae) as a plant model. We investigated the effect of Al-stress on the physiological performance, oxidative metabolism and expression of genes that encode antioxidant enzymes in two V. corymbosum cultivars maintained hydroponically with AlCl(3) (0 and 100 μM). Microscopic analyses of Al-treated root tips suggested a higher degree of Al-induced morphological injury in Bluegold (sensitive genotype) compared to Brigitta (resistant genotype). Furthermore, the results indicated that Brigitta had a greater ability to control oxidative stress under Al-toxicity, as reflected by enhancement of several antioxidative and physiological properties (radical scavenging activity: RSA, superoxide dismutase: SOD and catalase: CAT; maximum quantum yield: Fv/Fm, effective quantum yield: ФPSII, electron transport rate: ETR and non-photochemical quenching: NPQ). Finally, we analyzed the expression of genes homologous to GST and ALDH, which were identified in a global expression analysis. In the resistant genotype, the expression of these genes in response to Al-stress was greater in leaves than in roots. Copyright © 2011 Elsevier Masson SAS. All rights reserved.

Developing a diagnostic model for estimating terrestrial vegetation gross primary productivity using the photosynthetic quantum yield and Earth Observation data.

PubMed

Ogutu, Booker O; Dash, Jadunandan; Dawson, Terence P

2013-09-01

This article develops a new carbon exchange diagnostic model [i.e. Southampton CARbon Flux (SCARF) model] for estimating daily gross primary productivity (GPP). The model exploits the maximum quantum yields of two key photosynthetic pathways (i.e. C3 and C4 ) to estimate the conversion of absorbed photosynthetically active radiation into GPP. Furthermore, this is the first model to use only the fraction of photosynthetically active radiation absorbed by photosynthetic elements of the canopy (i.e. FAPARps ) rather than total canopy, to predict GPP. The GPP predicted by the SCARF model was comparable to in situ GPP measurements (R(2)  > 0.7) in most of the evaluated biomes. Overall, the SCARF model predicted high GPP in regions dominated by forests and croplands, and low GPP in shrublands and dry-grasslands across USA and Europe. The spatial distribution of GPP from the SCARF model over Europe and conterminous USA was comparable to those from the MOD17 GPP product except in regions dominated by croplands. The SCARF model GPP predictions were positively correlated (R(2)  > 0.5) to climatic and biophysical input variables indicating its sensitivity to factors controlling vegetation productivity. The new model has three advantages, first, it prescribes only two quantum yield terms rather than species specific light use efficiency terms; second, it uses only the fraction of PAR absorbed by photosynthetic elements of the canopy (FAPARps ) hence capturing the actual PAR used in photosynthesis; and third, it does not need a detailed land cover map that is a major source of uncertainty in most remote sensing based GPP models. The Sentinel satellites planned for launch in 2014 by the European Space Agency have adequate spectral channels to derive FAPARps at relatively high spatial resolution (20 m). This provides a unique opportunity to produce global GPP operationally using the Southampton CARbon Flux (SCARF) model at high spatial resolution. © 2013 John Wiley & Sons Ltd.

(11-22) semipolar InGaN emitters from green to amber on overgrown GaN on micro-rod templates

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

Bai, J., E-mail: j.bai@sheffield.ac.uk; Xu, B.; Guzman, F. G.

2015-12-28

We demonstrate semipolar InGaN single-quantum-well light emitting diodes (LEDs) in the green, yellow-green, yellow and amber spectral region. The LEDs are grown on our overgrown semipolar (11-22) GaN on micro-rod array templates, which are fabricated on (11-22) GaN grown on m-plane sapphire. Electroluminescence measurements on the (11-22) green LED show a reduced blue-shift in the emission wavelength with increasing driving current, compared to a reference commercial c-plane LED. The blue-shifts for the yellow-green and yellow LEDs are also significantly reduced. All these suggest an effective suppression in quantum confined Stark effect in our (11-22) LEDs. On-wafer measurements yield a linearmore » increase in the light output with the current, and external quantum efficiency demonstrates a significant improvement in the efficiency-droop compared to a commercial c-plane LED. Electro-luminescence polarization measurements show a polarization ratio of about 25% in our semipolar LEDs.« less

Quantizing the Toda lattice

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

Siddharthan, R.; Shastry, B.S.

In this work we study the quantum Toda lattice, developing the asymptotic Bethe ansatz method first used by Sutherland. Despite its known limitations we find, on comparing with Gutzwiller{close_quote}s exact method, that it works well in this particular problem and in fact becomes exact as {h_bar} grows large. We calculate ground state and excitation energies for finite-sized lattices, identify excitations as phonons and solitons on the basis of their quantum numbers, and find their dispersions. These are similar to the classical dispersions for small {h_bar}, and remain similar all the way up to {h_bar}=1, but then deviate substantially as wemore » go farther into the quantum regime. On comparing the sound velocities for various {h_bar} obtained thus with that predicted by conformal theory we conclude that the Bethe ansatz gives the energies per particle accurate to O(1/N{sup 2}). On that assumption we can find correlation functions. Thus the Bethe ansatz method can be used to yield much more than the thermodynamic properties which previous authors have calculated. {copyright} {ital 1997} {ital The American Physical Society}« less

Two Hymenophyllaceae species from contrasting natural environments exhibit a homoiochlorophyllous strategy in response to desiccation stress.

PubMed

Flores-Bavestrello, Alejandra; Król, Marianna; Ivanov, Alexander G; Hüner, Norman P A; García-Plazaola, José Ignacio; Corcuera, Luis J; Bravo, León A

2016-02-01

Hymenophyllaceae is a desiccation tolerant family of Pteridophytes which are poikilohydric epiphytes. Their fronds are composed by a single layer of cells and lack true mesophyll cells and stomata. Although they are associated with humid and shady environments, their vertical distribution varies along the trunk of the host plant with some species inhabiting the drier sides with a higher irradiance. The aim of this work was to compare the structure and function of the photosynthetic apparatus during desiccation and rehydration in two species, Hymenophyllum dentatum and Hymenoglossum cruentum, isolated from a contrasting vertical distribution along the trunk of their hosts. Both species were subjected to desiccation and rehydration kinetics to analyze frond phenotypic plasticity, as well as the structure, composition and function of the photosynthetic apparatus. Minimal differences in photosynthetic pigments were observed upon dehydration. Measurements of ϕPSII (effective quantum yield of PSII), ϕNPQ (quantum yield of the regulated energy dissipation of PSII), ϕNO (quantum yield of non-regulated energy dissipation of PSII), and TL (thermoluminescence) indicate that both species convert a functional photochemical apparatus into a structure which exhibits maximum quenching capacity in the dehydrated state with minimal changes in photosynthetic pigments and polypeptide compositions. This dehydration-induced conversion in the photosynthetic apparatus is completely reversible upon rehydration. We conclude that H. dentatum and H. cruentum are homoiochlorophyllous with respect to desiccation stress and exhibited no correlation between inherent desiccation tolerance and the vertical distribution along the host tree trunk. Copyright © 2015 Elsevier GmbH. All rights reserved.

Phototransformation of anthraquinone-2-sulphonate in aqueous solution.

PubMed

Bedini, Andrea; De Laurentiis, Elisa; Sur, Babita; Maurino, Valter; Minero, Claudio; Brigante, Marcello; Mailhot, Gilles; Vione, Davide

2012-09-01

Anthraquinone-2-sulphonate (AQ2S) is a triplet sensitiser that has recently been used to model the photoreactivity of chromophoric dissolved organic matter (CDOM). We show that the photolysis quantum yield of AQ2S under UVA irradiation varies from (3.4 ± 0.2) × 10(-3) at μM AQ2S levels to (1.8 ± 0.1) × 10(-2) at 3 mM AQ2S (μ±σ). This trend is consistent with a combination of direct phototransformation and transformation sensitised by a photogenerated reactive species. In both cases a transient water adduct of AQ2S would be involved. Depending on the initial quinone concentration, the adduct could undergo transformation, give back ground-state AQ2S or react with it. The prevalence of the latter process at high AQ2S concentration would account for the increased values of the photolysis quantum yield. When using AQ2S as a triplet sensitiser, one should not exceed an initial concentration of 0.1 mM. Under the latter conditions the sensitised process is negligible compared to the direct photolysis, providing a simpler system to be studied, and the photolysis quantum yield is independent of the initial AQ2S concentration. This paper also shows, by adoption of density functional theory calculations, that the triplet state of AQ2S has most of the spin density localised on C[double bond, length as m-dash]O, analogous to other photoactive quinones, which accounts for the oxidising character of the triplet state that tends to be reduced to a semiquinone radical.

Structural control of InP/ZnS core/shell quantum dots enables high-quality white LEDs.

PubMed

Kumar, Baskaran Ganesh; Sadeghi, Sadra; Melikov, Rustamzhon; Aria, Mohammad Mohammadi; Jalali, Houman Bahmani; Ow-Yang, Cleva W; Nizamoglu, Sedat

2018-08-24

Herein, we demonstrate that the structural and optical control of InP-based quantum dots (QDs) can lead to high-performance light-emitting diodes (LEDs). Zinc sulphide (ZnS) shells passivate the InP QD core and increase the quantum yield in green-emitting QDs by 13-fold and red-emitting QDs by 8-fold. The optimised QDs are integrated in the liquid state to eliminate aggregation-induced emission quenching and we fabricated white LEDs with a warm, neutral and cool-white appearance by the down-conversion mechanism. The QD-functionalized white LEDs achieve luminous efficiency (LE) up to 14.7 lm W -1 and colour-rendering index up to 80. The structural and optical control of InP/ZnS core/shell QDs enable 23-fold enhancement in LE of white LEDs compared to ones containing only QDs of InP core.

High power cascade diode lasers emitting near 2 μm

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

Hosoda, Takashi; Feng, Tao; Shterengas, Leon, E-mail: leon.shterengas@stonybrook.edu

2016-03-28

High-power two-stage cascade GaSb-based type-I quantum well diode lasers emitting near 2 μm were designed and fabricated. Coated devices with cavity length of 3 mm generated about 2 W of continuous wave power from 100-μm-wide aperture at the current of 6 A. The power conversion efficiency peaked at 20%. Carrier recycling between quantum well gain stages was realized using band-to-band tunneling in GaSb/AlSb/InAs heterostructure complemented with optimized electron and hole injector regions. Design optimization eliminated parasitic optical absorption and thermionic emission, and included modification of the InAs quantum wells of electron and composition and doping profile of hole injectors. Utilization of the cascade pumpingmore » scheme yielded 2 μm lasers with improved output power and efficiency compared to existing state-of-the-art diodes.« less

Strategy for synthesizing quantum dot-layered double hydroxide nanocomposites and their enhanced photoluminescence and photostability.

PubMed

Cho, Seungho; Jung, Sungwook; Jeong, Sanghwa; Bang, Jiwon; Park, Joonhyuck; Park, Youngrong; Kim, Sungjee

2013-01-08

Layered double hydroxide-quantum dot (LDH-QD) composites are synthesized via a room temperature LDH formation reaction in the presence of QDs. InP/ZnS (core/shell) QD, a heavy metal free QD, is used as a model constituent. Interactions between QDs (with negative zeta potentials), decorated with dihydrolipoic acids, and inherently positively charged metal hydroxide layers of LDH during the LDH formations are induced to form the LDH-QD composites. The formation of the LDH-QD composites affords significantly enhanced photoluminescence quantum yields and thermal- and photostabilities compared to their QD counterparts. In addition, the fluorescence from the solid LDH-QD composite preserved the initial optical properties of the QD colloid solution without noticeable deteriorations such as red-shift or deep trap emission. Based on their advantageous optical properties, we also demonstrate the pseudo white light emitting diode, down-converted by the LDH-QD composites.

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

Orfield, Noah J.; McBride, James R.; Wang, Feng

Physical variations in colloidal nanostructures give rise to heterogeneity in expressed optical behavior. This correlation between nanoscale structure and function demands interrogation of both atomic structure and photophysics at the level of single nanostructures to be fully understood. In this paper, by conducting detailed analyses of fine atomic structure, chemical composition, and time-resolved single-photon photoluminescence data for the same individual nanocrystals, we reveal inhomogeneity in the quantum yields of single nonblinking “giant” CdSe/CdS core/shell quantum dots (g-QDs). We find that each g-QD possesses distinctive single exciton and biexciton quantum yields that result mainly from variations in the degree of charging,more » rather than from volume or structure inhomogeneity. We further establish that there is a very limited nonemissive “dark” fraction (<2%) among the studied g-QDs and present direct evidence that the g-QD core must lack inorganic passivation for the g-QD to be “dark”. Finally and therefore, in contrast to conventional QDs, ensemble photoluminescence quantum yield is principally defined by charging processes rather than the existence of dark g-QDs.« less

Quantum state-resolved probing of strong-field-ionized xenon atoms using femtosecond high-order harmonic transient absorption spectroscopy.

PubMed

Loh, Zhi-Heng; Khalil, Munira; Correa, Raoul E; Santra, Robin; Buth, Christian; Leone, Stephen R

2007-04-06

Femtosecond high-order harmonic transient absorption spectroscopy is used to resolve the complete |j,m quantum state distribution of Xe+ produced by optical strong-field ionization of Xe atoms at 800 nm. Probing at the Xe N4/5 edge yields a population distribution rhoj,|m| of rho3/2,1/2ratiorho1/2,1/2ratiorho3/2,3/2=75+/-6 :12+/-3 :13+/-6%. The result is compared to a tunnel ionization calculation with the inclusion of spin-orbit coupling, revealing nonadiabatic ionization behavior. The sub-50-fs time resolution paves the way for tabletop extreme ultraviolet absorption probing of ultrafast dynamics.

Strongly Coupled Tin-Halide Perovskites to Modulate Light Emission: Tunable 550-640 nm Light Emission (FWHM 36-80 nm) with a Quantum Yield of up to 6.4.

PubMed

Chen, Min-Yi; Lin, Jin-Tai; Hsu, Chia-Shuo; Chang, Chung-Kai; Chiu, Ching-Wen; Chen, Hao Ming; Chou, Pi-Tai

2018-05-01

Colloidal perovskite quantum dots represent one of the most promising materials for applications in solar cells and photoluminescences. These devices require a low density of crystal defects and a high yield of photogenerated carriers, which are difficult to realize in tin-halide perovskite because of the intrinsic instability of tin during nucleation. Here, an enhancement in the luminescent property of tin-halide perovskite nanoplates (TPNPs) that are composed of strongly coupled layered structures with the chemical formula of PEA 2 SnX 4 (PEA = C 6 H 5 (CH 2 ) 2 NH 3 , X = Br, I) is reported. TPNPs (X = I) show an emission at a wavelength of 640 nm, with high quantum yield of 6.40 ± 0.14% and full width at half maximum (FWHM) as small as 36 nm. The presence of aliphatic carboxylic acid is found to play a key role in reducing the tin perovskite defect density, which significantly improves the emission intensity and stability of TPNPs. Upon mixing iodo- and bromo- precursors, the emission wavelength is successfully tuned from 640 nm (PEA 2 SnI 4 ) to 550 nm (PEA 2 SnBr 4 ), with a corresponding emission quantum yield and FWHM of 0.16-6.40% and 36-80 nm, respectively. The results demonstrate a major advance for the emission yield and tunability of tin-halide perovskites. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photoswitchable Fluorescent Diarylethene Derivatives with Thiophene 1,1-Dioxide Groups: Effect of Alkyl Substituents at the Reactive Carbons

PubMed Central

Sumi, Takaki; Irie, Masahiro

2017-01-01

Photoswitching and fluorescent properties of sulfone derivatives of 1,2-bis(2-alkyl-4-methyl-5-phenyl-3-thienyl)perfluorocyclopentene, 1–5, having methyl, ethyl, n-propyl, i-propyl, and i-butyl substituents at the reactive carbons (2- and 2′-positions) of the thiophene 1,1-dioxide rings were studied. Diarylethenes 1–5 underwent isomerization reactions between open-ring and closed-ring forms upon alternate irradiation with ultraviolet (UV) and visible light and showed fluorescence in the closed-ring forms. The alkyl substitution at the reactive carbons affects the fluorescent property of the closed-ring isomers. The closed-ring isomers 2b–5b with ethyl, n-propyl, i-propyl, and i-butyl substituents show higher fluorescence quantum yields than 1b with methyl substituents. In polar solvents, the fluorescence quantum yield of 1b markedly decreases, while 2b–5b maintain the relatively high fluorescence quantum yields. Although the cycloreversion quantum yields of the derivatives with methyl, ethyl, n-propyl, and i-propyl substituents are quite low and in the order of 10−5, introduction of i-butyl substituents was found to increase the yield up to the order of 10−3. These results indicate that appropriate alkyl substitution at the reactive carbons is indispensable for properly controlling the photoswitching and fluorescent properties of the photoswitchable fluorescent diarylethenes, which are potentially applicable to super-resolution fluorescence microscopies. PMID:28869489

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

Mthethwa, T.P.; Moloto, M.J., E-mail: mmoloto@uj.ac.za; De Vries, A.

Graphical abstract: SEM images of CdS/PMMA showing coiling as loading of CdS nanoparticles is increased. Thermal stability is increased with increase in %loading of both CdS and CdSe nanoparticles. Research highlights: {yields} TOPO-capped CdS and HDA-capped CdSe nanoparticles were synthesized and fully characterized. {yields} The nanoparticles were mixed with the polymer, PMMA using electrospinning technique using 2, 5 and 10% weight loadings. {yields} The mixture was spun to produce fibres with optical and thermal properties showing significant change and also the increase in loading causing bending or spiraling. {yields} Both TEM images for nanoparticles and SEM for fibres shows themore » morphology and sizes of the particles. -- Abstract: Electrospinning technique was used to fabricate poly(methyl methacrylate) (PMMA) fibres incorporating CdS and CdSe quantum dots (nanoparticles). Different nanoparticle loadings (2, 5 and 10 wt% with respect to PMMA) were used and the effect of the quantum dots on the properties of the fibres was studied. The optical properties of the hybrid composite fibres were investigated by photoluminescence and UV-vis spectrophotometry. Scanning electron microscopy (SEM), X-ray diffraction and FTIR spectrophotometry were also used to investigate the morphology and structure of the fibres. The optical studies showed that the size-tunable optical properties can be achieved in the polymer fibres by addition of quantum dots. SEM images showed that the morphologies of the fibres were dependent on the added amounts of quantum dots. A spiral type of morphology was observed with an increase in the concentration of CdS and CdSe nanoparticles. Less beaded structures and bigger diameter fibres were obtained at higher quantum dot concentrations. X-ray diffractometry detected the amorphous peaks of the polymer and even after the quantum dots were added and the FTIR analysis shows that there was no considerable interaction between the quantum dots and the polymer fibres at low concentration of quantum dots however at higher concentrations some interactions were observed which shows that QDs were present on the surfaces of the fibres.« less

High-Z Nanoparticle/Polymer Nanocomposites for Gamma-Ray Scintillation Detectors

NASA Astrophysics Data System (ADS)

Liu, Chao

An affordable and reliable solution for spectroscopic gamma-ray detection has long been sought after due to the needs from research, defense, and medical applications. Scintillators resolve gamma energy by proportionally converting a single high-energy photon into a number of photomultiplier-tube-detectable low-energy photons, which is considered a more affordable solution for general purposes compared to the delicate semiconductor detectors. An ideal scintillator should simultaneously exhibit the following characteristics: 1) high atomic number (Z) for high gamma stopping power and photoelectron production; 2) high light yield since the energy resolution is inversely proportional to the square root of light yield; 3) short emission decay lifetime; and 4) low cost and scalable production. However, commercial scintillators made from either inorganic single crystals or plastics fail to satisfy all requirements due to their intrinsic material properties and fabrication limitations. The concept of adding high-Z constituents into plastic scintillators to harness high Z, low cost, and fast emission in the resulting nanocomposite scintillators is not new in and of itself. Attempts have been made by adding organometallics, quantum dots, and scintillation nanocrystals into the plastic matrix. High-Z organometallics have long been used to improve the Z of plastic scintillators; however, their strong spin-orbit coupling effect entails careful triplet energy matching using expensive triplet emitters to avoid severe quenching of the light yield. On the other hand, reported quantum dot- and nanocrystal-polymer nanocomposites suffer from moderate Z and high optical loss due to aggregation and self-absorption at loadings higher than 10 wt%, limiting their potential for practical application. This dissertation strives to improve the performance of nanoparticle-based nanocomposite scintillators. One focus is to synthesize transparent nanocomposites with higher loadings of high-Z inorganic nanoparticles. A facile single-precursor method is first developed to synthesize HfO2 nanoparticles, the highest-Z simple oxide with band gap larger than polyvinyltoluene, with uniform size distribution around 5 nm. A nanoparticle-surface-modification protocol is then developed for the fabrication of transparent nanocomposite monoliths with high nanoparticle loadings (up to 40 wt%). Using this method, transparent HfO2-loaded blue-emitting nanocomposite scintillators (2 mm thick, transmittance at 550 nm >75%) have been fabricated capable of producing a full energy photopeak for 662 keV gamma rays, with the best deconvoluted photopeak energy resolution < 8%, representing a significant improvement over previous nanoparticle-based nanocomposite scintillators. Although the HfO2 work represents a great improvement over previous reports, it is also found in this system that the light yield deteriorates at higher nanoparticle loadings. This is attributed to the trapping of fast electron energy deposited in the non-emitting nanoparticles. To overcome this deterioration issue, a revisit to the previously proposed quantum-dot-loaded nanocomposite scintillator is made with significant improvements. Transparent, ultra-high-loading (up to 60 wt%) CdxZn1-xS/ZnS core/shell quantum dot/polymer nanocomposite monoliths are first synthesized by in situ copolymerization of the partially mathacrylate-functionalized quantum dots in a monomer solution. With efficient Forster resonance energy transfer from the high-atomic-number quantum dots to lower-band-gap organic dyes, quantum-dot-borne excitons are extracted for photon production. The resulting nanocomposites thus exhibit unprecedented simultaneous enhancements in both light yield (visible photons produced per MeV of gamma photon energy) and gamma attenuation power. In a best demonstration, a 60 wt% quantum-dot nanocomposite scintillator exhibits a light yield of 9255 photons/MeV and a photopeak resolution of 9.8% under 662 keV Cs-137 gamma irradiation, demonstrating the potential of this model system for future high-performance low-cost spectroscopic gamma detectors.

A synchronous game for binary constraint systems

NASA Astrophysics Data System (ADS)

Kim, Se-Jin; Paulsen, Vern; Schafhauser, Christopher

2018-03-01

Recently, Slofstra proved that the set of quantum correlations is not closed. We prove that the set of synchronous quantum correlations is not closed, which implies his result, by giving an example of a synchronous game that has a perfect quantum approximate strategy but no perfect quantum strategy. We also exhibit a graph for which the quantum independence number and the quantum approximate independence number are different. We prove new characterisations of synchronous quantum approximate correlations and synchronous quantum spatial correlations. We solve the synchronous approximation problem of Dykema and the second author, which yields a new equivalence of Connes' embedding problem in terms of synchronous correlations.

Raising yield potential in wheat: increasing photosynthesis capacity and efficiency

USDA-ARS?s Scientific Manuscript database

Increasing wheat yields to help to ensure food security is a major challenge. Meeting this challenge requires a quantum improvement in the yield potential of wheat. Past increases in yield potential have largely resulted from improvements in harvest index not through increased biomass. Further large...

Correlation complementarity yields bell monogamy relations.

PubMed

Kurzyński, P; Paterek, T; Ramanathan, R; Laskowski, W; Kaszlikowski, D

2011-05-06

We present a method to derive Bell monogamy relations by connecting the complementarity principle with quantum nonlocality. The resulting monogamy relations are stronger than those obtained from the no-signaling principle alone. In many cases, they yield tight quantum bounds on the amount of violation of single and multiple qubit correlation Bell inequalities. In contrast with the two-qubit case, a rich structure of possible violation patterns is shown to exist in the multipartite scenario.

The effect of axial ligands on the quantum yield of singlet oxygen of new silicon phthalocyanine

NASA Astrophysics Data System (ADS)

Lv, Huafei; Zhang, Xuemei; Yu, Xinxin; Pan, Sujuan; Xie, Shusen; Yang, Hongqin; Peng, Yiru

2016-10-01

The singlet oxygen (1O2) production abilitity is an important factor to assess their potential as effective of photosensitizers. In this paper, the 1O2 production rate, production rate constant and quantum yield of silicon(IV) phthalocyanine axially bearing 1-3 generation dendritic substituents were evaluated by a high performance liquid chromatographic method. The results show that the 1O2 production rate and production rate constant of these compounds increase gradually with dendritic generations increase. And the 1O2 quantum yield of silicon(IV) phthalocyanine with first generation dendritic ligand was the highest. This may be due to the isolation effect of the dendritic ligands on the phthalocyanine core. The parameters of the observed 1O2 production properties will provide valuable data for these dendrimer phthalocyanines as promising photosensitizer in PDT application.

Photochemical studies of a fluorescent chlorophyll catabolite--source of bright blue fluorescence in plant tissue and efficient sensitizer of singlet oxygen.

PubMed

Jockusch, Steffen; Turro, Nicholas J; Banala, Srinivas; Kräutler, Bernhard

2014-02-01

Fluorescent chlorophyll catabolites (FCCs) are fleeting intermediates of chlorophyll breakdown, which is seen as an enzyme controlled detoxification process of the chlorophylls in plants. However, some plants accumulate large amounts of persistent FCCs, such as in senescent leaves and in peels of yellow bananas. The photophysical properties of such a persistent FCC (Me-sFCC) were investigated in detail. FCCs absorb in the near UV spectral region and show blue fluorescence (max at 437 nm). The Me-sFCC fluorescence had a quantum yield of 0.21 (lifetime 1.6 ns). Photoexcited Me-sFCC intersystem crosses into the triplet state (quantum yield 0.6) and generates efficiently singlet oxygen (quantum yield 0.59). The efficient generation of singlet oxygen makes fluorescent chlorophyll catabolites phototoxic, but might also be useful as a (stress) signal and for defense of the plant tissue against infection by pathogens.

Fundamental Quantum 1/F Noise in Ultrasmall Semiconductor Devices and Their Optimal Design Principles

DTIC Science & Technology

1988-05-31

Hooge parameter. 2. 1 / f Noise of the Recombination Current Generated in the Depletion Region The quantum i/ f ...theory. There are two forms of quantum 11f noise . In the first place C~ and Cn4 p n to quantum 1 / f noise theory. This would yield Hooge parameters S...Fundamental Quantum 1 / f Noise in Ultrasmall S~ iodcrD’vesadOtm.Dsgn P in. 12. PERSONAL AUTHOR(S) Handel, Peter H. (Princioal investiaat r) 13a. TYPE

Proceedings of the Quantum Computation for Physical Modeling Workshop 2004. Held in North Falmouth, MA on 12-15 September 2004

DTIC Science & Technology

2005-10-01

late the difficulty of some basic 1-bit and n-bit quantum and classical operations in an simple unconstrained scenario. KEY WORDS: Time evolution... quantum circuit and design are presented for an optimized entangling probe attacking the BB84 Protocol of quantum key distribution (QKD) and yielding...unambiguous, at least some of the time. It follows that the BB84 (Bennett-Brassard 1984) proto- col of quantum key distribution has a vulnerability similar to

Interaction of Water-Soluble CdTe Quantum Dots with Bovine Serum Albumin

PubMed Central

2011-01-01

Semiconductor nanoparticles (quantum dots) are promising fluorescent markers, but it is very little known about interaction of quantum dots with biological molecules. In this study, interaction of CdTe quantum dots coated with thioglycolic acid (TGA) with bovine serum albumin was investigated. Steady state spectroscopy, atomic force microscopy, electron microscopy and dynamic light scattering methods were used. It was explored how bovine serum albumin affects stability and spectral properties of quantum dots in aqueous media. CdTe–TGA quantum dots in aqueous solution appeared to be not stable and precipitated. Interaction with bovine serum albumin significantly enhanced stability and photoluminescence quantum yield of quantum dots and prevented quantum dots from aggregating. PMID:27502633

New evidence for primordial action site of Fluazifop-P-butyl on Acanthospermum hispidum seedlings: From the effects on chlorophyll fluorescence characteristics and histological observation.

PubMed

Shang, Yuhong; Yang, Congjun; Liu, Zhihang; Song, Jiqing; Li, Pingliang; Li, Lingxu; Zhou, Fei; Xin, Hua; Wan, Fanghao; Matsumoto, Hiroshi; Luo, Xiaoyong

2017-10-01

Acanthospermum hispidum DC, an Asteraceae weed species, was very susceptible to fluazifop-P-butyl, but tolerant to other aryloxyphenoxypropionate herbicides, such as haloxyfop-P-methyl. However, other Asteraceae weeds including Bidens pilosa were all tolerant to fluazifop-P-butyl. Membrane lipid peroxidation by increasing the levels of reactive oxygen species (ROS) was proposed as an action mechanism of fluazifop-P-butyl in A. hispidum. To further clarify the primordial action site of fluazifop-P-butyl in this species, the effects on chlorophyll fluorescence characteristics and cytohistology of apical meristems were studied. Chlorophyll fluorescence characteristics (CFC) in sensitive A. hispidum seedlings were markedly affected by 10μM fluazifop-P-butyl, with the dark fluorescence yield (Fo), maximal fluorescence yield (Fm), maximal PS II quantum yield (Fv/Fm), effective photosystem II (PS II) quantum yield [Y(II)], and quantum yield of regulated energy dissipation [Y(NPQ)] declining, quantum yield of nonregulated energy dissipation [Y(NO)] rising, but these measures were not affected in Bidens pilosa. The effects of fluazifop-P-butyl on chlorophyll fluorescence properties were observed on the growing point before the mature leaves by about 4-6h. Haloxyfop-P-methyl, a control herbicide, had no effects on CFC of either A. hispidum or B. pilosa. In addition, damage to apical meristem cells of A. hispidum was observed at 6 HAT prior to changes in chlorophyll fluorescence parameters suggesting that the primary action site of fluazifop-P-butyl in this species is in the apical meristem and the effects on CFC may be the results of secondary action. Copyright © 2017 Elsevier Inc. All rights reserved.

Can time-dependent density functional theory predict intersystem crossing in organic chromophores? A case study on benzo(bis)-X-diazole based donor-acceptor-donor type molecules.

PubMed

Tam, Teck Lip Dexter; Lin, Ting Ting; Chua, Ming Hui

2017-06-21

Here we utilized new diagnostic tools in time-dependent density functional theory to explain the trend of intersystem crossing in benzo(bis)-X-diazole based donor-acceptor-donor type molecules. These molecules display a wide range of fluorescence quantum yields and triplet yields, making them excellent candidates for testing the validity of these diagnostic tools. We believe that these tools are cost-effective and can be applied to structurally similar organic chromophores to predict/explain the trends of intersystem crossing, and thus fluorescence quantum yields and triplet yields without the use of complex and expensive multireference configuration interaction or multireference pertubation theory methods.

Quantum coherence effects in natural light-induced processes: cis-trans photoisomerization of model retinal under incoherent excitation.

PubMed

Tscherbul, Timur V; Brumer, Paul

2015-12-14

We present a theoretical study of quantum coherence effects in the primary cis-trans photoisomerization of retinal in rhodopsin induced by incoherent solar light. Using the partial secular Bloch-Redfield quantum master equation approach based on a two-state two-mode linear vibronic coupling model of the retinal chromophore [S. Hahn and G. Stock, J. Phys. Chem. B, 2000, 104, 1146-1149], we show that a sudden turn-on of incoherent pumping can generate substantial Fano coherences among the excited states of retinal. These coherences are the most pronounced in the regime where the matrix elements of the transition dipole moment between the ground and excited eigenstates are parallel to one another. We show that even when the transition dipole moments are perpendicular (implying the absence of light-induced Fano coherence) a small amount of excited-state coherence is still generated due to the coupling to intramolecular vibrational modes and the protein environment, causing depopulation of the excited eigenstates. The overall effect of the coherences on the steady-state population and on the photoproduct quantum yield is shown to be small; however we observe a significant transient effect on the formation of the trans photoproduct, enhancing the photoreaction quantum yield by ∼11% at 200 fs. These calculations suggest that coupling to intramolecular vibrational modes and the protein environment play an important role in photoreaction dynamics, suppressing oscillations in the quantum yield associated with Fano interference.

Lunisolar tidal force and its relationship to chlorophyll fluorescence in Arabidopsis thaliana.

PubMed

Fisahn, Joachim; Klingelé, Emile; Barlow, Peter

2015-01-01

The yield of chlorophyll fluorescence Ft was measured in leaves of Arabidopsis thaliana over periods of several days under conditions of continuous illumination (LL) without the application of saturating light pulses. After linearization of the time series of the chlorophyll fluorescence yield (ΔFt), oscillations became apparent with periodicities in the circatidal range. Alignments of these linearized time series ΔFt with the lunisolar tidal acceleration revealed high degrees of synchrony and phase congruence. Similar congruence with the lunisolar tide was obtained with the linearized quantum yield of PSII (ΔФII), recorded after application of saturating light pulses. These findings strongly suggest that there is an exogenous timekeeper which is a stimulus for the oscillations detected in both the linearized yield of chlorophyll fluorescence (ΔFt) and the linearized quantum yield of PSII (ΔФII).

Lunisolar tidal force and its relationship to chlorophyll fluorescence in Arabidopsis thaliana

PubMed Central

Fisahn, Joachim; Klingelé, Emile; Barlow, Peter

2015-01-01

The yield of chlorophyll fluorescence Ft was measured in leaves of Arabidopsis thaliana over periods of several days under conditions of continuous illumination (LL) without the application of saturating light pulses. After linearization of the time series of the chlorophyll fluorescence yield (ΔFt), oscillations became apparent with periodicities in the circatidal range. Alignments of these linearized time series ΔFt with the lunisolar tidal acceleration revealed high degrees of synchrony and phase congruence. Similar congruence with the lunisolar tide was obtained with the linearized quantum yield of PSII (ΔФII), recorded after application of saturating light pulses. These findings strongly suggest that there is an exogenous timekeeper which is a stimulus for the oscillations detected in both the linearized yield of chlorophyll fluorescence (ΔFt) and the linearized quantum yield of PSII (ΔФII). PMID:26376108

A Time-Dependent Quantum Dynamics Study of the H2 + CH3 yields H + CH4 Reaction

NASA Technical Reports Server (NTRS)

Wang, Dunyou; Kwak, Dochan (Technical Monitor)

2002-01-01

We present a time-dependent wave-packet propagation calculation for the H2 + CH3 yields H + CH4 reaction in six degrees of freedom and for zero total angular momentum. Initial state selected reaction probability for different initial rotational-vibrational states are presented in this study. The cumulative reaction probability (CRP) is obtained by summing over initial-state-selected reaction probability. The energy-shift approximation to account for the contribution of degrees of freedom missing in the 6D calculation is employed to obtain an approximate full-dimensional CRP. Thermal rate constant is compared with different experiment results.

High quantum yield of the Egyptian blue family of infrared phosphors (MCuSi4O10, M = Ca, Sr, Ba)

NASA Astrophysics Data System (ADS)

Berdahl, Paul; Boocock, Simon K.; Chan, George C.-Y.; Chen, Sharon S.; Levinson, Ronnen M.; Zalich, Michael A.

2018-05-01

The alkaline earth copper tetra-silicates, blue pigments, are interesting infrared phosphors. The Ca, Sr, and Ba variants fluoresce in the near-infrared (NIR) at 909, 914, and 948 nm, respectively, with spectral widths on the order of 120 nm. The highest quantum yield ϕ reported thus far is ca. 10%. We use temperature measurements in sunlight to determine this parameter. The yield depends on the pigment loading (mass per unit area) ω with values approaching 100% as ω → 0 for the Ca and Sr variants. Although maximum quantum yield occurs near ω = 0, maximum fluorescence occurs near ω = 70 g m-2, at which ϕ = 0.7. The better samples show fluorescence decay times in the range of 130 to 160 μs. The absorbing impurity CuO is often present. Good phosphor performance requires long fluorescence decay times and very low levels of parasitic absorption. The strong fluorescence enhances prospects for energy applications such as cooling of sunlit surfaces (to reduce air conditioning requirements) and luminescent solar concentrators.

Temporal variability in chlorophyll fluorescence of back-reef corals in Ofu, American Samoa

USGS Publications Warehouse

Piniak, G.A.; Brown, E.K.

2009-01-01

Change in the yield of chlorophyll a fluorescence is a common indicator of thermal stress in corals. The present study reports temporal variability in quantum yield measurements for 10 coral species in Ofu, American Samoa - a place known to experience elevated and variable seawater temperatures. In winter, the zooxanthellae generally had higher dark-adapted maximum quantum yield (F v/Fm), higher light- adapted effective quantum yield (??F/F'm), and lower relative electron transport rates (rETR) than in the summer. Temporal changes appeared unrelated to the expected bleaching sensitivity of corals. All species surveyed, with the exception of Montipora grisea, demonstrated significant temporal changes in the three fluorescence parameters. Fluorescence responses were influenced by the microhabitat - temporal differences in fluorescence parameters were usually observed in the habitat with a more variable temperature regime (pool 300), while differences in Fv/Fm between species were observed only in the more environmentally stable habitat (pool 400). Such species-specific responses and microhabitat variability should be considered when attempting to determine whether observed in situ changes are normal seasonal changes or early signs of bleaching. ?? 2009 Marine Biological Laboratory.

Photodynamic therapy potential of thiol-stabilized CdTe quantum dot-group 3A phthalocyanine conjugates (QD-Pc).

PubMed

Tekdaş, Duygu Aydın; Durmuş, Mahmut; Yanık, Hülya; Ahsen, Vefa

2012-07-01

Thiol stabilized CdTe quantum dot (QD) nanoparticles were synthesized in aqueous phase and were used as energy donors to tetra-triethyleneoxythia substituted aluminum, gallium and indium phthalocyanines through fluorescence resonance energy transfer (FRET). Energy transfer occurred from the QDs to phthalocyanines upon photoexcitation of the QDs. An enhancement in efficiency of energy transfer with the nature of the carboxylic thiol stabilizer on the QDs was observed. As a result of the nanoparticle and the phthalocyanine mixing, the photoluminescence efficiency of the phthalocyanine moieties in the mixtures does not strictly follow the quantum yields of the bare phthalocyanines. The photochemistry study of phthalocyanines in the presence of the QDs revealed high singlet oxygen quantum yield, hence the possibility of using QDs in combination with phthalocyanines as photosensitizers in photodynamic therapy of cancer. The fluorescence of the CdTe quantum dots-phthalocyanine conjugates (QDs-Pc) were effectively quenched by addition of 1,4-benzoquinone. Copyright © 2012 Elsevier B.V. All rights reserved.

Scalable focused ion beam creation of nearly lifetime-limited single quantum emitters in diamond nanostructures

PubMed Central

Schröder, Tim; Trusheim, Matthew E.; Walsh, Michael; Li, Luozhou; Zheng, Jiabao; Schukraft, Marco; Sipahigil, Alp; Evans, Ruffin E.; Sukachev, Denis D.; Nguyen, Christian T.; Pacheco, Jose L.; Camacho, Ryan M.; Bielejec, Edward S.; Lukin, Mikhail D.; Englund, Dirk

2017-01-01

The controlled creation of defect centre—nanocavity systems is one of the outstanding challenges for efficiently interfacing spin quantum memories with photons for photon-based entanglement operations in a quantum network. Here we demonstrate direct, maskless creation of atom-like single silicon vacancy (SiV) centres in diamond nanostructures via focused ion beam implantation with ∼32 nm lateral precision and <50 nm positioning accuracy relative to a nanocavity. We determine the Si+ ion to SiV centre conversion yield to be ∼2.5% and observe a 10-fold conversion yield increase by additional electron irradiation. Low-temperature spectroscopy reveals inhomogeneously broadened ensemble emission linewidths of ∼51 GHz and close to lifetime-limited single-emitter transition linewidths down to 126±13 MHz corresponding to ∼1.4 times the natural linewidth. This method for the targeted generation of nearly transform-limited quantum emitters should facilitate the development of scalable solid-state quantum information processors. PMID:28548097

Scalable focused ion beam creation of nearly lifetime-limited single quantum emitters in diamond nanostructures

DOE PAGES

Schroder, Tim; Trusheim, Matthew E.; Walsh, Michael; ...

2017-05-26

The controlled creation of defect centre—nanocavity systems is one of the outstanding challenges for efficiently interfacing spin quantum memories with photons for photon-based entanglement operations in a quantum network. Here we demonstrate direct, maskless creation of atom-like single silicon vacancy (SiV) centres in diamond nanostructures via focused ion beam implantation with ~32 nm lateral precision and <50 nm positioning accuracy relative to a nanocavity. We determine the Si+ ion to SiV centre conversion yield to be ~2.5% and observe a 10-fold conversion yield increase by additional electron irradiation. Low-temperature spectroscopy reveals inhomogeneously broadened ensemble emission linewidths of ~51 GHz andmore » close to lifetime-limited single-emitter transition linewidths down to 126±13 MHz corresponding to ~1.4 times the natural linewidth. Furthermore, this method for the targeted generation of nearly transform-limited quantum emitters should facilitate the development of scalable solid-state quantum information processors.« less

Scalable focused ion beam creation of nearly lifetime-limited single quantum emitters in diamond nanostructures

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

Schroder, Tim; Trusheim, Matthew E.; Walsh, Michael

The controlled creation of defect centre—nanocavity systems is one of the outstanding challenges for efficiently interfacing spin quantum memories with photons for photon-based entanglement operations in a quantum network. Here we demonstrate direct, maskless creation of atom-like single silicon vacancy (SiV) centres in diamond nanostructures via focused ion beam implantation with ~32 nm lateral precision and <50 nm positioning accuracy relative to a nanocavity. We determine the Si+ ion to SiV centre conversion yield to be ~2.5% and observe a 10-fold conversion yield increase by additional electron irradiation. Low-temperature spectroscopy reveals inhomogeneously broadened ensemble emission linewidths of ~51 GHz andmore » close to lifetime-limited single-emitter transition linewidths down to 126±13 MHz corresponding to ~1.4 times the natural linewidth. Furthermore, this method for the targeted generation of nearly transform-limited quantum emitters should facilitate the development of scalable solid-state quantum information processors.« less

Improved Charge-Transfer Fluorescent Dyes

NASA Technical Reports Server (NTRS)

Meador, Michael

2005-01-01

Improved charge-transfer fluorescent dyes have been developed for use as molecular probes. These dyes are based on benzofuran nuclei with attached phenyl groups substituted with, variously, electron donors, electron acceptors, or combinations of donors and acceptors. Optionally, these dyes could be incorporated as parts of polymer backbones or as pendant groups or attached to certain surfaces via self-assembly-based methods. These dyes exhibit high fluorescence quantum yields -- ranging from 0.2 to 0.98, depending upon solvents and chemical structures. The wavelengths, quantum yields, intensities, and lifetimes of the fluorescence emitted by these dyes vary with (and, hence, can be used as indicators of) the polarities of solvents in which they are dissolved: In solvents of increasing polarity, fluorescence spectra shift to longer wavelengths, fluorescence quantum yields decrease, and fluorescence lifetimes increase. The wavelengths, quantum yields, intensities, and lifetimes are also expected to be sensitive to viscosities and/or glass-transition temperatures. Some chemical species -- especially amines, amino acids, and metal ions -- quench the fluorescence of these dyes, with consequent reductions in intensities, quantum yields, and lifetimes. As a result, the dyes can be used to detect these species. Another useful characteristic of these dyes is a capability for both two-photon and one-photon absorption. Typically, these dyes absorb single photons in the ultraviolet region of the spectrum (wavelengths < 400 nm) and emit photons in the long-wavelength ultraviolet, visible, and, when dissolved in some solvents, near-infrared regions. In addition, these dyes can be excited by two-photon absorption at near-infrared wavelengths (600 to 800 nm) to produce fluorescence spectra identical to those obtained in response to excitation by single photons at half the corresponding wavelengths (300 to 400 nm). While many prior fluorescent dyes exhibit high quantum yields, solvent-polarity- dependent fluorescence behavior, susceptibility to quenching by certain chemical species, and/or two-photon fluorescence, none of them has the combination of all of these attributes. Because the present dyes do have all of these attributes, they have potential utility as molecular probes in a variety of applications. Examples include (1) monitoring curing and deterioration of polymers; (2) monitoring protein expression; (3) high-throughput screening of drugs; (4) monitoring such chemical species as glucose, amines, amino acids, and metal ions; and (5) photodynamic therapy of cancers and other diseases.

Quantum dots/silica/polymer nanocomposite films with high visible light transmission and UV shielding properties

NASA Astrophysics Data System (ADS)

Mumin, Md Abdul; Xu, William Z.; Charpentier, Paul A.

2015-08-01

The dispersion of light-absorbing inorganic nanomaterials in transparent plastics such as poly(ethylene-co-vinyl acetate) (PEVA) is of enormous current interest in emerging solar materials, including photovoltaic (PV) modules and commercial greenhouse films. Nanocrystalline semiconductor or quantum dots (QDs) have the potential to absorb UV light and selectively emit visible light, which can control plant growth in greenhouses or enhance PV panel efficiencies. This work provides a new and simple approach for loading mesoporous silica-encapsulated QDs into PEVA. Highly luminescent CdS and CdS-ZnS core-shell QDs with 5 nm size were synthesized using a modified facile approach based on pyrolysis of the single-molecule precursors and capping the CdS QDs with a thin layer of ZnS. To make both the bare and core-shell structure QDs more resistant against photochemical reactions, a mesoporous silica layer was grown on the QDs through a reverse microemulsion technique based on hydrophobic interactions. By careful experimental tuning, this encapsulation technique enhanced the quantum yield (˜65%) and photostability compared to the bare QDs. Both the encapsulated bare and core-shell QDs were then melt-mixed with EVA pellets using a mini twin-screw extruder and pressed into thin films with controlled thickness. The results demonstrated for the first time that mesoporous silica not only enhanced the quantum yield and photostability of the QDs but also improved the compatibility and dispersibility of QDs throughout the PEVA films. The novel light selective films show high visible light transmission (˜90%) and decreased UV transmission (˜75%).

Quantum dots/silica/polymer nanocomposite films with high visible light transmission and UV shielding properties.

PubMed

Mumin, Md Abdul; Xu, William Z; Charpentier, Paul A

2015-08-07

The dispersion of light-absorbing inorganic nanomaterials in transparent plastics such as poly(ethylene-co-vinyl acetate) (PEVA) is of enormous current interest in emerging solar materials, including photovoltaic (PV) modules and commercial greenhouse films. Nanocrystalline semiconductor or quantum dots (QDs) have the potential to absorb UV light and selectively emit visible light, which can control plant growth in greenhouses or enhance PV panel efficiencies. This work provides a new and simple approach for loading mesoporous silica-encapsulated QDs into PEVA. Highly luminescent CdS and CdS-ZnS core-shell QDs with 5 nm size were synthesized using a modified facile approach based on pyrolysis of the single-molecule precursors and capping the CdS QDs with a thin layer of ZnS. To make both the bare and core-shell structure QDs more resistant against photochemical reactions, a mesoporous silica layer was grown on the QDs through a reverse microemulsion technique based on hydrophobic interactions. By careful experimental tuning, this encapsulation technique enhanced the quantum yield (∼65%) and photostability compared to the bare QDs. Both the encapsulated bare and core-shell QDs were then melt-mixed with EVA pellets using a mini twin-screw extruder and pressed into thin films with controlled thickness. The results demonstrated for the first time that mesoporous silica not only enhanced the quantum yield and photostability of the QDs but also improved the compatibility and dispersibility of QDs throughout the PEVA films. The novel light selective films show high visible light transmission (∼90%) and decreased UV transmission (∼75%).

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

Marseglia, L.; Saha, K.; Ajoy, A.

The practical implementation of quantum technologies such as quantum commu- nication and quantum cryptography relies on the development of indistinguishable, robust, and bright single photon sources that works at room temperature. The silicon- vacancy (SiV -) center in diamond has emerged as a possible candidate for a single photon source with all these characteristics. Unfortunately, due to the high refraction index mismatch between diamond and air, color centers in diamond show low photon out-coupling. This drawback can be overcome by fabrication of photonic structures that improve the in-coupling of excitation laser to the diamond defect as well as the out-couplingmore » emission from the color centers. An additional shortcoming is due to the random localization of native defects in the diamond sample. Here we demonstrate deterministic implantation of Si ions with high conversion effciency to single SiV -, targeted to fabricated nanowires. The co-localization of single SiV - defects with the nanostructures yields a ten times higher light coupling effciency as compared to single SiV - in the bulk. This result, with its intrinsic scalability, enables a new class of devices for integrated photonics and quantum information processing.« less

Photolysis of CH{sub 3}CHO at 248 nm: Evidence of triple fragmentation from primary quantum yield of CH{sub 3} and HCO radicals and H atoms

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

Morajkar, Pranay; Schoemaecker, Coralie; Fittschen, Christa, E-mail: christa.fittschen@univ-lille1.fr

2014-06-07

Radical quantum yields have been measured following the 248 nm photolysis of acetaldehyde, CH{sub 3}CHO. HCO radical and H atom yields have been quantified by time resolved continuous wave Cavity Ring Down Spectroscopy in the near infrared following their conversion to HO{sub 2} radicals by reaction with O{sub 2}. The CH{sub 3} radical yield has been determined using the same technique following their conversion into CH{sub 3}O{sub 2}. Absolute yields have been deduced for HCO radicals and H atoms through fitting of time resolved HO{sub 2} profiles, obtained under various O{sub 2} concentrations, to a complex model, while the CH{submore » 3} yield has been determined relative to the CH{sub 3} yield from 248 nm photolysis of CH{sub 3}I. Time resolved HO{sub 2} profiles under very low O{sub 2} concentrations suggest that another unknown HO{sub 2} forming reaction path exists in this reaction system besides the conversion of HCO radicals and H atoms by reaction with O{sub 2}. HO{sub 2} profiles can be well reproduced under a large range of experimental conditions with the following quantum yields: CH{sub 3}CHO + hν{sub 248nm} → CH{sub 3}CHO{sup *}, CH{sub 3}CHO{sup *} → CH{sub 3} + HCO ϕ{sub 1a} = 0.125 ± 0.03, CH{sub 3}CHO{sup *} → CH{sub 3} + H + CO ϕ{sub 1e} = 0.205 ± 0.04, CH{sub 3}CHO{sup *}→{sup o{sub 2}}CH{sub 3}CO + HO{sub 2} ϕ{sub 1f} = 0.07 ± 0.01. The CH{sub 3}O{sub 2} quantum yield has been determined in separate experiments as ϕ{sub CH{sub 3}} = 0.33 ± 0.03 and is in excellent agreement with the CH{sub 3} yields derived from the HO{sub 2} measurements considering that the triple fragmentation (R1e) is an important reaction path in the 248 nm photolysis of CH{sub 3}CHO. From arithmetic considerations taking into account the HO{sub 2} and CH{sub 3} measurements we deduce a remaining quantum yield for the molecular pathway: CH{sub 3}CHO{sup *} → CH{sub 4} + CO ϕ{sub 1b} = 0.6. All experiments can be consistently explained with absence of the formerly considered pathway: CH{sub 3}CHO{sup *} → CH{sub 3}CO + H ϕ{sub 1c} = 0.« less

Analysis of doxorubicin distribution in MCF-7 cells treated with drug-loaded nanoparticles by combination of two fluorescence-based techniques, confocal spectral imaging and capillary electrophoresis.

PubMed

Gautier, Juliette; Munnier, Emilie; Soucé, Martin; Chourpa, Igor; Douziech Eyrolles, Laurence

2015-05-01

The intracellular distribution of the antiancer drug doxorubicin (DOX) was followed qualitatively by fluorescence confocal spectral imaging (FCSI) and quantitatively by capillary electrophoresis (CE). FCSI permits the localization of the major fluorescent species in cell compartments, with spectral shifts indicating the polarity of the respective environment. However, distinction between drug and metabolites by FCSI is difficult due to their similar fluorochromes, and direct quantification of their fluorescence is complicated by quantum yield variation between different subcellular environments. On the other hand, capillary electrophoresis with fluorescence detection (CE-LIF) is a quantitative method capable of separating doxorubicin and its metabolites. In this paper, we propose a method for determining drug and metabolite concentration in enriched nuclear and cytosolic fractions of cancer cells by CE-LIF, and we compare these data with those of FCSI. Significant differences in the subcellular distribution of DOX are observed between the drug administered as a molecular solution or as a suspension of drug-loaded iron oxide nanoparticles coated with polyethylene glycol. Comparative analysis of the CE-LIF vs FCSI data may lead to a tentative calibration of this latter method in terms of DOX fluorescence quantum yields in the nucleus and more or less polar regions of the cytosol.

Coupling Light Emitting Diodes with Photocatalyst-Coated Optical Fibers Improves Quantum Yield of Pollutant Oxidation.

PubMed

Ling, Li; Tugaoen, Heather; Brame, Jonathon; Sinha, Shahnawaz; Li, Chuanhao; Schoepf, Jared; Hristovski, Kiril; Kim, Jae-Hong; Shang, Chii; Westerhoff, Paul

2017-11-21

A photocatalyst-coated optical fiber was coupled with a 318 nm ultraviolet-A light emitting diode, which activated the photocatalysts by interfacial photon-electron excitation while minimizing photonic energy losses due to conventional photocatalytic barriers. The light delivery mechanism was explored via modeling of evanescent wave energy produced upon total internal reflection and photon refraction into the TiO 2 surface coating. This work explores aqueous phase LED-irradiated optical fibers for treating organic pollutants and for the first time proposes a dual-mechanistic approach to light delivery and photocatalytic performance. Degradation of a probe organic pollutant was evaluated as a function of optical fiber coating thickness, fiber length, and photocatalyst attachment method and compared against the performance of an equivalent catalyst mass in a completely mixed slurry reactor. Measured and simulated photon fluence through the optical fibers decreased as a function of fiber length, coating thickness, or TiO 2 mass externally coated on the fiber. Thinner TiO 2 coatings achieved faster pollutant removal rates from solution, and dip coating performed better than sol-gel attachment methods. TiO 2 attached to optical fibers achieved a 5-fold higher quantum yield compared against an equivalent mass of TiO 2 suspended in a slurry solution.

Use of the fluorescence quantum yield for the determination of the number-average molecular weight of polymers of epicatechin with 4β→8 interflavin bonds

Treesearch

D. Cho; W.L. Mattice; L.J. Porter; Richard W. Hemingway

1989-01-01

Excitation at 280 nm produces a structureless emission band with a maximum at 321-324 nm for dilute solutions of catechin, epicatechin, and their oligomers in l,4-dioxane or water. The fluorescence quantum yield, Q, has been measured in these two solvents for five dimers, a trimer, a tetramer, a pentamer, a hexamer, and a polymer in which the monomer...

Photoisomerization of alfa calcidol by a sensitized quantum chain reaction.

PubMed

Estruch, Gastón A; Aramendía, Pedro F

2012-01-01

The production of vitamin D3 is a pharmaceutically relevant process, producing high added-value products. Precursors are extracts from vegetal origin but bearing mainly an E geometry in the 5,6 double bond. The synthesis of vitamin D3 (5-E-α-calcidol) with the correct Z stereochemistry in the 5,6 double bond from the E isomer using anthracene and triethylamine (TEA) as the sensitizer system was studied from the kinetic and mechanistic point of view. The sensitized isomerization of E-calcidol by irradiation of anthracene takes place only in deoxygenated solution and yields the Z isomer in ca 5% yield in the photostationary state. When TEA is added to the system, the E-Z reaction is not inhibited by oxygen any more, the quantum yield of photoisomerization to the Z isomer grows linearly with the concentration of E-calcidol, while conversions higher than 95% to the Z isomer are reached in the photostationary state and E-Z quantum yields as high as 45 at [E-calcidol] = 25 mM are reached. If TEA is replaced by 1,4-diazabicyclo[2.2.2]octane, the reaction rate drops to one-third at the same amine concentration. The observations can be explained by a quantum chain reaction mechanism. The high conversion achieved eliminates the need of isomer separation. © 2011 Wiley Periodicals, Inc. Photochemistry and Photobiology © 2011 The American Society of Photobiology.

Excitation-emission spectra and fluorescence quantum yields for fresh and aged biogenic secondary organic aerosols

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

Lee, Hyun Ji; Laskin, Alexander; Laskin, Julia

2013-05-10

Certain biogenic secondary organic aerosols (SOA) become absorbent and fluorescent when exposed to reduced nitrogen compounds such as ammonia, amines and their salts. Fluorescent SOA may potentially be mistaken for biological particles by detection methods relying on fluorescence. This work quantifies the spectral distribution and effective quantum yields of fluorescence of SOA generated from two monoterpenes, limonene and a-pinene, and two different oxidants, ozone (O3) and hydroxyl radical (OH). The SOA was generated in a smog chamber, collected on substrates, and aged by exposure to ~100 ppb ammonia vapor in air saturated with water vapor. Absorption and excitation-emission matrix (EEM)more » spectra of aqueous extracts of aged and control SOA samples were measured, and the effective absorption coefficients and fluorescence quantum yields (~0.005 for 349 nm excitation) were determined from the data. The strongest fluorescence for the limonene-derived SOA was observed for excitation = 420+- 50 nm and emission = 475 +- 38 nm. The window of the strongest fluorescence shifted to excitation = 320 +- 25 nm and emission = 425 +- 38 nm for the a-pinene-derived SOA. Both regions overlap with the excitation-emission matrix (EEM) spectra of some of the fluorophores found in primary biological aerosols. Our study suggests that, despite the low quantum yield, the aged SOA particles should have sufficient fluorescence intensities to interfere with the fluorescence detection of common bioaerosols.« less

High Photoluminescence Quantum Yield in Band Gap Tunable Bromide Containing Mixed Halide Perovskites.

PubMed

Sutter-Fella, Carolin M; Li, Yanbo; Amani, Matin; Ager, Joel W; Toma, Francesca M; Yablonovitch, Eli; Sharp, Ian D; Javey, Ali

2016-01-13

Hybrid organic-inorganic halide perovskite based semiconductor materials are attractive for use in a wide range of optoelectronic devices because they combine the advantages of suitable optoelectronic attributes and simultaneously low-cost solution processability. Here, we present a two-step low-pressure vapor-assisted solution process to grow high quality homogeneous CH3NH3PbI3-xBrx perovskite films over the full band gap range of 1.6-2.3 eV. Photoluminescence light-in versus light-out characterization techniques are used to provide new insights into the optoelectronic properties of Br-containing hybrid organic-inorganic perovskites as a function of optical carrier injection by employing pump-powers over a 6 orders of magnitude dynamic range. The internal luminescence quantum yield of wide band gap perovskites reaches impressive values up to 30%. This high quantum yield translates into substantial quasi-Fermi level splitting and high "luminescence or optically implied" open-circuit voltage. Most importantly, both attributes, high internal quantum yield and high optically implied open-circuit voltage, are demonstrated over the entire band gap range (1.6 eV ≤ Eg ≤ 2.3 eV). These results establish the versatility of Br-containing perovskite semiconductors for a variety of applications and especially for the use as high-quality top cell in tandem photovoltaic devices in combination with industry dominant Si bottom cells.

Excitation-emission spectra and fluorescence quantum yields for fresh and aged biogenic secondary organic aerosols.

PubMed

Lee, Hyun Ji Julie; Laskin, Alexander; Laskin, Julia; Nizkorodov, Sergey A

2013-06-04

Certain biogenic secondary organic aerosols (SOA) become absorbent and fluorescent when exposed to reduced nitrogen compounds such as ammonia, amines, and their salts. Fluorescent SOA may potentially be mistaken for biological particles by detection methods relying on fluorescence. This work quantifies the spectral distribution and effective quantum yields of fluorescence of water-soluble SOA generated from two monoterpenes, limonene and α-pinene, and two different oxidants, ozone (O3) and hydroxyl radical (OH). The SOA was generated in a smog chamber, collected on substrates, and aged by exposure to ∼100 ppb ammonia in air saturated with water vapor. Absorption and excitation-emission matrix (EEM) spectra of aqueous extracts of aged and control SOA samples were measured, and the effective absorption coefficients and fluorescence quantum yields (∼0.005 for 349 nm excitation) were determined from the data. The strongest fluorescence for the limonene-derived SOA was observed for λexcitation = 420 ± 50 nm and λemission = 475 ± 38 nm. The window of the strongest fluorescence shifted to λexcitation = 320 ± 25 nm and λemission = 425 ± 38 nm for the α-pinene-derived SOA. Both regions overlap with the EEM spectra of some of the fluorophores found in primary biological aerosols. Despite the low quantum yield, the aged SOA particles may have sufficient fluorescence intensities to interfere with the fluorescence detection of common bioaerosols.

Synthesis of Nitrogen- and Chlorine-Doped Graphene Quantum Dots for Cancer Cell Imaging.

PubMed

Nafiujjaman, Md; Joon, Hwang; Kwak, Kwang Soo; Lee, Yong-Kyu

2018-06-01

In this study, we synthesized high quantum yield nitrogen and chlorine-doped graphene quantum dots (Cl-GQDs-N) for cancer cell imaging using simple and high production yield hydrothermal method from low-cost fructose. Prepared Cl-GQDs-N are about 30 nm in diameter and these Cl-GQDs-N display powerful blue color photoluminescence under the 365 nm UV lamp. We have further investigated their optical performances under various conditions. In vitro study shows no toxicity effect in normal and cancer cells treated with Cl-GQDs-N. Finally, we believe that our synthesized Cl-GQDs-N will bring more application opportunities in the field of bioimaging, optoelectronics and beyond.

State-selected chemical reaction dynamics at the S matrix level - Final-state specificities of near-threshold processes at low and high energies

NASA Technical Reports Server (NTRS)

Chatfield, David C.; Truhlar, Donald G.; Schwenke, David W.

1992-01-01

State-to-state reaction probabilities are found to be highly final-state specific at state-selected threshold energies for the reactions O + H2 yield OH + H and H + H2 yield H2 + H. The study includes initial rotational states with quantum numbers 0-15, and the specificity is especially dramatic for the more highly rotationally excited reactants. The analysis is based on accurate quantum mechanical reactive scattering calculations. Final-state specificity is shown in general to increase with the rotational quantum number of the reactant diatom, and the trends are confirmed for both zero and nonzero values of the total angular momentum.

Near-Unity Quantum Yields of Biexciton Emission from CdSe=CdS Nanocrystals Measured Using Single-Particle Spectroscopy

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

Park, Young-Shin; Malko, Anton V.; Vela, Javier

2011-05-03

Biexciton photoluminescence (PL) quantum yields (Q 2X) of individual CdSe/CdS core-shell nanocrystal quantum dots with various shell thicknesses are derived from independent PL saturation and two-photon correlation measurements. We observe a near-unity Q{sub 2X} for some nanocrystals with an ultrathick 19-monolayer shell. High Q 2X’s are, however, not universal and vary widely among nominally identical nanocrystals indicating a significant dependence of Q 2X upon subtle structural differences. Interestingly, our measurements indicate that high Q 2X’s are not required to achieve complete suppression of PL intensity fluctuations in individual nanocrystals.

Stable CdS QDs with intense broadband photoluminescence and high quantum yields

NASA Astrophysics Data System (ADS)

Mandal, Abhijit; Saha, Jony; De, Goutam

2011-11-01

Aqueous synthesis of CdS quantum dots (QDs) using thiolactic acid (TLA) as a capping agent was reported. These QDs exhibited excellent colloidal and photostability over a span of 2 years and showed intense broadband and almost white photoluminescence suitable for solid state lighting devices. The photoluminescence (PL) property of the aqueous CdS QDs is optimized by adjusting various processing parameters. The highest quantum yield (QY) achieved for TLA capped CdS QDs of average size 3.5 nm was ˜50%. Luminescence lifetime measurements of CdS-TLA QDs indicated longer lifetimes and a larger contribution of the surface-related emission, indicating removal of quenching defects.

Peptide-Decorated Tunable-Fluorescence Graphene Quantum Dots.

PubMed

Sapkota, Bedanga; Benabbas, Abdelkrim; Lin, Hao-Yu Greg; Liang, Wentao; Champion, Paul; Wanunu, Meni

2017-03-22

We report here the synthesis of graphene quantum dots with tunable size, surface chemistry, and fluorescence properties. In the size regime 15-35 nm, these quantum dots maintain strong visible light fluorescence (mean quantum yield of 0.64) and a high two-photon absorption (TPA) cross section (6500 Göppert-Mayer units). Furthermore, through noncovalent tailoring of the chemistry of these quantum dots, we obtain water-stable quantum dots. For example, quantum dots with lysine groups bind strongly to DNA in solution and inhibit polymerase-based DNA strand synthesis. Finally, by virtue of their mesoscopic size, the quantum dots exhibit good cell permeability into living epithelial cells, but they do not enter the cell nucleus.

Photochemical processes on Titan: Irradiation of mixtures of gases that simulate Titan's atmosphere

NASA Astrophysics Data System (ADS)

Tran, Buu N.; Joseph, Jeffrey C.; Force, Michael; Briggs, Robert G.; Vuitton, Veronique; Ferris, James P.

2005-09-01

Photochemical reaction pathways in Titan's atmosphere were investigated by irradiation of the individual components and the mixture containing nitrogen, methane, hydrogen, acetylene, ethylene, and cyanoacetylene. The quantum yields for the loss of the reactants and the formation of products were determined. Photolysis of ethylene yields mainly saturated compounds (ethane, propane, and butane) while photolysis of acetylene yields the same saturated compounds as well as ethylene and diacetylene. Irradiation of cyanoacetylene yields mainly hydrogen cyanide and small amounts of acetonitrile. When an amount of methane corresponding to its mixing ratio on Titan was added to these mixtures the quantum yields for the loss of reactants decreased and the quantum yields for hydrocarbon formation increased indicative of a hydrogen atom abstraction from methane by the photochemically generated radicals. GC/MS analysis of the products formed by irradiation of mixtures of all these gases generated over 120 compounds which were mainly aliphatic hydrocarbons containing double and triple bonds along with much smaller amounts of aromatic compounds like benzene, toluene and phenylacetylene. The reaction pathways were investigated by the use of 13C acetylene in these gas mixtures. No polycyclic aromatic compounds were detected. Vapor pressures of these compounds under conditions present in Titan's atmosphere were calculated. The low molecular weight compounds likely to be present in the atmosphere and aerosols of Titan as a result of photochemical processes are proposed.

Bifurcation-based adiabatic quantum computation with a nonlinear oscillator network.

PubMed

Goto, Hayato

2016-02-22

The dynamics of nonlinear systems qualitatively change depending on their parameters, which is called bifurcation. A quantum-mechanical nonlinear oscillator can yield a quantum superposition of two oscillation states, known as a Schrödinger cat state, via quantum adiabatic evolution through its bifurcation point. Here we propose a quantum computer comprising such quantum nonlinear oscillators, instead of quantum bits, to solve hard combinatorial optimization problems. The nonlinear oscillator network finds optimal solutions via quantum adiabatic evolution, where nonlinear terms are increased slowly, in contrast to conventional adiabatic quantum computation or quantum annealing, where quantum fluctuation terms are decreased slowly. As a result of numerical simulations, it is concluded that quantum superposition and quantum fluctuation work effectively to find optimal solutions. It is also notable that the present computer is analogous to neural computers, which are also networks of nonlinear components. Thus, the present scheme will open new possibilities for quantum computation, nonlinear science, and artificial intelligence.

Bifurcation-based adiabatic quantum computation with a nonlinear oscillator network

NASA Astrophysics Data System (ADS)

Goto, Hayato

2016-02-01

The dynamics of nonlinear systems qualitatively change depending on their parameters, which is called bifurcation. A quantum-mechanical nonlinear oscillator can yield a quantum superposition of two oscillation states, known as a Schrödinger cat state, via quantum adiabatic evolution through its bifurcation point. Here we propose a quantum computer comprising such quantum nonlinear oscillators, instead of quantum bits, to solve hard combinatorial optimization problems. The nonlinear oscillator network finds optimal solutions via quantum adiabatic evolution, where nonlinear terms are increased slowly, in contrast to conventional adiabatic quantum computation or quantum annealing, where quantum fluctuation terms are decreased slowly. As a result of numerical simulations, it is concluded that quantum superposition and quantum fluctuation work effectively to find optimal solutions. It is also notable that the present computer is analogous to neural computers, which are also networks of nonlinear components. Thus, the present scheme will open new possibilities for quantum computation, nonlinear science, and artificial intelligence.

Effects of surface and interface traps on exciton and multi-exciton dynamics in core/shell quantum dots

NASA Astrophysics Data System (ADS)

Bozio, Renato; Righetto, Marcello; Minotto, Alessandro

2017-08-01

Exciton interactions and dynamics are the most important factors determining the exceptional photophysical properties of semiconductor quantum dots (QDs). In particular, best performances have been obtained for ingeniously engineered core/shell QDs. We have studied two factors entering in the exciton decay dynamics with adverse effects for the luminescence efficiency: exciton trapping at surface and interface traps, and non-radiative Auger recombination in QDs carrying either net charges or multiple excitons. In this work, we present a detailed study into the optical absorption, fluorescence dynamics and quantum yield, as well as ultrafast transient absorption properties of CdSe/CdS, CdSe/Cd0.5Zn0.5S, and CdSe/ZnS QDs as a function of shell thickness. It turns out that de-trapping processes play a pivotal role in determining steady state emission properties. By studying the excitation dependent photoluminescence quantum yields (PLQY) in different CdSe/CdxZn1-xS (x = 0, 0.5, 1) QDs, we demonstrate the different role played by hot and cold carrier trapping rates in determining fluorescence quantum yields. Finally, the use of global analysis allows us untangling the complex ultrafast transient absorption signals. Smoothing of interface potential, together with effective surface passivation, appear to be crucial factors in slowing down both Auger-based and exciton trapping recombination processes.

Synthesis and characterization of (3-Aminopropyl)trimethoxy-silane (APTMS) functionalized Gd2O3:Eu(3+) red phosphor with enhanced quantum yield.

PubMed

Jain, Akhil; Hirata, G A; Farías, M H; Castillón, F F

2016-02-12

We report the surface modification of nanocrystalline Gd2O3:Eu(3+) phosphor by (3-Aminopropyl)trimethoxysilane (APTMS). The nanoparticles were first coated with silica using the Stöber process, and then annealed at 650 °C for 2 h. Afterwards, APTMS was functionalized onto the silica layer to obtain Gd2O3:Eu(3+) nanoparticles bearing amine groups on the surface. The effect of silica coating, and the subsequent annealing process on the crystallization of the nanophosphor were analyzed by x-ray diffraction (XRD). High-resolution transmission electron microscopy (HR-TEM) confirmed the presence of a silica layer of ∼45 nm thickness. X-ray photoelectron (XPS) and Fourier transform infrared (FTIR) spectroscopy confirmed the presence of silica and the amine groups. Photoluminescence (PL) analysis demonstrated an increased emission after functionalization of nanoparticles. Absolute quantum yield (QY) measurements revealed an 18% enhancement in QY in functionalized nanoparticles compared with unmodified nanoparticles, which is of great importance for their biomedical applications.

Synthesis and characterization of (3-Aminopropyl)trimethoxy-silane (APTMS) functionalized Gd2O3:Eu3+ red phosphor with enhanced quantum yield

NASA Astrophysics Data System (ADS)

Jain, Akhil; Hirata, G. A.; Farías, M. H.; Castillón, F. F.

2016-02-01

We report the surface modification of nanocrystalline Gd2O3:Eu3+ phosphor by (3-Aminopropyl)trimethoxysilane (APTMS). The nanoparticles were first coated with silica using the Stöber process, and then annealed at 650 °C for 2 h. Afterwards, APTMS was functionalized onto the silica layer to obtain Gd2O3:Eu3+ nanoparticles bearing amine groups on the surface. The effect of silica coating, and the subsequent annealing process on the crystallization of the nanophosphor were analyzed by x-ray diffraction (XRD). High-resolution transmission electron microscopy (HR-TEM) confirmed the presence of a silica layer of ∼45 nm thickness. X-ray photoelectron (XPS) and Fourier transform infrared (FTIR) spectroscopy confirmed the presence of silica and the amine groups. Photoluminescence (PL) analysis demonstrated an increased emission after functionalization of nanoparticles. Absolute quantum yield (QY) measurements revealed an 18% enhancement in QY in functionalized nanoparticles compared with unmodified nanoparticles, which is of great importance for their biomedical applications.

Emitting color tunable carbon dots by adjusting solvent towards light-emitting devices

NASA Astrophysics Data System (ADS)

Zhu, Jinyang; Bai, Xue; Bai, Jialin; Pan, Gencai; Zhu, Yongsheng; Zhai, Yue; Shao, He; Chen, Xu; Dong, Biao; Zhang, Hanzhuang; Song, Hongwei

2018-02-01

Carbon dots (CDs), one of the most significant classes of carbon-based nanophosphors, have attracted extensive attention in recent years. However, few attempts have been reported for realizing CDs with tunable emissions, especially for obtaining the red-light emissions with high photoluminescence quantum yields. Herein, we synthesized CDs with different chromatic blue, green and red emissions by facilely changing the reaction solvent during hydrothermal conditions. The photoluminescence quantum yields of 34%, 19% and 47% for the blue, green and red emissions, respectively, were achieved. Furthermore, the solid-state CD/PVA composite films were constructed through mixing the CDs with PVA polymer, in which the self-quenching of photoluminescence of CDs had been successfully avoided benefiting from the formation of hydrogen bonds between the CDs and PVA molecules. Finally, the warm white light emitting diode (WLED) was fabricated by integrating CD/PVA film on a UV-LED chip. The WLED exhibited the Commission International de l’Eclairage coordinates (CIE) of (0.38, 0.34), correlated color temperature of 3913 K and color rendering index of 91, respectively, which were comparable with the commercial WLEDs.

Photophysicochemical properties and photodynamic therapy activity of highly water-soluble Zn(II) phthalocyanines.

PubMed

Oluwole, David O; Sarı, Fatma Aslıhan; Prinsloo, Earl; Dube, Edith; Yuzer, Abdulcelil; Nyokong, Tebello; Ince, Mine

2018-05-29

The syntheses of two zinc(II) phthalocyanines (ZnPcs) having either imidazole (ZnPc 1) or pyridiloxy (ZnPc 2) moieties as their macrocycle substituents are reported. Quaternization of the ZnPcs with methyl iodide afforded water soluble cationic phthalocyanines. The photophysical, photochemical properties and photodynamic therapy (PDT) activity of the ZnPcs were studied in solution. The fluorescence quantum yield and lifetime of ZnPc 1 were higher as compared to ZnPc 2. ZnPc 2 afforded higher triplet state (Φ T ) and singlet oxygen quantum yields (Φ Δ ) in comparison to ZnPc 1. The PDT activity of ZnPcs was investigated against human breast adenocarcinoma cells (MCF-7). The two compounds afforded a very minimal in vitro dark cytotoxicity with 85% viable cells at concentration ≤80 μM. On irradiation of the cells having the ZnPcs, ≥50% cell death was recorded for ZnPc 1 which was also evidenced by the cells photo-micrograph. Copyright © 2018 Elsevier B.V. All rights reserved.

Synthesis and fluorescence properties of some difluoroboron β-diketonate complexes and composite containing PMMA

NASA Astrophysics Data System (ADS)

Xing, Dongye; Hou, Yanjun; Niu, Haijun

2018-03-01

A series of difluoroboron β-diketonate complexes, containing the indon-β-diketonate ligand carrying methyl or methoxyl substituents was synthesized. The crystal structures of the complexes were confirmed by single crystal X-ray diffraction studies. The fluorescence properties of compounds were studied in solution state, solid state and on PMMA polymer matrix. The photophysical data of compounds 2a-2d exhibited strong fluorescence and photostability under the ultraviolet light (Hg lamp). The complex 2b showed higher fluorescence intensity in solution state as compared to other complexes of the series. The complexes 2c and 2d showed higher fluorescence intensity in the solid state, which are ascribed to the stronger π-π interactions between ligands in the solid state. The introduction of methoxyl or methyl groups on the benzene rings enhanced the absorption intensity, emission intensity, quantum yields and fluorescence lifetimes due to their electron-donating nature. Furthermore, the complex 2b was doped into the PMMA to produce hybrid materials, where the PMMA matrix acted as sensitizer for the central boron ion to enhance the fluorescence emission intensity and quantum yields.

Luminescent carbon quantum dots with high quantum yield as a single white converter for white light emitting diodes

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

Feng, X. T.; Zhang, Y.; Liu, X. G., E-mail: liuxuguang@tyut.edu.cn

Carbon quantum dots (CQDs) with high quantum yield (51.4%) were synthesized by a one-step hydrothermal method using thiosalicylic acid and ethylenediamine as precursor. The CQDs have the average diameter of 2.3 nm and possess excitation-independent emission wavelength in the range from 320 to 440 nm excitation. Under an ultraviolet (UV) excitation, the CQDs aqueous solutions emit bright blue fluorescence directly and exhibit broad emission with a high spectral component ratio of 67.4% (blue to red intensity to total intensity). We applied the CQDs as a single white-light converter for white light emitting diodes (WLEDs) using a UV-LED chip as the excitation lightmore » source. The resulted WLED shows superior performance with corresponding color temperature of 5227 K and the color coordinates of (0.34, 0.38) belonging to the white gamut.« less

Near-unity quantum yields from chloride treated CdTe colloidal quantum dots

DOE PAGES

Page, Robert C.; Espinobarro-Velazquez, Daniel; Leontiadou, Marina A.; ...

2014-10-27

Colloidal quantum dots (CQDs) are promising materials for novel light sources and solar energy conversion. However, trap states associated with the CQD surface can produce non-radiative charge recombination that significantly reduces device performance. Here a facile post-synthetic treatment of CdTe CQDs is demonstrated that uses chloride ions to achieve near-complete suppression of surface trapping, resulting in an increase of photoluminescence (PL) quantum yield (QY) from ca. 5% to up to 97.2 ± 2.5%. The effect of the treatment is characterised by absorption and PL spectroscopy, PL decay, scanning transmission electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy. We find thismore » process also dramatically improves the air-stability of the CQDs: before treatment the PL is largely quenched after 1 hour of air-exposure, whilst the treated samples showed a PL QY of nearly 50% after more than 12 hours.« less

Application of JAERI quantum molecular dynamics model for collisions of heavy nuclei

NASA Astrophysics Data System (ADS)

Ogawa, Tatsuhiko; Hashimoto, Shintaro; Sato, Tatsuhiko; Niita, Koji

2016-06-01

The quantum molecular dynamics (QMD) model incorporated into the general-purpose radiation transport code PHITS was revised for accurate prediction of fragment yields in peripheral collisions. For more accurate simulation of peripheral collisions, stability of the nuclei at their ground state was improved and the algorithm to reject invalid events was modified. In-medium correction on nucleon-nucleon cross sections was also considered. To clarify the effect of this improvement on fragmentation of heavy nuclei, the new QMD model coupled with a statistical decay model was used to calculate fragment production cross sections of Ag and Au targets and compared with the data of earlier measurement. It is shown that the revised version can predict cross section more accurately.

O+OH-->O(2)+H: A key reaction for interstellar chemistry. New theoretical results and comparison with experiment.

PubMed

Lique, F; Jorfi, M; Honvault, P; Halvick, P; Lin, S Y; Guo, H; Xie, D Q; Dagdigian, P J; Kłos, J; Alexander, M H

2009-12-14

We report extensive, fully quantum, time-independent (TID) calculations of cross sections at low collision energies and rate constants at low temperatures for the O+OH reaction, of key importance in the production of molecular oxygen in cold, dark, interstellar clouds and in the chemistry of the Earth's atmosphere. Our calculations are compared with TID calculations within the J-shifting approximation, with wave-packet calculations, and with quasiclassical trajectory calculations. The fully quantum TID calculations yield rate constants higher than those from the more approximate methods and are qualitatively consistent with a low-temperature extrapolation of earlier experimental values but not with the most recent experiments at the lowest temperatures.

Photodissociation of HBr/LiF(001): A quantum mechanical model

NASA Technical Reports Server (NTRS)

Seideman, Tamar

1993-01-01

The photodissociation dynamics of HBr adsorbed on a LiF(001) surface is studied using time-independent quantum mechanics. The photodissociation lineshape and the Br(P(sub 1/2)-2)/Br(P(sub 3/2)-2) yield ratio are computed and compared with the corresponding quantities for gas phase photodissociation. The angular distribution of the hydrogen photofragments following excitation of adsorbed HBr is computed and found to agree qualitatively with experimental data. The effect of polarization of the photon is illustrated and discussed. The field polarization is found to affect significantly the magnitude of the photodissociation signal but not the angular dependence of the photofragment distribution, in agreement with experiment and in accord with expectations for a strongly aligned adsorbed phase.

Photodissociation of HBr/LiF(001) - A quantum mechanical model

NASA Technical Reports Server (NTRS)

Seideman, Tamar

1993-01-01

The photodissociation dynamics of HBr adsorbed on an LiF(001) surface is studied using time-independent quantum mechanics. The photodissociation line shape and the Br(2P(1/2))/Br(2P(3/2)) yield ratio are computed and compared with the corresponding quantities for gas phase photodissociation. The angular distribution of the hydrogen photofragments following excitation of adsorbed HBr is computed and found to agree qualitatively with experimental data. The effect of polarization of the photon is illustrated and discussed. We find the field polarization to affect significantly the magnitude of the photodissociation signal but not the angular dependence of the photofragment distribution, in agreement with experiment and in accord with expectations for a strongly aligned adsorbed phase.

Phytoplankton natural fluorescence variability in the Sargasso Sea

NASA Astrophysics Data System (ADS)

Westberry, T. K.; Siegel, D. A.

2003-03-01

Phytoplankton fluorescence has been used historically as a means of assessing phytoplankton biomass, rates of primary production (PP) and physiological status in laboratory, in situ, and satellite based investigations. Assumptions about the quantum yield of phytoplankton fluorescence, φf, are often overlooked and can become problematic when fluorescence based methods are applied. A time series of φf observations from the northwestern Sargasso Sea is presented with the goal of understanding the controls on fluorescence and its applicability for assessing upper ocean biological processes. Accurate estimates of φf require accounting for Raman scattering and the conversion of planar to scalar irradiance. Variability in φf occurs on both seasonal and episodic time scales. Seasonal variations show maxima in the surface layer during summer months while lower, more uniform values are found throughout the winter when deep mixing occurs. Large episodic variations in φf are observed throughout the record which dwarf seasonal changes. Predictions of depth-dependent and depth-integrated PP rates using φf and natural fluorescence fluxes are only marginally successful ( r2˜50%), although comparable with results from global bio-optical models for the Sargasso Sea. Improvements in PP predictions are hindered by weak statistical relationships with other parameters. φf is largely decoupled from the quantum yield of carbon assimilation, φc, indicating that an inverse relationship between fluorescence and photosynthesis does not exist. Consequently, variability in the quantum yield of thermal de-excitation, φh, is found to be of similar magnitude as φf on the timescales observed. These observations show that assumptions about photochemical energy flow through the phytoplankton community must be made carefully and that the fluorescence-photosynthesis relationship is not straightforward.

Combined low temperature-high light effects on gas exchange properties of jojoba leaves.

PubMed

Loreto, F; Bongi, G

1989-12-01

Jojoba (Simmondsia chinensis [Link] Schneider) is an important crop in desert climates. A relatively high frequency of periods of chilling and high photon flux density (PFD) in this environment makes photoinhibition likely, resulting in a reduction of assimilation capacity in overwintering leaves. This could explain the low net photosynthesis found in shoots from the field (4-6 micromoles per square meter per second) when compared to greenhouse grown plants (12-15 micromoles per square meter per second). The responses of photosynthesis and stomatal conductance to changes in absorbed PFD and in substomatal partial pressure of CO(2) were measured on jojoba leaves recovering from chilling temperature (4 degrees C) in high or low PFD. No measurable gas exchange was found immediately after chilling in either high or low PFD. For leaves chilled in low PFD, the original quantum yield was restored after 24 hours. The time course of recovery from chilling in high PFD was much longer. Quantum yield recovered to 60% of its original value in 72 hours but failed to recover fully after 1 week. Measurements of PSII chlorophyll fluorescence at 77 K showed that the reduced quantum yield was caused by photoinhibition. The ratio of variable to maximal fluorescence fell from a control level of 0.82 to 0.41 after the photoinhibitory treatment and recovery was slow. We also found a large increase in net assimilation rate and little closure of stomata as CO(2) was increased from ambient partial pressure of 35 to 85 pascals. For plants grown in full light, the increase in net assimilation rate was 100%. The photosynthetic response at high CO(2) concentration may constitute an ecological advantage of jojoba as a crop in the future.

Combined Low Temperature-High Light Effects on Gas Exchange Properties of Jojoba Leaves 1

PubMed Central

Loreto, Francesco; Bongi, Guido

1989-01-01

Jojoba (Simmondsia chinensis [Link] Schneider) is an important crop in desert climates. A relatively high frequency of periods of chilling and high photon flux density (PFD) in this environment makes photoinhibition likely, resulting in a reduction of assimilation capacity in overwintering leaves. This could explain the low net photosynthesis found in shoots from the field (4-6 micromoles per square meter per second) when compared to greenhouse grown plants (12-15 micromoles per square meter per second). The responses of photosynthesis and stomatal conductance to changes in absorbed PFD and in substomatal partial pressure of CO2 were measured on jojoba leaves recovering from chilling temperature (4°C) in high or low PFD. No measurable gas exchange was found immediately after chilling in either high or low PFD. For leaves chilled in low PFD, the original quantum yield was restored after 24 hours. The time course of recovery from chilling in high PFD was much longer. Quantum yield recovered to 60% of its original value in 72 hours but failed to recover fully after 1 week. Measurements of PSII chlorophyll fluorescence at 77 K showed that the reduced quantum yield was caused by photoinhibition. The ratio of variable to maximal fluorescence fell from a control level of 0.82 to 0.41 after the photoinhibitory treatment and recovery was slow. We also found a large increase in net assimilation rate and little closure of stomata as CO2 was increased from ambient partial pressure of 35 to 85 pascals. For plants grown in full light, the increase in net assimilation rate was 100%. The photosynthetic response at high CO2 concentration may constitute an ecological advantage of jojoba as a crop in the future. PMID:16667220

Method for resurrecting negative electron affinity photocathodes after exposure to an oxidizing gas

DOEpatents

Mulhollan, Gregory A; Bierman, John C

2012-10-30

A method by which negative electron affinity photocathodes (201), single crystal, amorphous, or otherwise ordered, can be made to recover their quantum yield following exposure to an oxidizing gas has been discovered. Conventional recovery methods employ the use of cesium as a positive acting agent (104). In the improved recovery method, an electron beam (205), sufficiently energetic to generate a secondary electron cloud (207), is applied to the photocathode in need of recovery. The energetic beam, through the high secondary electron yield of the negative electron affinity surface (203), creates sufficient numbers of low energy electrons which act on the reduced-yield surface so as to negate the effects of absorbed oxidizing atoms thereby recovering the quantum yield to a pre-decay value.

Quantum walk on a chimera graph

NASA Astrophysics Data System (ADS)

Xu, Shu; Sun, Xiangxiang; Wu, Jizhou; Zhang, Wei-Wei; Arshed, Nigum; Sanders, Barry C.

2018-05-01

We analyse a continuous-time quantum walk on a chimera graph, which is a graph of choice for designing quantum annealers, and we discover beautiful quantum walk features such as localization that starkly distinguishes classical from quantum behaviour. Motivated by technological thrusts, we study continuous-time quantum walk on enhanced variants of the chimera graph and on diminished chimera graph with a random removal of vertices. We explain the quantum walk by constructing a generating set for a suitable subgroup of graph isomorphisms and corresponding symmetry operators that commute with the quantum walk Hamiltonian; the Hamiltonian and these symmetry operators provide a complete set of labels for the spectrum and the stationary states. Our quantum walk characterization of the chimera graph and its variants yields valuable insights into graphs used for designing quantum-annealers.

Convenient determination of luminescence quantum yield using a combined electronic absorption and emission spectrometer

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

Prakash, John; Mishra, Ashok Kumar

2016-01-15

It is possible to measure luminescence quantum yield in a facile way, by designing an optical spectrometer capable of obtaining electronic absorption as well as luminescence spectra, with a setup that uses the same light source and detector for both the spectral measurements. Employment of a single light source and single detector enables use of the same correction factor profile for spectral corrections. A suitable instrumental scaling factor is used for adjusting spectral losses.

Production of NO2 from Photolysis of Peroxyacetyl Nitrate

NASA Technical Reports Server (NTRS)

Mazely, Troy L.; Friedl, Randall R.; Sander, Stanley P.

1965-01-01

Peroxyacetyl nitrate (PAN) vapor was photolyzed at 248 nm, and the NO2 photoproduct was detected by laser-induced fluorescence. The quantum yield for the production of NO2 from PAN photolysis was determined by comparison to HNO3 photolysis data taken under identical experimental conditions. The average of data collected over a range of total pressures, precursor concentrations, and buffer gases was 0.83 +/- 0.09 for the NO2 quantum yield, where the statistical uncertainty is 2 standard deviations.

Wakimoto realization of drinfeld current for the elliptic quantum algebra U{sub q,p}( widehat(sl{sub 3}) )

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

Kojima, T., E-mail: kojima@math.cst.nihon-u.ac.j

2010-02-15

We study a free field realization of the elliptic quantum algebra U{sub q,p}( widehat(sl{sub 3}) ) for arbitrary level k. We give the free field realization of elliptic analog of Drinfeld current associated with U{sub q,p}( widehat(sl{sub 3}) ) for arbitrary level k. In the limit p {yields} 0, q {yields} 1 our realization reproduces Wakimoto realization for the affine Lie algebra ( widehat(sl{sub 3}) ) .

Protein-induced Photophysical Changes to the Amyloid Indicator Dye Thioflavin T

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

L Wolfe; M Calabrese; A Nath

2011-12-31

The small molecule thioflavin T (ThT) is a defining probe for the identification and mechanistic study of amyloid fiber formation. As such, ThT is fundamental to investigations of serious diseases such as Alzheimer's disease, Parkinson disease, and type II diabetes. For each disease, a different protein undergoes conformational conversion to a {beta}-sheet rich fiber. The fluorescence of ThT exhibits an increase in quantum yield upon binding these fibers. Despite its widespread use, the structural basis for binding specificity and for the changes to the photophysical properties of ThT remain poorly understood. Here, we report the co-crystal structures of ThT withmore » two alternative states of {beta}-2 microglobulin ({beta}2m); one monomeric, the other an amyloid-like oligomer. In the latter, the dye intercalates between {beta}-sheets orthogonal to the {beta}-strands. Importantly, the fluorophore is bound in such a manner that a photophysically relevant torsion is limited to a range of angles generally associated with low, not high, quantum yield. Quantum mechanical assessment of the fluorophore shows the electronic distribution to be strongly stabilized by aromatic interactions with the protein. Monomeric {beta}2m gives little increase in ThT fluorescence despite showing three fluorophores, at two binding sites, in configurations generally associated with high quantum yield. Our efforts fundamentally extend existing understanding about the origins of amyloid-induced photophysical changes. Specifically, the {beta}-sheet interface that characterizes amyloid acts both sterically and electronically to stabilize the fluorophore's ground state electronic distribution. By preventing the fluorophore from adopting its preferred excited state configuration, nonradiative relaxation pathways are minimized and quantum yield is increased.« less

Protein-induced photophysical changes to the amyloid indicator dye thioflavin T

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

Wolfe, Leslie S.; Calabrese, Matthew F.; Nath, Abhinav

2010-10-04

The small molecule thioflavin T (ThT) is a defining probe for the identification and mechanistic study of amyloid fiber formation. As such, ThT is fundamental to investigations of serious diseases such as Alzheimer's disease, Parkinson disease, and type II diabetes. For each disease, a different protein undergoes conformational conversion to a {beta}-sheet rich fiber. The fluorescence of ThT exhibits an increase in quantum yield upon binding these fibers. Despite its widespread use, the structural basis for binding specificity and for the changes to the photophysical properties of ThT remain poorly understood. Here, we report the co-crystal structures of ThT withmore » two alternative states of {beta}-2 microglobulin ({beta}2m); one monomeric, the other an amyloid-like oligomer. In the latter, the dye intercalates between {beta}-sheets orthogonal to the {beta}-strands. Importantly, the fluorophore is bound in such a manner that a photophysically relevant torsion is limited to a range of angles generally associated with low, not high, quantum yield. Quantum mechanical assessment of the fluorophore shows the electronic distribution to be strongly stabilized by aromatic interactions with the protein. Monomeric {beta}2m gives little increase in ThT fluorescence despite showing three fluorophores, at two binding sites, in configurations generally associated with high quantum yield. Our efforts fundamentally extend existing understanding about the origins of amyloid-induced photophysical changes. Specifically, the {beta}-sheet interface that characterizes amyloid acts both sterically and electronically to stabilize the fluorophore's ground state electronic distribution. By preventing the fluorophore from adopting its preferred excited state configuration, nonradiative relaxation pathways are minimized and quantum yield is increased.« less

Hybrid Molecule-Nanocrystal Photon Upconversion Across the Visible and Near-Infrared

DTIC Science & Technology

2015-07-10

applications in solar energy, biological imaging , and data storage. In this Letter, CdSe and PbSe semiconductor nanocrystals are combined with molecular...Goldschmidt, J. C. Absolute Upconversion Quantum Yield of β-NaYF4 Doped with Er3+ and External Quantum Efficiency of Upconverter Solar Cell Devices...C. Peak External Photocurrent Quantum Efficiency Exceeding 100% via MEG in a Quantum Dot Solar Cell . Science 2011, 334, 1530−1533. (37) Choi, J.-H

Aqueous synthesis of highly luminescent AgInS2-ZnS quantum dots and their biological applications

NASA Astrophysics Data System (ADS)

Regulacio, Michelle D.; Win, Khin Yin; Lo, Seong Loong; Zhang, Shuang-Yuan; Zhang, Xinhai; Wang, Shu; Han, Ming-Yong; Zheng, Yuangang

2013-02-01

Highly emissive and air-stable AgInS2-ZnS quantum dots (ZAIS QDs) with quantum yields of up to 20% have been successfully synthesized directly in aqueous media in the presence of polyacrylic acid (PAA) and mercaptoacetic acid (MAA) as stabilizing and reactivity-controlling agents. The as-prepared water-dispersible ZAIS QDs are around 3 nm in size, possess the tetragonal chalcopyrite crystal structure, and exhibit long fluorescence lifetimes (>100 ns). In addition, these ZAIS QDs are found to exhibit excellent optical and colloidal stability in physiologically relevant pH values as well as very low cytotoxicity, which render them particularly suitable for biological applications. Their potential use in biological labelling of baculoviral vectors is demonstrated.Highly emissive and air-stable AgInS2-ZnS quantum dots (ZAIS QDs) with quantum yields of up to 20% have been successfully synthesized directly in aqueous media in the presence of polyacrylic acid (PAA) and mercaptoacetic acid (MAA) as stabilizing and reactivity-controlling agents. The as-prepared water-dispersible ZAIS QDs are around 3 nm in size, possess the tetragonal chalcopyrite crystal structure, and exhibit long fluorescence lifetimes (>100 ns). In addition, these ZAIS QDs are found to exhibit excellent optical and colloidal stability in physiologically relevant pH values as well as very low cytotoxicity, which render them particularly suitable for biological applications. Their potential use in biological labelling of baculoviral vectors is demonstrated. Electronic supplementary information (ESI) available: Quantum yields, EDX spectrum and photoluminescence decay curves. See DOI: 10.1039/c3nr34159c

Measurement of Quantum Yield, Quantum Requirement, and Energetic Efficiency of the O2-Evolving System of Photosynthesis by a Simple Dye Reaction

NASA Astrophysics Data System (ADS)

Ros Barcelò, A.; Zapata, J. M.

1996-11-01

Photosynthesis is the conversion of absorbed radiant energy from sunlight into various forms of chemical energy by the chloroplasts of higher green plants. The overall process of photosynthesis consists of the oxidation of water (with the release of O2 as a product) and the reduction of CO2 to form carbohydrates. In the test tube electrons produced by the photolytic cleavage of H2) may be deviated from their true acceptor by inserting a suitable dye in the electron chain; i.e.; 2,6-dichlorophenol indophenol (DCPIP) (E'o = + 0.217 V), which is blue in the oxidized quinone form and which becomes colorless when reduced to the phenolic form. This dye-electrom acceptor also has the advantage that it accepts electroms directly from the quinone (Qa) electron-acceptor of the photosystem II< the reaction center associated with the O2-evolving (or water-slplitting) system. Based in the bleaching of DCPIP by illuminated spinach leaf chloroplasts, a classroom laboratory protocol has been developed to determine the quantum yield (QY = micromol O2 s-1 / micromol photons s-1, the quantum requirement (1/QY) and the energetic efficiency (f = chemical energy stored / light energy supplied) of the O2-evolving system of photosynthesis. Although values for the quantum yield, the quantum requirement and the energetic efficiency calculated in the classroom laboratory differ widely from those expected theoretically, these calculations are useful for illustrating the transformation of light energy into chemical energy by the chloroplasts of green plants.

Transparent Ultra-High-Loading Quantum Dot/Polymer Nanocomposite Monolith for Gamma Scintillation.

PubMed

Liu, Chao; Li, Zhou; Hajagos, Tibor Jacob; Kishpaugh, David; Chen, Dustin Yuan; Pei, Qibing

2017-06-27

Spectroscopic gamma-photon detection has widespread applications for research, defense, and medical purposes. However, current commercial detectors are either prohibitively expensive for wide deployment or incapable of producing the characteristic gamma photopeak. Here we report the synthesis of transparent, ultra-high-loading (up to 60 wt %) Cd x Zn 1-x S/ZnS core/shell quantum dot/polymer nanocomposite monoliths for gamma scintillation by in situ copolymerization of the partially methacrylate-functionalized quantum dots in a monomer solution. The efficient Förster resonance energy transfer of the high-atomic-number quantum dots to lower-band-gap organic dyes enables the extraction of quantum-dot-borne excitons for photon production, resolving the problem of severe light yield deterioration found in previous nanoparticle-loaded scintillators. As a result, the nanocomposite scintillator exhibited simultaneous improvements in both light yield (visible photons produced per MeV of gamma-photon energy) and gamma attenuation. With these enhancements, a 662 keV Cs-137 gamma photopeak with 9.8% resolution has been detected using a 60 wt % quantum-dot nanocomposite scintillator, demonstrating the potential of such a nanocomposite system in the development of high-performance low-cost spectroscopic gamma detectors.

Compact quantum dot-antibody conjugates for FRET immunoassays with subnanomolar detection limits.

PubMed

Mattera, Lucia; Bhuckory, Shashi; Wegner, K David; Qiu, Xue; Agnese, Fabio; Lincheneau, Christophe; Senden, Tim; Djurado, David; Charbonnière, Loïc J; Hildebrandt, Niko; Reiss, Peter

2016-06-07

A novel two-step approach for quantum dot (QD) functionalization and bioconjugation is presented, which yields ultra-compact, stable, and highly luminescent antibody-QD conjugates suitable for use in FRET immunoassays. Hydrophobic InPZnS/ZnSe/ZnS (emission wavelength: 530 nm), CdSe/ZnS (605 nm), and CdSeTe/ZnS (705 nm) QDs were surface functionalized with zwitterionic penicillamine, enabling aqueous phase transfer under conservation of the photoluminescence properties. Post-functionalization with a heterobifunctional crosslinker, containing a lipoic acid group and a maleimide function, enabled the subsequent coupling to sulfhydryl groups of proteins. This was demonstrated by QD conjugation with fragmented antibodies (F(ab)). The obtained F(ab)-QD conjugates range among the smallest antibody-functionalized nanoprobes ever reported, with a hydrodynamic diameter <13 nm, PL quantum yield up to 66% at 705 nm, and colloidal stability of several months in various buffers. They were applied as FRET acceptors in homogeneous, time-gated immunoassays using Tb-antibodies as FRET donors, both coupled by an immunological sandwich complex between the two antibodies and a PSA (prostate specific antigen) biomarker. The advantages of the compact surface coating for FRET could be demonstrated by an 6.2 and 2.5 fold improvement of the limit of detection (LOD) for PSA compared to commercially available hydrophilic QDs emitting at 605 and 705 nm, respectively. While the commercial QDs contain identical inorganic cores responsible for their fluorescence, they are coated with a comparably thick amphiphilic polymer layer leading to much larger hydrodynamic diameters (>26 nm without biomolecules). The LODs of 0.8 and 3.7 ng mL(-1) obtained in 50 μL serum samples are below the clinical cut-off level of PSA (4 ng mL(-1)) and demonstrate their direct applicability in clinical diagnostics.

Synthesis and photophysical properties of aluminium tris-(4-morpholine-8-hydroxyquinoline).

PubMed

Omar, Walaa A E

2013-11-01

Aluminium tris(4-morpholinyl-8-hydroxyquinoline) has been synthesized and characterized. The photoluminescence measurements showed that the new derivative is blue shifted and has relative photoluminescence quantum yield two times higher compared to the pristine Al tris(8-hydroxyquinoline). Deferential scanning colorimetric studies revealed that the newly synthesized Alq3 derivative in this work is amorphous material with the highest transition glass temperature value among the reported amorphous Alq3 derivatives.

Efficient tools for quantum metrology with uncorrelated noise

NASA Astrophysics Data System (ADS)

Kołodyński, Jan; Demkowicz-Dobrzański, Rafał

2013-07-01

Quantum metrology offers enhanced performance in experiments on topics such as gravitational wave-detection, magnetometry or atomic clock frequency calibration. The enhancement, however, requires a delicate tuning of relevant quantum features, such as entanglement or squeezing. For any practical application, the inevitable impact of decoherence needs to be taken into account in order to correctly quantify the ultimate attainable gain in precision. We compare the applicability and the effectiveness of various methods of calculating the ultimate precision bounds resulting from the presence of decoherence. This allows us to place a number of seemingly unrelated concepts into a common framework and arrive at an explicit hierarchy of quantum metrological methods in terms of the tightness of the bounds they provide. In particular, we show a way to extend the techniques originally proposed in Demkowicz-Dobrzański et al (2012 Nature Commun. 3 1063), so that they can be efficiently applied not only in the asymptotic but also in the finite number of particles regime. As a result, we obtain a simple and direct method, yielding bounds that interpolate between the quantum enhanced scaling characteristic for a small number of particles and the asymptotic regime, where quantum enhancement amounts to a constant factor improvement. Methods are applied to numerous models, including noisy phase and frequency estimation, as well as the estimation of the decoherence strength itself.

Quantum efficiency measurements of eROSITA pnCCDs

NASA Astrophysics Data System (ADS)

Ebermayer, Stefanie; Andritschke, Robert; Elbs, Johannes; Meidinger, Norbert; Strüder, Lothar; Hartmann, Robert; Gottwald, Alexander; Krumrey, Michael; Scholze, Frank

2010-07-01

For the eROSITA X-ray telescope, which is planned to be launched in 2012, detectors were developed and fabricated at the MPI Semiconductor Laboratory. The fully depleted, back-illuminated pnCCDs have an ultrathin pn-junction to improve the low-energy X-ray response function and quantum efficiency. The device thickness of 450 μm is fully sensitive to X-ray photons yielding high quantum efficiency of more than 90% at photon energies of 10 keV. An on-chip filter is deposited on top of the entrance window to suppress visible and UV light which would interfere with the X-ray observations. The pnCCD type developed for the eROSITA telescope was characterized in terms of quantum efficiency and spectral response function. The described measurements were performed in 2009 at the synchrotron radiation sources BESSY II and MLS as cooperation between the MPI Semiconductor Laboratory and the Physikalisch-Technische Bundesanstalt (PTB). Quantum efficiency measurements over a wide range of photon energies from 3 eV to 11 keV as well as spectral response measurements are presented. For X-ray energies from 3 keV to 10 keV the quantum efficiency of the CCD including on-chip filter is shown to be above 90% with an attenuation of visible light of more than five orders of magnitude. A detector response model is described and compared to the measurements.

Water catalysis and anticatalysis in photochemical reactions: observation of a delayed threshold effect in the reaction quantum yield.

PubMed

Kramer, Zeb C; Takahashi, Kaito; Skodje, Rex T

2010-11-03

The possible catalysis of photochemical reactions by water molecules is considered. Using theoretical simulations, we investigate the HF-elimination reaction of fluoromethanol in small water clusters initiated by the overtone excitation of the hydroxyl group. The reaction occurs in competition with the process of water evaporation that dissipates the excitation and quenches the reaction. Although the transition state barrier is stabilized by over 20 kcal/mol through hydrogen bonding with water, the quantum yield versus energy shows a pronounced delayed threshold that effectively eliminates the catalytic effect. It is concluded that the quantum chemistry calculations of barrier lowering are not sufficient to infer water catalysis in some photochemical reactions, which instead require dynamical modeling.

Templated self-assembly of quantum dots from aqueous solution using protein scaffolds

NASA Astrophysics Data System (ADS)

Szuchmacher Blum, Amy; Soto, Carissa M.; Wilson, Charmaine D.; Whitley, Jessica L.; Moore, Martin H.; Sapsford, Kim E.; Lin, Tianwei; Chatterji, Anju; Johnson, John E.; Ratna, Banahalli R.

2006-10-01

Short, histidine-containing peptides can be conjugated to lysine-containing protein scaffolds to controllably attach quantum dots (QDs) to the scaffold, allowing for generic attachment of quantum dots to any protein without the use of specially engineered domains. This technique was used to bind quantum dots from aqueous solution to both chicken IgG and cowpea mosaic virus (CPMV), a 30 nm viral particle. These quantum dot protein assemblies were studied in detail. The IgG QD complexes were shown to retain binding specificity to their antigen after modification. The CPMV QD complexes have a local concentration of quantum dots greater than 3000 nmol ml-1, and show a 15% increase in fluorescence quantum yield over free quantum dots in solution.

Bifunctional Diaminoterephthalate Fluorescent Dye as Probe for Cross-Linking Proteins.

PubMed

Wallisch, Melanie; Sulmann, Stefan; Koch, Karl-Wilhelm; Christoffers, Jens

2017-05-11

Diaminoterephthalates are fluorescent dyes and define scaffolds, which can be orthogonally functionalized at their two carboxylate residues with functional residues bearing task specific reactive groups. The synthesis of monofunctionalized dyes with thiol groups for surface binding, an azide for click chemistry, and a biotinoylated congener for streptavidin binding is reported. Two bifunctionalized dyes were prepared: One with an azide for click chemistry and a biotin for streptavidin binding, the other with a maleimide for reaction with thiol and a cyclooctyne moiety for ligation with copper-free click chemistry. In general, the compounds are red to orange, fluorescent materials with an absorption at about 450 nm and an emission at 560 nm with quantum yields between 2-41 %. Of particular interest is the maleimide-functionalized compound, which shows low fluorescence quantum yield (2 %) by itself. After addition of a thiol, the fluorescence is "turned on"; quantum yield 41 %. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A high quantum yield molecule-protein complex fluorophore for near-infrared II imaging

PubMed Central

Antaris, Alexander L.; Chen, Hao; Diao, Shuo; Ma, Zhuoran; Zhang, Zhe; Zhu, Shoujun; Wang, Joy; Lozano, Alexander X.; Fan, Quli; Chew, Leila; Zhu, Mark; Cheng, Kai; Hong, Xuechuan; Dai, Hongjie; Cheng, Zhen

2017-01-01

Fluorescence imaging in the second near-infrared window (NIR-II) allows visualization of deep anatomical features with an unprecedented degree of clarity. NIR-II fluorophores draw from a broad spectrum of materials spanning semiconducting nanomaterials to organic molecular dyes, yet unfortunately all water-soluble organic molecules with >1,000 nm emission suffer from low quantum yields that have limited temporal resolution and penetration depth. Here, we report tailoring the supramolecular assemblies of protein complexes with a sulfonated NIR-II organic dye (CH-4T) to produce a brilliant 110-fold increase in fluorescence, resulting in the highest quantum yield molecular fluorophore thus far. The bright molecular complex allowed for the fastest video-rate imaging in the second NIR window with ∼50-fold reduced exposure times at a fast 50 frames-per-second (FPS) capable of resolving mouse cardiac cycles. In addition, we demonstrate that the NIR-II molecular complexes are superior to clinically approved ICG for lymph node imaging deep within the mouse body. PMID:28524850

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

Filip, Radim; Marek, Petr; Fiurasek, Jaromir

We analyze a reversibility of optimal Gaussian 1{yields}2 quantum cloning of a coherent state using only local operations on the clones and classical communication between them and propose a feasible experimental test of this feature. Performing Bell-type homodyne measurement on one clone and anticlone, an arbitrary unknown input state (not only a coherent state) can be restored in the other clone by applying appropriate local unitary displacement operation. We generalize this concept to a partial reversal of the cloning using only local operations and classical communication (LOCC) and we show that this procedure converts the symmetric cloner to an asymmetricmore » cloner. Further, we discuss a distributed LOCC reversal in optimal 1{yields}M Gaussian cloning of coherent states which transforms it to optimal 1{yields}M{sup '} cloning for M{sup '}

Calculated quantum yield of photosynthesis of phytoplankton in the Marine Light-Mixed Layers (59 deg N, 21 deg W)

NASA Technical Reports Server (NTRS)

Carder, K. L.; Lee, Z. P.; Marra, John; Steward, R. G.; Perry, M. J.

1995-01-01

The quantum yield of photosynthesis (mol C/mol photons) was calculated at six depths for the waters of the Marine Light-Mixed Layer (MLML) cruise of May 1991. As there were photosynthetically available radiation (PAR) but no spectral irradiance measurements for the primary production incubations, three ways are presented here for the calculation of the absorbed photons (AP) by phytoplankton for the purpose of calculating phi. The first is based on a simple, nonspectral model; the second is based on a nonlinear regression using measured PAR values with depth; and the third is derived through remote sensing measurements. We show that the results of phi calculated using the nonlinear regreesion method and those using remote sensing are in good agreement with each other, and are consistent with the reported values of other studies. In deep waters, however, the simple nonspectral model may cause quantum yield values much higher than theoretically possible.

Photosensitized electron transport across lipid vesicle walls: Enhancement of quantum yield by ionophores and transmembrane potentials

PubMed Central

Laane, Colja; Ford, William E.; Otvos, John W.; Calvin, Melvin

1981-01-01

The photosensitized reduction of heptylviologen in the bulk aqueous phase of phosphatidylcholine vesicles containing EDTA inside and a membrane-bound tris(2,2′-bipyridine)ruthenium(2+) derivative is enhanced by a factor of 6.5 by the addition of valinomycin in the presence of K+. A 3-fold stimulation by gramicidin and carbonyl cyanide m-chlorophenylhydrazone is observed. The results suggest that, under these conditions, the rate of photoinduced electron transfer across vesicle walls in the absence of ion carriers is limited by cotransport of cations. The rate of electron transfer across vesicle walls could be influenced further by generating transmembrane potentials with K+ gradients in the presence of valinomycin. When vesicles are made with transmembrane potentials, interior more negative, the quantum yield of heptylviologen reduction is doubled, and, conversely, when vesicles are made with transmembrane potentials, interior more positive, the quantum yield is decreased and approaches the value found in the absence of valinomycin. PMID:16593002

Synthesis and spectroscopic properties of some new difluoroboron bis-β-diketonate derivatives.

PubMed

Pi, Yan; Wang, Dun-Jia; Liu, Hua; Hu, Yan-Jun; Wei, Xian-Hong; Zheng, Jing

2014-10-15

Six new bis-β-diketones (RCOCH2CO-C7H7N-COCH2COR) were synthesized from 3,5-diacetyl-2,6-dimethylpyridine via Claisen condensation with the corresponding esters, and then reacted with boron trifluoride etherate to afford difluoroboron bis-β-diketonate derivatives. Their spectroscopic properties were investigated by UV-vis, FTIR, (1)H NMR and fluorescence spectroscopic techniques. It was found that these boron complexes exhibited violet or blue fluorescence emission at 422-445nm and possessed high extinction coefficients. The results indicate that the extending π-conjugation can increase the fluorescence intensity and quantum yield for these boron complexes. Especially, the compound 2b displayed the stronger fluorescence intensity and the highest fluorescence quantum yield (Φu=0.94) in these boron compounds. However, compounds 2c and 2d had the lower fluorescence intensity and quantum yield as a result of the heavy atom effect of the chlorine atom in the molecules. Copyright © 2014 Elsevier B.V. All rights reserved.

Synthesis and spectroscopic properties of some new difluoroboron bis-β-diketonate derivatives

NASA Astrophysics Data System (ADS)

Pi, Yan; Wang, Dun-Jia; Liu, Hua; Hu, Yan-Jun; Wei, Xian-Hong; Zheng, Jing

2014-10-01

Six new bis-β-diketones (RCOCH2CO-C7H7N-COCH2COR) were synthesized from 3,5-diacetyl-2,6-dimethylpyridine via Claisen condensation with the corresponding esters, and then reacted with boron trifluoride etherate to afford difluoroboron bis-β-diketonate derivatives. Their spectroscopic properties were investigated by UV-vis, FTIR, 1H NMR and fluorescence spectroscopic techniques. It was found that these boron complexes exhibited violet or blue fluorescence emission at 422-445 nm and possessed high extinction coefficients. The results indicate that the extending π-conjugation can increase the fluorescence intensity and quantum yield for these boron complexes. Especially, the compound 2b displayed the stronger fluorescence intensity and the highest fluorescence quantum yield (Φu = 0.94) in these boron compounds. However, compounds 2c and 2d had the lower fluorescence intensity and quantum yield as a result of the heavy atom effect of the chlorine atom in the molecules.

Determination of apparent quantum yield spectra of DMS photo-degradation in an in situ iron-induced Northeast Pacific Ocean bloom

NASA Astrophysics Data System (ADS)

Bouillon, René-Christian; Miller, William L.

2004-03-01

The wavelength dependence of the photochemical removal efficiency for DMS was studied for samples from an iron-induced bloom in the Northeastern Pacific Ocean. In July 2002, a 64 km2 patch of ocean was iron-fertilized near Ocean Station Papa (50°12'N 144°45'W). Only small changes in pseudo-first-order apparent quantum yield (AQY*DMS(λ)) were observed outside the iron-patch. However, inside the patch, AQY*DMS(λ) decreased considerably over the two weeks following the initial iron injection. A positive strong correlation was found between pseudo-first-order apparent quantum yield determined at 330 nm (AQY*DMS(330 nm)) and NO3- concentrations. We propose that NO3--photolysis has a substantial influence on DMS photo-degradation rates in oceanic waters. This finding demonstrates that in addition to control DMS production, marine phytoplankton could indirectly influence the DMS photochemical loss rate via its control on NO3- distribution.

A high quantum yield molecule-protein complex fluorophore for near-infrared II imaging

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

Antaris, Alexander L.; Chen, Hao; Diao, Shuo

Fluorescence imaging in the second near-infrared window (NIR-II) allows visualization of deep anatomical features with an unprecedented degree of clarity. NIR-II fluorophores draw from a broad spectrum of materials spanning semiconducting nanomaterials to organic molecular dyes, yet unfortunately all water-soluble organic molecules with 41,000 nm emission suffer from low quantum yields that have limited temporal resolution and penetration depth. We report tailoring the supramolecular assemblies of protein complexes with a sulfonated NIR-II organic dye (CH-4T) to produce a brilliant 110-fold increase in fluorescence, resulting in the highest quantum yield molecular fluorophore thus far. The bright molecular complex allowed for themore » fastest video-rate imaging in the second NIR window with B50-fold reduced exposure times at a fast 50 frames-per-second (FPS) capable of resolving mouse cardiac cycles. Additionally, we demonstrate that the NIR-II molecular complexes are superior to clinically approved ICG for lymph node imaging deep within the mouse body.« less

A high quantum yield molecule-protein complex fluorophore for near-infrared II imaging

DOE PAGES

Antaris, Alexander L.; Chen, Hao; Diao, Shuo; ...

2017-05-19

Fluorescence imaging in the second near-infrared window (NIR-II) allows visualization of deep anatomical features with an unprecedented degree of clarity. NIR-II fluorophores draw from a broad spectrum of materials spanning semiconducting nanomaterials to organic molecular dyes, yet unfortunately all water-soluble organic molecules with 41,000 nm emission suffer from low quantum yields that have limited temporal resolution and penetration depth. We report tailoring the supramolecular assemblies of protein complexes with a sulfonated NIR-II organic dye (CH-4T) to produce a brilliant 110-fold increase in fluorescence, resulting in the highest quantum yield molecular fluorophore thus far. The bright molecular complex allowed for themore » fastest video-rate imaging in the second NIR window with B50-fold reduced exposure times at a fast 50 frames-per-second (FPS) capable of resolving mouse cardiac cycles. Additionally, we demonstrate that the NIR-II molecular complexes are superior to clinically approved ICG for lymph node imaging deep within the mouse body.« less

[Optical and spectral parameters in Ce3+ -doped gadolinium gallium aluminum garnet glass-ceramics].

PubMed

Gong, Hua; Zhao, Xin; Yu, Xiao-bo; Setsuhisa, Tanabe; Lin, Hai

2010-01-01

The crystalline phases of Ce3+ -doped gadolinium gallium aluminum garnet (GGAG) glass-ceramics were investigated by X-ray diffraction, and the fluorescence spectra were recorded under the pumping of blue light-emitting diode (LED) using an integrating sphere of 10-inch in diameter, which connected to a CCD detector. The spectral power distribution of the glass-ceramics was obtained from the measured spectra first, and then the quantum yield was derived based on the photon distribution. The quantum yield of Ce3+ emission in GGAG glass-ceramics is 29.2%, meanwhile, the color coordinates and the correlated color temperature (CCT) of combined white light were proved to be x = 0.319, y = 0.349 and 6086 K, respectively. Although the quantum yield is a little smaller than the value in Ce3+ -doped YAG glass-ceramics, the CCT of the combined white light is much smaller than that in the latter. The optical behavior of GGAG glass-ceramics provides new vision for developing comfortable LED lighting devices.

Excitonic Emission of Monolayer Semiconductors Near-Field Coupled to High-Q Microresonators

NASA Astrophysics Data System (ADS)

Javerzac-Galy, Clément; Kumar, Anshuman; Schilling, Ryan D.; Piro, Nicolas; Khorasani, Sina; Barbone, Matteo; Goykhman, Ilya; Khurgin, Jacob B.; Ferrari, Andrea C.; Kippenberg, Tobias J.

2018-05-01

We present quantum yield measurements of single layer $\\textrm{WSe}_2$ (1L-$\\textrm{WSe}_2$) integrated with high-Q ($Q>10^6$) optical microdisk cavities, using an efficient ($\\eta>$90%) near-field coupling scheme based on a tapered optical fiber. Coupling of the excitonic emission is achieved by placing 1L-WSe$_2$ to the evanescent cavity field. This preserves the microresonator high intrinsic quality factor ($Q>10^6$) below the bandgap of 1L-WSe$_2$. The nonlinear excitation power dependence of the cavity quantum yield is in agreement with an exciton-exciton annihilation model. The cavity quantum yield is $\\textrm{QY}_\\textrm{c}\\sim10^{-3}$, consistent with operation in the \\textit{broad emitter} regime (i.e. the emission lifetime of 1L-WSe$_2$ is significantly shorter than the bare cavity decay time). This scheme can serve as a precise measurement tool for the excitonic emission of layered materials into cavity modes, for both in plane and out of plane excitation.

Relative quantum yield of I-asterisk(2P1/2) in the tunable laser UV photodissociation of i-C3F7I and n-C3F7I - Effect of temperature and exciplex emission

NASA Technical Reports Server (NTRS)

Smedley, J. E.; Leone, S. R.

1983-01-01

Wavelength-specific relative quantum yields of metastable I from pulsed laser photodissociation of i-C3F7I and n-C3F7I in the range 265-336 nm are determined by measuring the time-resolved infrared emission from the atomic I(P-2(1/2) P-2(3/2) transition. It is shown that although this yield appears to be unity from 265 to 298 nm, it decreases dramatically at longer wavelengths. Values are also reported for the enhancement of emission from metastable I due to exciplex formation at several temperatures. The exciplex formation emission increases linearly with parent gas pressure, but decreases with increasing temperature. Absorption spectra of i- and n-C3F7I between 303 and 497 K are presented, and the effect of temperature on the quantum yields at selected wavelengths greater than 300 nm, where increasing the temperature enhances the absorption considerably, are given. The results are discussed in regard to the development of solar-pumped iodine lasers.

Increasing selectivity for TNT-based explosive detection by synchronous luminescence and derivative spectroscopy with quantum yields of selected aromatic amines.

PubMed

Sheaff, Chrystal N; Eastwood, Delyle; Wai, Chien M

2007-01-01

The detection of explosive material is at the forefront of current analytical problems. A detection method is desired that is not restricted to detecting only explosive materials, but is also capable of identifying the origin and type of explosive. It is essential that a detection method have the selectivity to distinguish among compounds in a mixture of explosives. The nitro compounds found in explosives have low fluorescent yields or are considered to be non-fluorescent; however, after reduction, the amino compounds exhibit relatively high fluorescence. We discuss how to increase selectivity of explosive detection using fluorescence; this includes synchronous luminescence and derivative spectroscopy with appropriate smoothing. By implementing synchronous luminescence and derivative spectroscopy, we were able to resolve the reduction products of one major TNT-based explosive compound, 2,4-diaminotoluene, and the reduction products of other minor TNT-based explosives in a mixture. We also report for the first time the quantum yields of these important compounds. Relative quantum yields are useful in establishing relative fluorescence intensities and are an important spectroscopic measurement of molecules. Our approach allows for rapid, sensitive, and selective detection with the discrimination necessary to distinguish among various explosives.

High Photoluminescence Quantum Yield in Band Gap Tunable Bromide Containing Mixed Halide Perovskites

DOE PAGES

Sutter-Fella, Carolin M.; Li, Yanbo; Amani, Matin; ...

2015-12-21

Hybrid organic-inorganic halide perovskite based semiconductor materials are attractive for use in a wide range of optoelectronic devices because they combine the advantages of suitable optoelectronic attributes and simultaneously low-cost solution processability. Here, we present a two-step low-pressure vapor-assisted solution process to grow high quality homogeneous CH 3NH 3PbI 3-xBr x perovskite films over the full band gap range of 1.6-2.3 eV. Photoluminescence light-in versus light-out characterization techniques are used to provide new insights into the optoelectronic properties of Br-containing hybrid organic-inorganic perovskites as a function of optical carrier injection by employing pump-powers over a 6 orders of magnitude dynamicmore » range. The internal luminescence quantum yield of wide band gap perovskites reaches impressive values up to 30%. This high quantum yield translates into substantial quasi-Fermi level splitting and high "luminescence or optically implied" open-circuit voltage. Most importantly, both attributes, high internal quantum yield and high optically implied open-circuit voltage, are demonstrated over the entire band gap range (1.6 eV ≤ E g ≤ 2.3 eV). These results establish the versatility of Br-containing perovskite semiconductors for a variety of applications and especially for the use as high-quality top cell in tandem photovoltaic devices in combination with industry dominant Si bottom cells. (Figure Presented).« less

Experimental implementation of local adiabatic evolution algorithms by an NMR quantum information processor.

PubMed

Mitra, Avik; Ghosh, Arindam; Das, Ranabir; Patel, Apoorva; Kumar, Anil

2005-12-01

Quantum adiabatic algorithm is a method of solving computational problems by evolving the ground state of a slowly varying Hamiltonian. The technique uses evolution of the ground state of a slowly varying Hamiltonian to reach the required output state. In some cases, such as the adiabatic versions of Grover's search algorithm and Deutsch-Jozsa algorithm, applying the global adiabatic evolution yields a complexity similar to their classical algorithms. However, using the local adiabatic evolution, the algorithms given by J. Roland and N.J. Cerf for Grover's search [J. Roland, N.J. Cerf, Quantum search by local adiabatic evolution, Phys. Rev. A 65 (2002) 042308] and by Saurya Das, Randy Kobes, and Gabor Kunstatter for the Deutsch-Jozsa algorithm [S. Das, R. Kobes, G. Kunstatter, Adiabatic quantum computation and Deutsh's algorithm, Phys. Rev. A 65 (2002) 062301], yield a complexity of order N (where N=2(n) and n is the number of qubits). In this paper, we report the experimental implementation of these local adiabatic evolution algorithms on a 2-qubit quantum information processor, by Nuclear Magnetic Resonance.

Observable measure of quantum coherence in finite dimensional systems.

PubMed

Girolami, Davide

2014-10-24

Quantum coherence is the key resource for quantum technology, with applications in quantum optics, information processing, metrology, and cryptography. Yet, there is no universally efficient method for quantifying coherence either in theoretical or in experimental practice. I introduce a framework for measuring quantum coherence in finite dimensional systems. I define a theoretical measure which satisfies the reliability criteria established in the context of quantum resource theories. Then, I present an experimental scheme implementable with current technology which evaluates the quantum coherence of an unknown state of a d-dimensional system by performing two programmable measurements on an ancillary qubit, in place of the O(d2) direct measurements required by full state reconstruction. The result yields a benchmark for monitoring quantum effects in complex systems, e.g., certifying nonclassicality in quantum protocols and probing the quantum behavior of biological complexes.

Primary photophysical properties of moxifloxacin--a fluoroquinolone antibiotic.

PubMed

Lorenzo, Fernando; Navaratnam, Suppiah; Edge, Ruth; Allen, Norman S

2008-01-01

The photophysical properties of the fluoroquinolone antibiotic moxifloxacin (MOX) were investigated in aqueous media. MOX in water, at pH 7.4, shows two intense absorption bands at 287 and 338 nm (epsilon = 44,000 and 17,000 dm(3) mol(-1) cm(-1), respectively). The absorption and emission properties of MOX are pH-dependent, pK(a) values for the protonation equilibria of both the ground (6.1 and 9.6) and excited singlet states (6.8 and 9.1) of MOX were determined spectroscopically. MOX fluoresces weakly, the quantum yield for fluorescence emission being maximum (0.07) at pH 8. Phosphorescence from the excited triplet state in frozen ethanol solution has a quantum yield of 0.046. Laser flash photolysis and pulse radiolysis studies have been carried out to characterize the transient species of MOX in aqueous solution. On laser excitation, MOX undergoes monophotonic photoionization with a quantum yield of 0.14. This leads to the formation of a long-lived cation radical whose absorption is maximum at 470 nm (epsilon(470) = 3400 dm(3) mol(-1) cm(-1)). The photoionization process releases hydrated electron which rapidly reacts (k = 2.8 x 10(10) dm(3) mol(-1) s(-1)) with ground state MOX, yielding a long-lived anion radical with maximum absorption at 390 nm (epsilon(390) = 2400 dm(3) mol(-1) cm(-1)). The cation radical of MOX is able to oxidize protein components tryptophan and tyrosine. The bimolecular rate constants for these reactions are 2.3 x 10(8) dm(3) mol(-1) s(-1) and 1.3 x 10(8) dm(3) mol(-1) s(-1), respectively. Singlet oxygen sensitized by the MOX triplet state was also detected only in oxygen-saturated D(2)O solutions, with a quantum yield of 0.075.

Rose bengal in poly(2-hydroxyethyl methacrylate) thin films: self-quenching by photoactive energy traps

NASA Astrophysics Data System (ADS)

Ezquerra Riega, Sergio D.; Rodríguez, Hernán B.; San Román, Enrique

2017-03-01

The effect of dye concentration on the fluorescence,ΦF, and singlet molecular oxygen,ΦΔ, quantum yields of rose bengal loaded poly(2-hydroxyethyl methacrylate) thin films (∼200 nm thick) was investigated, with the aim of understanding the effect of molecular interactions on the photophysical properties of dyes in crowded constrained environments. Films were characterized by absorption and fluorescence spectroscopy, singlet molecular oxygen (1O2) production was quantified using a chemical monitor, and the triplet decay was determined by laser flash-photolysis. For the monomeric dilute dye, ΦF = 0.05 ± 0.01 and ΦΔ = 0.76 ± 0.14. The effect of humidity and the photostability of the dye were also investigated. Spectral changes in absorption and fluorescence in excess of 0.05 M and concentration self-quenching after 0.01 M are interpreted in the context of a quenching radius model. Calculations of energy migration and trapping rates were performed assuming random distribution of the dye. Best fits of fluorescence quantum yields with concentration are obtained in the whole concentration range with a quenching radius r Q = 1.5 nm, in the order of molecular dimensions. Agreement is obtained only if dimeric traps are considered photoactive, with an observed fluorescence quantum yield ratio ΦF,trap/ΦF,monomer ≈ 0.35. Fluorescent traps are capable of yielding triplet states and 1O2. Results show that the excited state generation efficiency, calculated as the product between the absorption factor and the fluorescence quantum yield, is maximized at around 0.15 M, a very high concentration for random dye distributions. Relevant information for the design of photoactive dyed coatings is provided.

Catalysis of heat-to-work conversion in quantum machines

PubMed Central

Ghosh, A.; Latune, C. L.; Davidovich, L.; Kurizki, G.

2017-01-01

We propose a hitherto-unexplored concept in quantum thermodynamics: catalysis of heat-to-work conversion by quantum nonlinear pumping of the piston mode which extracts work from the machine. This concept is analogous to chemical reaction catalysis: Small energy investment by the catalyst (pump) may yield a large increase in heat-to-work conversion. Since it is powered by thermal baths, the catalyzed machine adheres to the Carnot bound, but may strongly enhance its efficiency and power compared with its noncatalyzed counterparts. This enhancement stems from the increased ability of the squeezed piston to store work. Remarkably, the fraction of piston energy that is convertible into work may then approach unity. The present machine and its counterparts powered by squeezed baths share a common feature: Neither is a genuine heat engine. However, a squeezed pump that catalyzes heat-to-work conversion by small investment of work is much more advantageous than a squeezed bath that simply transduces part of the work invested in its squeezing into work performed by the machine. PMID:29087326

Catalysis of heat-to-work conversion in quantum machines

NASA Astrophysics Data System (ADS)

Ghosh, A.; Latune, C. L.; Davidovich, L.; Kurizki, G.

2017-11-01

We propose a hitherto-unexplored concept in quantum thermodynamics: catalysis of heat-to-work conversion by quantum nonlinear pumping of the piston mode which extracts work from the machine. This concept is analogous to chemical reaction catalysis: Small energy investment by the catalyst (pump) may yield a large increase in heat-to-work conversion. Since it is powered by thermal baths, the catalyzed machine adheres to the Carnot bound, but may strongly enhance its efficiency and power compared with its noncatalyzed counterparts. This enhancement stems from the increased ability of the squeezed piston to store work. Remarkably, the fraction of piston energy that is convertible into work may then approach unity. The present machine and its counterparts powered by squeezed baths share a common feature: Neither is a genuine heat engine. However, a squeezed pump that catalyzes heat-to-work conversion by small investment of work is much more advantageous than a squeezed bath that simply transduces part of the work invested in its squeezing into work performed by the machine.

Quantum Enhanced Inference in Markov Logic Networks

NASA Astrophysics Data System (ADS)

Wittek, Peter; Gogolin, Christian

2017-04-01

Markov logic networks (MLNs) reconcile two opposing schools in machine learning and artificial intelligence: causal networks, which account for uncertainty extremely well, and first-order logic, which allows for formal deduction. An MLN is essentially a first-order logic template to generate Markov networks. Inference in MLNs is probabilistic and it is often performed by approximate methods such as Markov chain Monte Carlo (MCMC) Gibbs sampling. An MLN has many regular, symmetric structures that can be exploited at both first-order level and in the generated Markov network. We analyze the graph structures that are produced by various lifting methods and investigate the extent to which quantum protocols can be used to speed up Gibbs sampling with state preparation and measurement schemes. We review different such approaches, discuss their advantages, theoretical limitations, and their appeal to implementations. We find that a straightforward application of a recent result yields exponential speedup compared to classical heuristics in approximate probabilistic inference, thereby demonstrating another example where advanced quantum resources can potentially prove useful in machine learning.

Lead selenide quantum dot polymer nanocomposites

NASA Astrophysics Data System (ADS)

Waldron, Dennis L.; Preske, Amanda; Zawodny, Joseph M.; Krauss, Todd D.; Gupta, Mool C.

2015-02-01

Optical absorption and fluorescence properties of PbSe quantum dots (QDs) in an Angstrom Bond AB9093 epoxy polymer matrix to form a nanocomposite were investigated. To the authors’ knowledge, this is the first reported use of AB9093 as a QD matrix material and it was shown to out-perform the more common poly(methyl methacrylate) matrix in terms of preserving the optical properties of the QD, resulting in the first reported quantum yield (QY) for PbSe QDs in a polymer matrix, 26%. The 1-s first excitonic absorption peak of the QDs in a polymer matrix red shifted 65 nm in wavelength compared to QDs in a hexane solution, while the emission peak in the polymer matrix red shifted by 38 nm. The fluorescence QY dropped from 55% in hexane to 26% in the polymer matrix. A time resolved fluorescence study of the QDs showed single exponential lifetimes of 2.34 and 1.34 μs in toluene solution and the polymer matrix respectively.

Catalysis of heat-to-work conversion in quantum machines.

PubMed

Ghosh, A; Latune, C L; Davidovich, L; Kurizki, G

2017-11-14

We propose a hitherto-unexplored concept in quantum thermodynamics: catalysis of heat-to-work conversion by quantum nonlinear pumping of the piston mode which extracts work from the machine. This concept is analogous to chemical reaction catalysis: Small energy investment by the catalyst (pump) may yield a large increase in heat-to-work conversion. Since it is powered by thermal baths, the catalyzed machine adheres to the Carnot bound, but may strongly enhance its efficiency and power compared with its noncatalyzed counterparts. This enhancement stems from the increased ability of the squeezed piston to store work. Remarkably, the fraction of piston energy that is convertible into work may then approach unity. The present machine and its counterparts powered by squeezed baths share a common feature: Neither is a genuine heat engine. However, a squeezed pump that catalyzes heat-to-work conversion by small investment of work is much more advantageous than a squeezed bath that simply transduces part of the work invested in its squeezing into work performed by the machine.

Highly luminescent core-shell InP/ZnX (X = S, Se) quantum dots prepared via a phosphine synthetic route.

PubMed

Mordvinova, Natalia; Vinokurov, Alexander; Kuznetsova, Tatiana; Lebedev, Oleg I; Dorofeev, Sergey

2017-01-24

Here we report a simple method for the creation of highly luminescent core-shell InP/ZnX (X = S, Se) quantum dots (QDs) on the basis of a phosphine synthetic route. In this method a Zn precursor was added to the reaction mixture at the beginning of the synthesis to form an In(Zn)P alloy structure, which promoted the formation of a ZnX shell. Core-shell InP/ZnX QDs exhibit highly intensive emission with a quantum yield over 50%. The proposed method is primarily important for practical applications. Advantages of this method compared to the widely used SILAR technique are discussed. We further demonstrate that the SILAR approach consisting of consequent addition of Zn and chalcogen precursors to pre-prepared non-doped InP colloidal nanoparticles is not quite suitable for shell growth without the addition of special activator agents or the use of very reactive precursors.

Quantum Enhanced Inference in Markov Logic Networks.

PubMed

Wittek, Peter; Gogolin, Christian

2017-04-19

Markov logic networks (MLNs) reconcile two opposing schools in machine learning and artificial intelligence: causal networks, which account for uncertainty extremely well, and first-order logic, which allows for formal deduction. An MLN is essentially a first-order logic template to generate Markov networks. Inference in MLNs is probabilistic and it is often performed by approximate methods such as Markov chain Monte Carlo (MCMC) Gibbs sampling. An MLN has many regular, symmetric structures that can be exploited at both first-order level and in the generated Markov network. We analyze the graph structures that are produced by various lifting methods and investigate the extent to which quantum protocols can be used to speed up Gibbs sampling with state preparation and measurement schemes. We review different such approaches, discuss their advantages, theoretical limitations, and their appeal to implementations. We find that a straightforward application of a recent result yields exponential speedup compared to classical heuristics in approximate probabilistic inference, thereby demonstrating another example where advanced quantum resources can potentially prove useful in machine learning.

Quantum Enhanced Inference in Markov Logic Networks

PubMed Central

Wittek, Peter; Gogolin, Christian

2017-01-01

Markov logic networks (MLNs) reconcile two opposing schools in machine learning and artificial intelligence: causal networks, which account for uncertainty extremely well, and first-order logic, which allows for formal deduction. An MLN is essentially a first-order logic template to generate Markov networks. Inference in MLNs is probabilistic and it is often performed by approximate methods such as Markov chain Monte Carlo (MCMC) Gibbs sampling. An MLN has many regular, symmetric structures that can be exploited at both first-order level and in the generated Markov network. We analyze the graph structures that are produced by various lifting methods and investigate the extent to which quantum protocols can be used to speed up Gibbs sampling with state preparation and measurement schemes. We review different such approaches, discuss their advantages, theoretical limitations, and their appeal to implementations. We find that a straightforward application of a recent result yields exponential speedup compared to classical heuristics in approximate probabilistic inference, thereby demonstrating another example where advanced quantum resources can potentially prove useful in machine learning. PMID:28422093

InP/ZnSe/ZnS core-multishell quantum dots for improved luminescence efficiency

NASA Astrophysics Data System (ADS)

Greco, Tonino; Ippen, Christian; Wedel, Armin

2012-04-01

Semiconductor quantum dots (QDs) exhibit unique optical properties like size-tunable emission color, narrow emission peak, and high luminescence efficiency. QDs are therefore investigated towards their application in light-emitting devices (QLEDs), solar cells, and for bio-imaging purposes. In most cases QDs made from cadmium compounds like CdS, CdSe or CdTe are studied because of their facile and reliable synthesis. However, due to the toxicity of Cd compounds and the corresponding regulation (e.g. RoHS directive in Europe) these materials are not feasible for customer applications. Indium phosphide is considered to be the most promising alternative because of the similar band gap (InP 1.35 eV, CdSe 1.73 eV). InP QDs do not yet reach the quality of CdSe QDs, especially in terms of photoluminescence quantum yield and peak width. Typically, QDs are coated with another semiconductor material of wider band gap, often ZnS, to passivate surface defects and thus improve luminescence efficiency. Concerning CdSe QDs, multishell coatings like CdSe/CdS/ZnS or CdSe/ZnSe/ZnS have been shown to be advantageous due to the improved compatibility of lattice constants. Here we present a method to improve the luminescence efficiency of InP QDs by coating a ZnSe/ZnS multishell instead of a ZnS single shell. ZnSe exhibits an intermediate lattice constant of 5.67 Å between those of InP (5.87 Å) and ZnS (5.41 Å) and thus acts as a wetting layer. As a result, InP/ZnSe/ZnS is introduced as a new core-shell quantum dot material which shows improved photoluminescence quantum yield (up to 75 %) compared to the conventional InP/ZnS system.

Bifurcation-based adiabatic quantum computation with a nonlinear oscillator network

PubMed Central

Goto, Hayato

2016-01-01

The dynamics of nonlinear systems qualitatively change depending on their parameters, which is called bifurcation. A quantum-mechanical nonlinear oscillator can yield a quantum superposition of two oscillation states, known as a Schrödinger cat state, via quantum adiabatic evolution through its bifurcation point. Here we propose a quantum computer comprising such quantum nonlinear oscillators, instead of quantum bits, to solve hard combinatorial optimization problems. The nonlinear oscillator network finds optimal solutions via quantum adiabatic evolution, where nonlinear terms are increased slowly, in contrast to conventional adiabatic quantum computation or quantum annealing, where quantum fluctuation terms are decreased slowly. As a result of numerical simulations, it is concluded that quantum superposition and quantum fluctuation work effectively to find optimal solutions. It is also notable that the present computer is analogous to neural computers, which are also networks of nonlinear components. Thus, the present scheme will open new possibilities for quantum computation, nonlinear science, and artificial intelligence. PMID:26899997

Quantum random access memory.

PubMed

Giovannetti, Vittorio; Lloyd, Seth; Maccone, Lorenzo

2008-04-25

A random access memory (RAM) uses n bits to randomly address N=2(n) distinct memory cells. A quantum random access memory (QRAM) uses n qubits to address any quantum superposition of N memory cells. We present an architecture that exponentially reduces the requirements for a memory call: O(logN) switches need be thrown instead of the N used in conventional (classical or quantum) RAM designs. This yields a more robust QRAM algorithm, as it in general requires entanglement among exponentially less gates, and leads to an exponential decrease in the power needed for addressing. A quantum optical implementation is presented.

Graph C ∗-algebras and Z2-quotients of quantum spheres

NASA Astrophysics Data System (ADS)

Hajac, Piotr M.; Matthes, Rainer; Szymański, Wojciech

2003-06-01

We consider two Z2-actions on the Podleś generic quantum spheres. They yield, as noncommutative quotient spaces, the Klimek-Lesmewski q-disc and the quantum real projective space, respectively. The C ∗-algebas of all these quantum spaces are described as graph C ∗-algebras. The K-groups of the thus presented C ∗-algebras are then easily determined from the general theory of graph C ∗-algebas. For the quantum real projective space, we also recall the classification of the classes of irreducible ∗-representations of its algebra and give a linear basis for this algebra.

Plasmonic enhancement of electroluminescence

NASA Astrophysics Data System (ADS)

Guzatov, D. V.; Gaponenko, S. V.; Demir, H. V.

2018-01-01

Here plasmonic effect specifically on electroluminescence (EL) is studied in terms of radiative and nonradiative decay rates for a dipole near a metal spherical nanoparticle (NP). Contribution from scattering is taken into account and is shown to play a decisive role in EL enhancement owing to pronounced size-dependent radiative decay enhancement and weak size effect on non-radiative counterpart. Unlike photoluminescence where local incident field factor mainly determines the enhancement possibility and level, EL enhancement is only possible by means of quantum yield rise, EL enhancement being feasible only for an intrinsic quantum yield Q0 < 1. The resulting plasmonic effect is independent of intrinsic emitter lifetime but is exclusively defined by the value of Q0, emission spectrum, NP diameter and emitter-metal spacing. For 0.1< Q0 < 0.25, Ag nanoparticles are shown to enhance LED/OLED intensity by several times over the whole visible whereas Au particles feature lower effect within the red-orange range only. Independently of positive effect on quantum yield, metal nanoparticles embedded in an electroluminescent device will improve its efficiency at high currents owing to enhanced overall recombination rate which will diminish manifestation of Auger processes. The latter are believed to be responsible for the known undesirable efficiency droop in semiconductor commercial quantum well based LEDs at higher current. For the same reason plasmonics can diminish quantum dot photodegradation from Auger process induced non-radiative recombination and photoionization thus opening a way to avoid negative Auger effects in emerging colloidal semiconductor LEDs.

What limits photosynthetic energy conversion efficiency in nature? Lessons from the oceans.

PubMed

Falkowski, Paul G; Lin, Hanzhi; Gorbunov, Maxim Y

2017-09-26

Constraining photosynthetic energy conversion efficiency in nature is challenging. In principle, two yield measurements must be made simultaneously: photochemistry, fluorescence and/or thermal dissipation. We constructed two different, extremely sensitive and precise active fluorometers: one measures the quantum yield of photochemistry from changes in variable fluorescence, the other measures fluorescence lifetimes in the picosecond time domain. By deploying the pair of instruments on eight transoceanic cruises over six years, we obtained over 200 000 measurements of fluorescence yields and lifetimes from surface waters in five ocean basins. Our results revealed that the average quantum yield of photochemistry was approximately 0.35 while the average quantum yield of fluorescence was approximately 0.07. Thus, closure on the energy budget suggests that, on average, approximately 58% of the photons absorbed by phytoplankton in the world oceans are dissipated as heat. This extraordinary inefficiency is associated with the paucity of nutrients in the upper ocean, especially dissolved inorganic nitrogen and iron. Our results strongly suggest that, in nature, most of the time, most of the phytoplankton community operates at approximately half of its maximal photosynthetic energy conversion efficiency because nutrients limit the synthesis or function of essential components in the photosynthetic apparatus.This article is part of the themed issue 'Enhancing photosynthesis in crop plants: targets for improvement'. © 2017 The Author(s).

Core/Shell NaGdF4:Nd3+/NaGdF4 Nanocrystals with Efficient Near-Infrared to Near-Infrared Downconversion Photoluminescence for Bioimaging Applications

PubMed Central

Chen, Guanying; Ohulchanskyy, Tymish Y.; Liu, Sha; Law, Wing-Cheung; Wu, Fang; Swihart, Mark T.; Ågren, Hans; Prasad, Paras N.

2012-01-01

We have synthesized core/shell NaGdF4:Nd3+/NaGdF4 nanocrystals with an average size of 15 nm and exceptionally high photoluminescence (PL) quantum yield. When excited at 740 nm, the nanocrystals manifest spectrally distinguished, near infrared to near infrared (NIR-to-NIR) downconversion PL peaked at ~900, ~1050, and ~1300 nm. The absolute quantum yield of NIR-to-NIR PL reached 40% for core-shell nanoparticles dispersed in hexane. Time-resolved PL measurements revealed that this high quantum yield was achieved through suppression of nonradiative recombination originating from surface states and cross relaxations between dopants. NaGdF4:Nd3+/NaGdF4 nanocrystals, synthesized in organic media, were further converted to be water-dispersible by eliminating the capping ligand of oleic acid. NIR-to-NIR PL bioimaging was demonstrated both in vitro and in vivo through visualization of the NIR-to-NIR PL at ~900 nm under incoherent lamp light excitation. The fact that both excitation and the PL of these nanocrystals are in the biological window of optical transparency, combined with their high quantum efficiency, spectral sharpness and photostability, makes these nanocrystals extremely promising as optical biomaging probes. PMID:22401578

Dynamical basis sets for algebraic variational calculations in quantum-mechanical scattering theory

NASA Technical Reports Server (NTRS)

Sun, Yan; Kouri, Donald J.; Truhlar, Donald G.; Schwenke, David W.

1990-01-01

New basis sets are proposed for linear algebraic variational calculations of transition amplitudes in quantum-mechanical scattering problems. These basis sets are hybrids of those that yield the Kohn variational principle (KVP) and those that yield the generalized Newton variational principle (GNVP) when substituted in Schlessinger's stationary expression for the T operator. Trial calculations show that efficiencies almost as great as that of the GNVP and much greater than the KVP can be obtained, even for basis sets with the majority of the members independent of energy.

Lanthanide complexes with 2-(tosylamino)benzylidene-N-benzoylhydrazone, which exhibit high NIR emission.

PubMed

Utochnikova, V V; Kovalenko, A D; Burlov, A S; Marciniak, L; Ananyev, I V; Kalyakina, A S; Kurchavov, N A; Kuzmina, N P

2015-07-28

New NIR emitting materials were found among the lanthanide complexes with 2-(tosylamino)benzylidene-N-benzoylhydrazone. Complexes of Nd(3+), Er(3+) and Yb(3+), as well as Eu(3+), Gd(3+) and Lu(3+), were synthesized for the first time. Owing to the absence of vibration quenching the ytterbium complex was found to exhibit a photoluminescence quantum yield of 1.4%. Since the sensitization efficiency was calculated to be 55%, the losses in the quantum yield are probably due to Yb-Yb resonant energy transfer.

Tunable UV Laser Photolysis of NF2: Quantum Yield for NF(a1 delta) Production.

DTIC Science & Technology

1988-05-25

UV Laser Photolysis of NF2: Quantum Yield for NF(a A) Production ’v0 LR. F. HEIDNER, H . HELVAJIAN , 4and J. B. KOFFEND Aerophysics Laboratory...experiments, the chemistry of NF2 with various hydrocarbons has been studied. It has also been shown that the addition-elimination reaction between H and NF2...COMPLI R LEN SP, 3 ,HAND L BE AM~ H O [ I , , i 1 CAIHOC IAM COOLED GaAs CAPACITANCE PHOTOTUIBE MANOMETER _ LENS /’~ ~L + . ANMEE _.... BANDPASS FILTER

Loop-quantum-gravity vertex amplitude.

PubMed

Engle, Jonathan; Pereira, Roberto; Rovelli, Carlo

2007-10-19

Spin foam models are hoped to provide the dynamics of loop-quantum gravity. However, the most popular of these, the Barrett-Crane model, does not have the good boundary state space and there are indications that it fails to yield good low-energy n-point functions. We present an alternative dynamics that can be derived as a quantization of a Regge discretization of Euclidean general relativity, where second class constraints are imposed weakly. Its state space matches the SO(3) loop gravity one and it yields an SO(4)-covariant vertex amplitude for Euclidean loop gravity.

Interpretation of quantum yields exceeding unity in photoelectrochemical systems

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

Szklarczyk, M.; Allen, R.E.

1986-10-20

In photoelectrochemical systems involving light shining on a semiconductor interfaced with an electrolyte, the quantum yield as a function of photon frequency ..nu.. is observed to exhibit a peak at h..nu..roughly-equal2E/sub g/, where E/sub g/ is the band gap of the semiconductor. The maximum in this peak is sometimes found to exceed unity. We provide an interpretation involving surface states and inelastic electron-electron scattering. The theory indicates that the effect should be observable for p-type semiconductors, but not n-type.

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

Damtie, Fikeraddis A., E-mail: Fikeraddis.Damtie@teorfys.lu.se; Wacker, Andreas, E-mail: Andreas.Wacker@fysik.lu.se; Karki, Khadga J., E-mail: Khadga.Karki@chemphys.lu.se

Multiple exciton generation (MEG) is a process in which more than one electron hole pair is generated per absorbed photon. It allows us to increase the efficiency of solar energy harvesting. Experimental studies have shown the multiple exciton generation yield of 1.2 in isolated colloidal quantum dots. However real photoelectric devices require the extraction of electron hole pairs to electric contacts. We provide a systematic study of the corresponding quantum coherent processes including extraction and injection and show that a proper design of extraction and injection rates enhances the yield significantly up to values around 1.6.

Synthesis and photophysical properties of aluminium tris-(4-morpholine-8-hydroxyquinoline)

PubMed Central

Omar, Walaa A.E.

2012-01-01

Aluminium tris(4-morpholinyl-8-hydroxyquinoline) has been synthesized and characterized. The photoluminescence measurements showed that the new derivative is blue shifted and has relative photoluminescence quantum yield two times higher compared to the pristine Al tris(8-hydroxyquinoline). Deferential scanning colorimetric studies revealed that the newly synthesized Alq3 derivative in this work is amorphous material with the highest transition glass temperature value among the reported amorphous Alq3 derivatives. PMID:25685461

Bright nanowire single photon source based on SiV centers in diamond

DOE PAGES

Marseglia, L.; Saha, K.; Ajoy, A.; ...

2018-01-01

The practical implementation of quantum technologies such as quantum commu- nication and quantum cryptography relies on the development of indistinguishable, robust, and bright single photon sources that works at room temperature. The silicon- vacancy (SiV -) center in diamond has emerged as a possible candidate for a single photon source with all these characteristics. Unfortunately, due to the high refraction index mismatch between diamond and air, color centers in diamond show low photon out-coupling. This drawback can be overcome by fabrication of photonic structures that improve the in-coupling of excitation laser to the diamond defect as well as the out-couplingmore » emission from the color centers. An additional shortcoming is due to the random localization of native defects in the diamond sample. Here we demonstrate deterministic implantation of Si ions with high conversion effciency to single SiV -, targeted to fabricated nanowires. The co-localization of single SiV - defects with the nanostructures yields a ten times higher light coupling effciency as compared to single SiV - in the bulk. This result, with its intrinsic scalability, enables a new class of devices for integrated photonics and quantum information processing.« less

Generalized Gibbs state with modified Redfield solution: Exact agreement up to second order

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

Thingna, Juzar; Wang, Jian-Sheng; Haenggi, Peter

A novel scheme for the steady state solution of the standard Redfield quantum master equation is developed which yields agreement with the exact result for the corresponding reduced density matrix up to second order in the system-bath coupling strength. We achieve this objective by use of an analytic continuation of the off-diagonal matrix elements of the Redfield solution towards its diagonal limit. Notably, our scheme does not require the provision of yet higher order relaxation tensors. Testing this modified method for a heat bath consisting of a collection of harmonic oscillators we assess that the system relaxes towards its correctmore » coupling-dependent, generalized quantum Gibbs state in second order. We numerically compare our formulation for a damped quantum harmonic system with the nonequilibrium Green's function formalism: we find good agreement at low temperatures for coupling strengths that are even larger than expected from the very regime of validity of the second-order Redfield quantum master equation. Yet another advantage of our method is that it markedly reduces the numerical complexity of the problem; thus, allowing to study efficiently large-sized system Hilbert spaces.« less

Comparison of the Light-Harvesting Networks of Plant and Cyanobacterial Photosystem I

PubMed Central

Şener, Melih K.; Jolley, Craig; Ben-Shem, Adam; Fromme, Petra; Nelson, Nathan; Croce, Roberta; Schulten, Klaus

2005-01-01

With the availability of structural models for photosystem I (PSI) in cyanobacteria and plants it is possible to compare the excitation transfer networks in this ubiquitous photosystem from two domains of life separated by over one billion years of divergent evolution, thus providing an insight into the physical constraints that shape the networks' evolution. Structure-based modeling methods are used to examine the excitation transfer kinetics of the plant PSI-LHCI supercomplex. For this purpose an effective Hamiltonian is constructed that combines an existing cyanobacterial model for structurally conserved chlorophylls with spectral information for chlorophylls in the Lhca subunits. The plant PSI excitation migration network thus characterized is compared to its cyanobacterial counterpart investigated earlier. In agreement with observations, an average excitation transfer lifetime of ∼49 ps is computed for the plant PSI-LHCI supercomplex with a corresponding quantum yield of 95%. The sensitivity of the results to chlorophyll site energy assignments is discussed. Lhca subunits are efficiently coupled to the PSI core via gap chlorophylls. In contrast to the chlorophylls in the vicinity of the reaction center, previously shown to optimize the quantum yield of the excitation transfer process, the orientational ordering of peripheral chlorophylls does not show such optimality. The finding suggests that after close packing of chlorophylls was achieved, constraints other than efficiency of the overall excitation transfer process precluded further evolution of pigment ordering. PMID:15994896

Loop Quantum Gravity.

PubMed

Rovelli, Carlo

2008-01-01

The problem of describing the quantum behavior of gravity, and thus understanding quantum spacetime , is still open. Loop quantum gravity is a well-developed approach to this problem. It is a mathematically well-defined background-independent quantization of general relativity, with its conventional matter couplings. Today research in loop quantum gravity forms a vast area, ranging from mathematical foundations to physical applications. Among the most significant results obtained so far are: (i) The computation of the spectra of geometrical quantities such as area and volume, which yield tentative quantitative predictions for Planck-scale physics. (ii) A physical picture of the microstructure of quantum spacetime, characterized by Planck-scale discreteness. Discreteness emerges as a standard quantum effect from the discrete spectra, and provides a mathematical realization of Wheeler's "spacetime foam" intuition. (iii) Control of spacetime singularities, such as those in the interior of black holes and the cosmological one. This, in particular, has opened up the possibility of a theoretical investigation into the very early universe and the spacetime regions beyond the Big Bang. (iv) A derivation of the Bekenstein-Hawking black-hole entropy. (v) Low-energy calculations, yielding n -point functions well defined in a background-independent context. The theory is at the roots of, or strictly related to, a number of formalisms that have been developed for describing background-independent quantum field theory, such as spin foams, group field theory, causal spin networks, and others. I give here a general overview of ideas, techniques, results and open problems of this candidate theory of quantum gravity, and a guide to the relevant literature.

Extending Bell's beables to encompass dissipation, decoherence, and the quantum-to-classical transition through quantum trajectories

NASA Astrophysics Data System (ADS)

Lorenzen, F.; de Ponte, M. A.; Moussa, M. H. Y.

2009-09-01

In this paper, employing the Itô stochastic Schrödinger equation, we extend Bell’s beable interpretation of quantum mechanics to encompass dissipation, decoherence, and the quantum-to-classical transition through quantum trajectories. For a particular choice of the source of stochasticity, the one leading to a dissipative Lindblad-type correction to the Hamiltonian dynamics, we find that the diffusive terms in Nelsons stochastic trajectories are naturally incorporated into Bohm’s causal dynamics, yielding a unified Bohm-Nelson theory. In particular, by analyzing the interference between quantum trajectories, we clearly identify the decoherence time, as estimated from the quantum formalism. We also observe the quantum-to-classical transition in the convergence of the infinite ensemble of quantum trajectories to their classical counterparts. Finally, we show that our extended beables circumvent the problems in Bohm’s causal dynamics regarding stationary states in quantum mechanics.

Bidentate Ligand-Passivated CsPbI3 Perovskite Nanocrystals for Stable Near-Unity Photoluminescence Quantum Yield and Efficient Red Light-Emitting Diodes.

PubMed

Pan, Jun; Shang, Yuequn; Yin, Jun; De Bastiani, Michele; Peng, Wei; Dursun, Ibrahim; Sinatra, Lutfan; El-Zohry, Ahmed M; Hedhili, Mohamed N; Emwas, Abdul-Hamid; Mohammed, Omar F; Ning, Zhijun; Bakr, Osman M

2018-01-17

Although halide perovskite nanocrystals (NCs) are promising materials for optoelectronic devices, they suffer severely from chemical and phase instabilities. Moreover, the common capping ligands like oleic acid and oleylamine that encapsulate the NCs will form an insulating layer, precluding their utility in optoelectronic devices. To overcome these limitations, we develop a postsynthesis passivation process for CsPbI 3 NCs by using a bidentate ligand, namely 2,2'-iminodibenzoic acid. Our passivated NCs exhibit narrow red photoluminescence with exceptional quantum yield (close to unity) and substantially improved stability. The passivated NCs enabled us to realize red light-emitting diodes (LEDs) with 5.02% external quantum efficiency and 748 cd/m 2 luminance, surpassing by far LEDs made from the nonpassivated NCs.

Activation energy of light induced isomerization of resveratrol.

PubMed

Figueiras, Teresa Sofia; Neves-Petersen, Maria Teresa; Petersen, Steffen B

2011-09-01

Isomerization of trans-stilbenes is known to be induced by light. The two isomers have distinct absorption, fluorescence excitation and emission spectra. Resveratrol, 3,4',5-trihydroxystilbene, is a member of the stilbene family. The interest of the scientific community in resveratrol has increased over the last years due to its biomedical properties. Whereas there is a growing confidence that trans-resveratrol is non-toxic, very little is known about the pharmacology of cis-resveratrol. Of this very reason there is considerable interest in knowing the energetics of the trans-cis conversion. Cis-resveratrol is characterized by a large fluorescence quantum yield when compared to trans-resveratrol. In the present paper we report a detailed analysis of the spectral changes induced in trans-resveratrol upon 260 nm excitation for different time periods. Spectral changes have been monitored with UV-visible absorption and steady-state fluorescence spectroscopy at pH 4 at 20, 25, 30, 35, 40, 45 and 50 °C. Continuous 260 nm excitation induces a blue shift in the absorption and fluorescence excitation spectra of resveratrol and a 14 nm blue shift in its fluorescence emission. The photoisomerization yield is reported as a function of 260 nm excitation time. 330 min continuous excitation led to ~60% isomerization yield. The kinetics of trans-cis isomerization has been monitored following the increase in fluorescence quantum yield upon continuous 260 nm excitation of trans-resveratrol. The study was carried out at the above mentioned temperatures in order to obtain the Arrhenius activation energy of photoisomerization. Activation energy and pre-exponential factor were 3.7 ± 0.3 kcal.mol(-1) and 10.6 ± 1.6 s(-1), respectively. The activation energy is comparable with previously reported values for the photoisomerization of other stilbenes.

Dose-Rate Effects in Breaking DNA Strands by Short Pulses of Extreme Ultraviolet Radiation.

PubMed

Vyšín, Luděk; Burian, Tomáš; Ukraintsev, Egor; Davídková, Marie; Grisham, Michael E; Heinbuch, Scott; Rocca, Jorge J; Juha, Libor

2018-05-01

In this study, we examined dose-rate effects on strand break formation in plasmid DNA induced by pulsed extreme ultraviolet (XUV) radiation. Dose delivered to the target molecule was controlled by attenuating the incident photon flux using aluminum filters as well as by changing the DNA/buffer-salt ratio in the irradiated sample. Irradiated samples were examined using agarose gel electrophoresis. Yields of single- and double-strand breaks (SSBs and DSBs) were determined as a function of the incident photon fluence. In addition, electrophoresis also revealed DNA cross-linking. Damaged DNA was inspected by means of atomic force microscopy (AFM). Both SSB and DSB yields decreased with dose rate increase. Quantum yields of SSBs at the highest photon fluence were comparable to yields of DSBs found after synchrotron irradiation. The average SSB/DSB ratio decreased only slightly at elevated dose rates. In conclusion, complex and/or clustered damages other than cross-links do not appear to be induced under the radiation conditions applied in this study.

Development of a Photoemission Surface for 1.06 Micron Wavelength

DOT National Transportation Integrated Search

1973-02-01

Development of a negative affirmity photoemitter with 10% quantum effieciency at the Nd3+ laser wavelengths near 1.06 microns. : Observed quantum yield of 7.55% (electrons per incident photon - 11% per absorbed photon) at 1.06 microns, from an InGaAs...

Faithful nonclassicality indicators and extremal quantum correlations in two-qubit states

NASA Astrophysics Data System (ADS)

Girolami, Davide; Paternostro, Mauro; Adesso, Gerardo

2011-09-01

The state disturbance induced by locally measuring a quantum system yields a signature of nonclassical correlations beyond entanglement. Here, we present a detailed study of such correlations for two-qubit mixed states. To overcome the asymmetry of quantum discord and the unfaithfulness of measurement-induced disturbance (severely overestimating quantum correlations), we propose an ameliorated measurement-induced disturbance as nonclassicality indicator, optimized over joint local measurements, and we derive its closed expression for relevant two-qubit states. We study its analytical relation with discord, and characterize the maximally quantum-correlated mixed states, that simultaneously extremize both quantifiers at given von Neumann entropy: among all two-qubit states, these states possess the most robust quantum correlations against noise.

Graphene quantum dots as enhanced plant growth regulators: effects on coriander and garlic plants.

PubMed

Chakravarty, Disha; Erande, Manisha B; Late, Dattatray J

2015-10-01

We report investigations on the use of graphene quantum dots for growth enhancement in coriander (Coriandrum sativam L.) and garlic (Allium sativum) plants. The as-received seeds of coriander and garlic were treated with 0.2 mg mL(-1) of graphene quantum dots for 3 h before planting. Graphene quantum dots enhanced the growth rate in coriander and garlic plants, including leaves, roots, shoots, flowers and fruits, when the seeds were treated with graphene quantum dots. Our investigations open up the opportunity to use graphene quantum dots as plant growth regulators that can be used in a variety of other food plants for high yield. © 2015 Society of Chemical Industry.

A general quantitative pH sensor developed with dicyandiamide N-doped high quantum yield graphene quantum dots.

PubMed

Wu, Zhu Lian; Gao, Ming Xuan; Wang, Ting Ting; Wan, Xiao Yan; Zheng, Lin Ling; Huang, Cheng Zhi

2014-04-07

A general quantitative pH sensor for environmental and intracellular applications was developed by the facile hydrothermal preparation of dicyandiamide (DCD) N-doped high quantum yield (QY) graphene quantum dots (GQDs) using citric acid (CA) as the carbon source. The obtained N-doped GQDs have excellent photoluminesence (PL) properties with a relatively high QY of 36.5%, suggesting that N-doped chemistry could promote the QY of carbon nanomaterials. The possible mechanism for the formation of the GQDs involves the CA self-assembling into a nanosheet structure through intermolecular H-bonding at the initial stage of the reaction, and then the pure graphene core with many function groups formed through the dehydration between the carboxyl and hydroxyl of the intermolecules under hydrothermal conditions. These N-doped GQDs have low toxicity, and are photostable and pH-sensitive between 1.81 to 8.96, giving a general pH sensor with a wide range of applications from real water to intracellular contents.

The effect of annulation of benzene rings on the photophysics and electronic structure of tetraazachlorin molecules

NASA Astrophysics Data System (ADS)

Pershukevich, P. P.; Volkovich, D. I.; Gladkov, L. L.; Dudkin, S. V.; Kuzmitsky, V. A.; Makarova, E. A.; Solovyev, K. N.

2017-10-01

The photophysics and electronic structure of tribenzotetraazachlorins (H2, Zn, and Mg), which are novel analogues of phtalocyanines, have been studied experimentally and theoretically. At 293 K, the electronic absorption, fluorescence, and fluorescence excitation spectra are recorded and the fluorescence quantum yield and lifetime, as well as the quantum yield of singlet oxygen generation, are measured; at 77 K, the fluorescence, fluorescence excitation, and fluorescence polarization spectra are recorded and the fluorescence lifetime values are measured. The dependences of the absorption spectra and photophysical parameters on the structure variation are analyzed in detail. Quantum-chemical calculations of the electronic structure and absorption spectra of tribenzotetraazachlorins (H2, Mg) are performed using the INDO/Sm method (modified INDO/S method) based on molecular-geometry optimization by the DFT PBE/TZVP method. The results of quantum-chemical calculations of the electronic absorption spectra are in very good agreement with the experimental data for the transitions to two lower electronic states.

Colloidal Spherical Quantum Wells with Near-Unity Photoluminescence Quantum Yield and Suppressed Blinking.

PubMed

Jeong, Byeong Guk; Park, Young-Shin; Chang, Jun Hyuk; Cho, Ikjun; Kim, Jai Kyeong; Kim, Heesuk; Char, Kookheon; Cho, Jinhan; Klimov, Victor I; Park, Philip; Lee, Doh C; Bae, Wan Ki

2016-10-02

Thick inorganic shell endows colloidal nanocrystals (NCs) with enhanced photochemical stability and suppression of photoluminescence intermittency (also known as blinking). However, the progress of using thick-shell heterostructure NCs in applications has been limited, due to low photoluminescence quantum yield (PL QY  60%) at room temperature. Here, we demonstrate thick-shell NCs with CdS/CdSe/CdS seed/spherical quantum well/shell (SQW) geometry that exhibit near-unity PL QY at room temperature and suppression of blinking. In SQW NCs, the lattice mismatch is diminished between the emissive CdSe layer and the surrounding CdS layers as a result of coherent strain, which suppresses the formation of misfit defects and consequently permits ~ 100% PL QY for SQW NCs with thick CdS shell (≥ 5 nm). High PL QY of thick-shell SQW NCs are preserved even in concentrated dispersion and in film under thermal stress, which makes them promising candidates for applications in solid-state lightings and luminescent solar concentrators.

A study of Kapton degradation under simulated shuttle environment

NASA Technical Reports Server (NTRS)

Eck, T. G.; Hoffman, R. W.

1986-01-01

A system was developed which employs a source of low energy oxygen ion to simulate the shuttle low Earth orbit environment. This source, together with diagnostic tools including surface analysis ans mass spectroscopic capability, was used to measure the dependence of ion energy of the oxygen induced CO signals from pyrolytic graphite and Kapton. For graphite the CO signal was examined at energies ranging form 4.5 to 465 eV and for Kapton from 4.5 to 188 eV. While the relative quantum yields inferred from the data are reasonably precise, there are large uncertainties in the absolute yields because of the assumptions necessary to covert the measured signal strengths to quantum yields. These assumptions are discussed in detail.

Phase transfer of 1- and 2-dimensional Cd-based nanocrystals

NASA Astrophysics Data System (ADS)

Kodanek, Torben; Banbela, Hadeel M.; Naskar, Suraj; Adel, Patrick; Bigall, Nadja C.; Dorfs, Dirk

2015-11-01

In this work, luminescent CdSe@CdS dot-in-rod nanocrystals, CdSe@CdS/ZnS nanorods as well as CdSe-CdS core-crown nanoplatelets were transferred into aqueous phase via ligand exchange reactions. For this purpose, bifunctional thiol-based ligands were employed, namely mercaptoacetic acid (MAA), 3-mercaptopropionic acid (MPA), 11-mercaptoundecanoic acid (MUA) as well as 2-(dimethylamino)ethanthiol (DMAET). Systematic investigations by means of photoluminescence quantum yield measurements as well as photoluminescence decay measurements have shown that the luminescence properties of the transferred nanostructures are affected by hole traps (induced by the thiol ligands themselves) as well as by spatial insulation and passivation against the environment. The influence of the tips of the nanorods on the luminescence is, however, insignificant. Accordingly, different ligands yield optimum results for different nanoparticle samples, mainly depending on the inorganic passivation of the respective samples. In case of CdSe@CdS nanorods, the highest emission intensities have been obtained by using short-chain ligands for the transfer preserving more than 50% of the pristine quantum yield of the hydrophobic nanorods. As opposed to this, the best possible quantum efficiency for the CdSe@CdS/ZnS nanorods has been achieved via MUA. The gained knowledge could be applied to transfer for the first time 2-dimensional CdSe-CdS core-crown nanoplatelets into water while preserving significant photoluminescence (up to 12% quantum efficiency).In this work, luminescent CdSe@CdS dot-in-rod nanocrystals, CdSe@CdS/ZnS nanorods as well as CdSe-CdS core-crown nanoplatelets were transferred into aqueous phase via ligand exchange reactions. For this purpose, bifunctional thiol-based ligands were employed, namely mercaptoacetic acid (MAA), 3-mercaptopropionic acid (MPA), 11-mercaptoundecanoic acid (MUA) as well as 2-(dimethylamino)ethanthiol (DMAET). Systematic investigations by means of photoluminescence quantum yield measurements as well as photoluminescence decay measurements have shown that the luminescence properties of the transferred nanostructures are affected by hole traps (induced by the thiol ligands themselves) as well as by spatial insulation and passivation against the environment. The influence of the tips of the nanorods on the luminescence is, however, insignificant. Accordingly, different ligands yield optimum results for different nanoparticle samples, mainly depending on the inorganic passivation of the respective samples. In case of CdSe@CdS nanorods, the highest emission intensities have been obtained by using short-chain ligands for the transfer preserving more than 50% of the pristine quantum yield of the hydrophobic nanorods. As opposed to this, the best possible quantum efficiency for the CdSe@CdS/ZnS nanorods has been achieved via MUA. The gained knowledge could be applied to transfer for the first time 2-dimensional CdSe-CdS core-crown nanoplatelets into water while preserving significant photoluminescence (up to 12% quantum efficiency). Electronic supplementary information (ESI) available: Further TEM images, further extinction spectra, particle size distribution and discussion about optical properties of the hydrophobic nanostructures. See DOI: 10.1039/c5nr06221g

Observables, measurements and phase operators from a Bohmian perspective

NASA Technical Reports Server (NTRS)

Daumer, Martin; Goldstein, Sheldon

1993-01-01

Bohmian mechanics is a deterministic theory of point particles in motion. While avoiding all the paradoxes of nonrelativistic quantum mechanics, it yields the quantum formalism itself--especially the role of self-adjoint operators--as a macroscopic measurement formalism. As an 'application' it is shown that much of the confusion connected with the phase operator for the electromagnetic field arises from a misunderstanding of the role of operators in quantum theory.

General Relativity without paradigm of space-time covariance, and resolution of the problem of time

NASA Astrophysics Data System (ADS)

Soo, Chopin; Yu, Hoi-Lai

2014-01-01

The framework of a theory of gravity from the quantum to the classical regime is presented. The paradigm shift from full space-time covariance to spatial diffeomorphism invariance, together with clean decomposition of the canonical structure, yield transparent physical dynamics and a resolution of the problem of time. The deep divide between quantum mechanics and conventional canonical formulations of quantum gravity is overcome with a Schrödinger equation for quantum geometrodynamics that describes evolution in intrinsic time. Unitary time development with gauge-invariant temporal ordering is also viable. All Kuchar observables become physical; and classical space-time, with direct correlation between its proper times and intrinsic time intervals, emerges from constructive interference. The framework not only yields a physical Hamiltonian for Einstein's theory, but also prompts natural extensions and improvements towards a well behaved quantum theory of gravity. It is a consistent canonical scheme to discuss Horava-Lifshitz theories with intrinsic time evolution, and of the many possible alternatives that respect 3-covariance (rather than the more restrictive 4-covariance of Einstein's theory), Horava's "detailed balance" form of the Hamiltonian constraint is essentially pinned down by this framework. Issues in quantum gravity that depend on radiative corrections and the rigorous definition and regularization of the Hamiltonian operator are not addressed in this work.

Laboratory study of nitrate photolysis in Antarctic snow. I. Observed quantum yield, domain of photolysis, and secondary chemistry

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

Meusinger, Carl; Johnson, Matthew S.; Berhanu, Tesfaye A.

2014-06-28

Post-depositional processes alter nitrate concentration and nitrate isotopic composition in the top layers of snow at sites with low snow accumulation rates, such as Dome C, Antarctica. Available nitrate ice core records can provide input for studying past atmospheres and climate if such processes are understood. It has been shown that photolysis of nitrate in the snowpack plays a major role in nitrate loss and that the photolysis products have a significant influence on the local troposphere as well as on other species in the snow. Reported quantum yields for the main reaction spans orders of magnitude – apparently amore » result of whether nitrate is located at the air-ice interface or in the ice matrix – constituting the largest uncertainty in models of snowpack NO{sub x} emissions. Here, a laboratory study is presented that uses snow from Dome C and minimizes effects of desorption and recombination by flushing the snow during irradiation with UV light. A selection of UV filters allowed examination of the effects of the 200 and 305 nm absorption bands of nitrate. Nitrate concentration and photon flux were measured in the snow. The quantum yield for loss of nitrate was observed to decrease from 0.44 to 0.003 within what corresponds to days of UV exposure in Antarctica. The superposition of photolysis in two photochemical domains of nitrate in snow is proposed: one of photolabile nitrate, and one of buried nitrate. The difference lies in the ability of reaction products to escape the snow crystal, versus undergoing secondary (recombination) chemistry. Modeled NO{sub x} emissions may increase significantly above measured values due to the observed quantum yield in this study. The apparent quantum yield in the 200 nm band was found to be ∼1%, much lower than reported for aqueous chemistry. A companion paper presents an analysis of the change in isotopic composition of snowpack nitrate based on the same samples as in this study.« less

Predawn and high intensity application of supplemental blue light decreases the quantum yield of PSII and enhances the amount of phenolic acids, flavonoids, and pigments in Lactuca sativa

PubMed Central

Ouzounis, Theoharis; Razi Parjikolaei, Behnaz; Fretté, Xavier; Rosenqvist, Eva; Ottosen, Carl-Otto

2015-01-01

To evaluate the effect of blue light intensity and timing, two cultivars of lettuce [Lactuca sativa cv. “Batavia” (green) and cv. “Lollo Rossa” (red)] were grown in a greenhouse compartment in late winter under natural light and supplemental high pressure sodium (SON-T) lamps yielding 90 (±10) μmol m−2 s−1 for up to 20 h, but never between 17:00 and 21:00. The temperature in the greenhouse compartments was 22/11°C day/night, respectively. The five light-emitting diode (LED) light treatments were Control (no blue addition), 1B 06-08 (Blue light at 45 μmol m−2 s−1 from 06:00 to 08:00), 1B 21-08 (Blue light at 45 μmol m−2 s−1 from 21:00 to 08:00), 2B 17-19 (Blue at 80 μmol m−2 s−1 from 17:00 to 19:00), and 1B 17-19 (Blue at 45 μmol m−2 s−1 from 17:00 to 19:00). Total fresh and dry weight was not affected with additional blue light; however, plants treated with additional blue light were more compact. The stomatal conductance in the green lettuce cultivar was higher for all treatments with blue light compared to the Control. Photosynthetic yields measured with chlorophyll fluorescence showed different response between the cultivars; in red lettuce, the quantum yield of PSII decreased and the yield of non-photochemical quenching increased with increasing blue light, whereas in green lettuce no difference was observed. Quantification of secondary metabolites showed that all four treatments with additional blue light had higher amount of pigments, phenolic acids, and flavonoids compared to the Control. The effect was more prominent in red lettuce, highlighting that the results vary among treatments and compounds. Our results indicate that not only high light level triggers photoprotective heat dissipation in the plant, but also the specific spectral composition of the light itself at low intensities. However, these plant responses to light are cultivar dependent. PMID:25767473

Terahertz quantum cascade laser as local oscillator in a heterodyne receiver.

PubMed

Hübers, Heinz-Wilhelm; Pavlov, S; Semenov, A; Köhler, R; Mahler, L; Tredicucci, A; Beere, H; Ritchie, D; Linfield, E

2005-07-25

Terahertz quantum cascade lasers have been investigated with respect to their performance as a local oscillator in a heterodyne receiver. The beam profile has been measured and transformed in to a close to Gaussian profile resulting in a good matching between the field patterns of the quantum cascade laser and the antenna of a superconducting hot electron bolometric mixer. Noise temperature measurements with the hot electron bolometer and a 2.5 THz quantum cascade laser yielded the same result as with a gas laser as local oscillator.

"Evaluations" of Observables Versus Measurements in Quantum Theory

NASA Astrophysics Data System (ADS)

Nisticò, Giuseppe; Sestito, Angela

2016-03-01

In Quantum Physics there are circumstances where the direct measurement of a given observable encounters difficulties; in some of these cases, however, its value can be "evaluated", i.e. it can be inferred by measuring another observable characterized by perfect correlation with the observable of interest. Though an evaluation is often interpreted as a measurement of the evaluated observable, we prove that the two concepts cannot be identified in Quantum Physics, because the identification yields contradictions. Then, we establish the conceptual status of evaluations in Quantum Theory and how they are related to measurements.

Divide and conquer approach to quantum Hamiltonian simulation

NASA Astrophysics Data System (ADS)

Hadfield, Stuart; Papageorgiou, Anargyros

2018-04-01

We show a divide and conquer approach for simulating quantum mechanical systems on quantum computers. We can obtain fast simulation algorithms using Hamiltonian structure. Considering a sum of Hamiltonians we split them into groups, simulate each group separately, and combine the partial results. Simulation is customized to take advantage of the properties of each group, and hence yield refined bounds to the overall simulation cost. We illustrate our results using the electronic structure problem of quantum chemistry, where we obtain significantly improved cost estimates under very mild assumptions.

Static properties of ferromagnetic quantum chains: Numerical results and experimental data on two S=1/2 systems (invited)

NASA Astrophysics Data System (ADS)

Kopinga, K.; Delica, T.; Leschke, H.

1990-05-01

New results of a variant of the numerically exact quantum transfer matrix method have been compared with experimental data on the static properties of [C6H11NH3]CuBr3(CHAB), a ferromagnetic system with about 5% easy-plane anisotropy. Above T=3.5 K, the available data on the zero-field heat capacity, the excess heat capacity ΔC=C(B)-C(B=0), and the magnetization are described with an accuracy comparable to the experimental error. Calculations of the spin-spin correlation functions reveal that the good description of the experimental correlation length in CHAB by a classical spin model is largely accidental. The zero-field susceptibility, which can be deduced from these correlation functions, is in fair agreement with the reported experimental data between 4 and 100 K. The method also seems to yield accurate results for the chlorine isomorph, CHAC, a system with about 2% uniaxial anisotropy.

Is the flower fluorescence relevant in biocommunication?

NASA Astrophysics Data System (ADS)

Iriel, Analía; Lagorio, María Gabriela

2010-10-01

Flower fluorescence has been previously proposed as a potential visual signal to attract pollinators. In this work, this point was addressed by quantitatively measuring the fluorescence quantum yield ( Φ f) for flowers of Bellis perennis (white, yellow, pink, and purple), Ornithogalum thyrsoides (petals and ovaries), Limonium sinuatum (white and yellow), Lampranthus productus (yellow), Petunia nyctaginiflora (white), Bougainvillea spectabilis (white and yellow), Antirrhinum majus (white and yellow), Eustoma grandiflorum (white and blue), Citrus aurantium (petals and stigma), and Portulaca grandiflora (yellow). The highest values were obtained for the ovaries of O. thyrsoides ( Φ f = 0.030) and for Citrus aurantium petals ( Φ f = 0.014) and stigma ( Φ f = 0.013). Emitted photons as fluorescence were compared with reflected photons. It was concluded that the fluorescence emission is negligible compared to the reflected light, even for the most fluorescent samples, and it may not be considered as an optical signal in biocommunication. The work was complemented with the calculation of quantum catches for each studied flower species to describe the visual sensitization of eye photoreceptors.

Quantum confinement effects across two-dimensional planes in MoS{sub 2} quantum dots

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

Gan, Z. X.; Liu, L. Z.; Wu, H. Y.

2015-06-08

The low quantum yield (∼10{sup −5}) has restricted practical use of photoluminescence (PL) from MoS{sub 2} composed of a few layers, but the quantum confinement effects across two-dimensional planes are believed to be able to boost the PL intensity. In this work, PL from 2 to 9 nm MoS{sub 2} quantum dots (QDs) is excluded from the solvent and the absorption and PL spectra are shown to be consistent with the size distribution. PL from MoS{sub 2} QDs is also found to be sensitive to aggregation due to the size effect.

Coherent quantum dynamics of a superconducting flux qubit.

PubMed

Chiorescu, I; Nakamura, Y; Harmans, C J P M; Mooij, J E

2003-03-21

We have observed coherent time evolution between two quantum states of a superconducting flux qubit comprising three Josephson junctions in a loop. The superposition of the two states carrying opposite macroscopic persistent currents is manipulated by resonant microwave pulses. Readout by means of switching-event measurement with an attached superconducting quantum interference device revealed quantum-state oscillations with high fidelity. Under strong microwave driving, it was possible to induce hundreds of coherent oscillations. Pulsed operations on this first sample yielded a relaxation time of 900 nanoseconds and a free-induction dephasing time of 20 nanoseconds. These results are promising for future solid-state quantum computing.

Investigations of quantum pendulum dynamics in a spin-1 BEC

NASA Astrophysics Data System (ADS)

Hoang, Thai; Gerving, Corey; Land, Ben; Anquez, Martin; Hamley, Chris; Chapman, Michael

2013-05-01

We investigate the quantum spin dynamics of a spin-1 BEC initialized to an unstable critical point of the dynamical phase space. The subsequent evolution of the collective states of the system is analogous to an inverted simple pendulum in the quantum limit and yields non-classical states with quantum correlations. For short evolution times in the low depletion limit, we observe squeezed states and for longer times beyond the low depletion limit we observe highly non-Gaussian distributions. C.D. Hamley, C.S. Gerving, T.M. Hoang, E.M. Bookjans, and M.S. Chapman, ``Spin-Nematic Squeezed Vacuum in a Quantum Gas,'' Nature Physics 8, 305-308 (2012).

Quantum non-Gaussianity and quantification of nonclassicality

NASA Astrophysics Data System (ADS)

Kühn, B.; Vogel, W.

2018-05-01

The algebraic quantification of nonclassicality, which naturally arises from the quantum superposition principle, is related to properties of regular nonclassicality quasiprobabilities. The latter are obtained by non-Gaussian filtering of the Glauber-Sudarshan P function. They yield lower bounds for the degree of nonclassicality. We also derive bounds for convex combinations of Gaussian states for certifying quantum non-Gaussianity directly from the experimentally accessible nonclassicality quasiprobabilities. Other quantum-state representations, such as s -parametrized quasiprobabilities, insufficiently indicate or even fail to directly uncover detailed information on the properties of quantum states. As an example, our approach is applied to multi-photon-added squeezed vacuum states.

Complementarity of quantum discord and classically accessible information

DOE PAGES

Zwolak, Michael P.; Zurek, Wojciech H.

2013-05-20

The sum of the Holevo quantity (that bounds the capacity of quantum channels to transmit classical information about an observable) and the quantum discord (a measure of the quantumness of correlations of that observable) yields an observable-independent total given by the quantum mutual information. This split naturally delineates information about quantum systems accessible to observers – information that is redundantly transmitted by the environment – while showing that it is maximized for the quasi-classical pointer observable. Other observables are accessible only via correlations with the pointer observable. In addition, we prove an anti-symmetry property relating accessible information and discord. Itmore » shows that information becomes objective – accessible to many observers – only as quantum information is relegated to correlations with the global environment, and, therefore, locally inaccessible. Lastly, the resulting complementarity explains why, in a quantum Universe, we perceive objective classical reality while flagrantly quantum superpositions are out of reach.« less

Decoherence and dissipation for a quantum system coupled to a local environment

NASA Technical Reports Server (NTRS)

Gallis, Michael R.

1994-01-01

Decoherence and dissipation in quantum systems has been studied extensively in the context of Quantum Brownian Motion. Effective decoherence in coarse grained quantum systems has been a central issue in recent efforts by Zurek and by Hartle and Gell-Mann to address the Quantum Measurement Problem. Although these models can yield very general classical phenomenology, they are incapable of reproducing relevant characteristics expected of a local environment on a quantum system, such as the characteristic dependence of decoherence on environment spatial correlations. I discuss the characteristics of Quantum Brownian Motion in a local environment by examining aspects of first principle calculations and by the construction of phenomenological models. Effective quantum Langevin equations and master equations are presented in a variety of representations. Comparisons are made with standard results such as the Caldeira-Leggett master equation.

Deterministic generation of multiparticle entanglement by quantum Zeno dynamics.

PubMed

Barontini, Giovanni; Hohmann, Leander; Haas, Florian; Estève, Jérôme; Reichel, Jakob

2015-09-18

Multiparticle entangled quantum states, a key resource in quantum-enhanced metrology and computing, are usually generated by coherent operations exclusively. However, unusual forms of quantum dynamics can be obtained when environment coupling is used as part of the state generation. In this work, we used quantum Zeno dynamics (QZD), based on nondestructive measurement with an optical microcavity, to deterministically generate different multiparticle entangled states in an ensemble of 36 qubit atoms in less than 5 microseconds. We characterized the resulting states by performing quantum tomography, yielding a time-resolved account of the entanglement generation. In addition, we studied the dependence of quantum states on measurement strength and quantified the depth of entanglement. Our results show that QZD is a versatile tool for fast and deterministic entanglement generation in quantum engineering applications. Copyright © 2015, American Association for the Advancement of Science.

Quantum information processing in the radical-pair mechanism: Haberkorn's theory violates the Ozawa entropy bound

NASA Astrophysics Data System (ADS)

Mouloudakis, K.; Kominis, I. K.

2017-02-01

Radical-ion-pair reactions, central for understanding the avian magnetic compass and spin transport in photosynthetic reaction centers, were recently shown to be a fruitful paradigm of the new synthesis of quantum information science with biological processes. We show here that the master equation so far constituting the theoretical foundation of spin chemistry violates fundamental bounds for the entropy of quantum systems, in particular the Ozawa bound. In contrast, a recently developed theory based on quantum measurements, quantum coherence measures, and quantum retrodiction, thus exemplifying the paradigm of quantum biology, satisfies the Ozawa bound as well as the Lanford-Robinson bound on information extraction. By considering Groenewold's information, the quantum information extracted during the reaction, we reproduce the known and unravel other magnetic-field effects not conveyed by reaction yields.

Characterization of cap-shaped silver particles for surface-enhanced fluorescence effects.

PubMed

Yamaguchi, Tetsuji; Kaya, Takatoshi; Takei, Hiroyuki

2007-05-15

Surface-enhanced fluorescence has potentially many desirable properties as an analytical method for medical diagnostics, but the effect observed so far is rather modest and only in conjunction with fluorophores with low quantum yields. Coupled with the fact that preparation of suitable surfaces at low costs has been difficult, this has limited its utilities. Here we report a novel method for forming uniform and reproducible surfaces with respectable enhancement ratios even for high-quantum-yield fluorophores. Formation of dense surface-adsorbed latex spheres on a flat surface via partial aggregation, followed by evaporation of silver, results in a film consisting of cap-shaped silver particles at high densities. Binding of fluorescence biomolecules, either through physisorption or antigen-antibody reaction, was performed, and enhancements close to 50 have been observed with fluorophores such as R-phycoerythrin and Alexa 546-labeled, bovine serum albumin, both of which have quantum yields around 0.8. We attribute this to the unique shape of the silver particle and the presence of abundant gaps among adjacent particles at high densities. The effectiveness of the new surface is also demonstrated with IL-6 sandwich assays.

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

De Chiara, Gabriele; Fazio, Rosario; Montangero, Simone

In this paper we present an approach to quantum cloning with unmodulated spin networks. The cloner is realized by a proper design of the network and a choice of the coupling between the qubits. We show that in the case of phase covariant cloner the XY coupling gives the best results. In the 1{yields}2 cloning we find that the value for the fidelity of the optimal cloner is achieved, and values comparable to the optimal ones in the general N{yields}M case can be attained. If a suitable set of network symmetries are satisfied, the output fidelity of the clones doesmore » not depend on the specific choice of the graph. We show that spin network cloning is robust against the presence of static imperfections. Moreover, in the presence of noise, it outperforms the conventional approach. In this case the fidelity exceeds the corresponding value obtained by quantum gates even for a very small amount of noise. Furthermore, we show how to use this method to clone qutrits and qudits. By means of the Heisenberg coupling it is also possible to implement the universal cloner although in this case the fidelity is 10% off that of the optimal cloner.« less

Lead-free/rare earth-free Green-light-emitting crystal based on organic-inorganic hybrid [(C10H16N)2][MnBr4] with high emissive quantum yields and large crystal size

NASA Astrophysics Data System (ADS)

Cai, Xing-Wei; Zhao, Yu-Yuan; Li, Hong; Huang, Cui-Ping; Zhou, Zhen

2018-06-01

With the flourishing development of emitting materials, tremendous technological progress has been accomplished. However, they still face great challenges in convenient economical environmental-friendly large-scale commercial production. Herein we designed this organic-inorganic hybrid lead-free compound, an emerging class of high-efficiency emitting materials, [(C10H16N)2][MnBr4] (1), which emits intense greenish photoluminescence with a high emissive quantum yields of 72.26%, was prepared through the convenient economical solution method. What's more, compared with rare earth fluorescent materials (especially green-emitting Tb), Mn material is rich in natural resources and low commercial cost, which would possess an increasingly predominant advantage in the preparation of luminescent materials. Additionally, the exceptional thermal stability as well as the low-cost/convenient preparation process makes crystal 1 with the large size of more than 1 cm to be an ideal technologically important green-emitting material and it would open up a new route towards the commercialization process of lead-free/rare earth-free hybrid emitting materials in display and sensing.

Photophysics of covalently functionalized single wall carbon nanotubes with verteporfin

NASA Astrophysics Data System (ADS)

Staicu, Angela; Smarandache, Adriana; Pascu, Alexandru; Pascu, Mihail Lucian

2017-09-01

Covalently functionalized single wall carbon nanotubes (SWCNT) with the photosensitizer verteporfin (VP) were synthesized and studied. Photophysical properties of the obtained compounds like optical absorption, laser-induced fluorescence and generated singlet oxygen were investigated. In order to highlight the features of the conjugated compound, its photophysical characteristics were compared with those of the mixtures of the initial components. The optical absorption data evidenced a compound that combines features of the primary SWCNTs and VP. This is the also the case of the laser induced fluorescence of the synthesized product. Moreover, fluorescence quantum yield (Φf) of the compound (Φf = 2.4%) is smaller than for the mixture of SWCNT and VP in (Φf = 3.2%). The behavior is expected, because linked VP (carrying the fluorescent moiety) transfers easier a part of its excitation energy to the SWCNT in the covalent structure. Relative to the quantum yield of singlet oxygen generation (ΦΔ) by Methylene Blue, it was found that the ΦΔ for the conjugated VP-SWCNT is 51% while for the mixture ΦΔ is 23%. The results indicate covalently functionalized single walled carbon nanotubes with verteporfin as potential compounds of interest in targeted drug delivery and photodynamic therapy.

Halogen Radicals Promote the Photodegradation of Microcystins in Estuarine Systems.

PubMed

Parker, Kimberly M; Reichwaldt, Elke S; Ghadouani, Anas; Mitch, William A

2016-08-16

The transport of microcystin, a hepatotoxin produced by cyanobacteria (e.g., Microcystis aeruginosa), to estuaries can adversely affect estuarine and coastal ecosystems. We evaluated whether halogen radicals (i.e., reactive halogen species (RHS)) could significantly contribute to microcystin photodegradation during transport within estuaries. Experiments in synthetic and natural water samples demonstrated that the presence of seawater halides increased quantum yields for microcystin indirect photodegradation by factors of 3-6. Additional experiments indicated that photoproduced RHS were responsible for this effect. Despite the fact that dissolved organic matter (DOM) concentrations decreased in more saline waters, the calculated photochemical half-life of microcystin decreased 6-fold with increasing salinity along a freshwater-estuarine transect due to the halide-associated increase in quantum yield. Modeling of microcystin photodegradation along this transect indicated that the time scale for RHS-mediated microcystin photodegradation is comparable to the time scale of transport. Microcystin concentrations decline by ∼98% along the transect when considering photodegradation by RHS, but only by ∼54% if this pathway were ignored. These results suggest the importance of considering RHS-mediated photodegradation in future models of microcystin fate in freshwater-estuarine systems.

Spraying Brassinolide improves Sigma Broad tolerance in foxtail millet (Setaria italica L.) through modulation of antioxidant activity and photosynthetic capacity.

PubMed

Yuan, Xiang-Yang; Zhang, Li-Guang; Huang, Lei; Yang, Hui-Jie; Zhong, Yan-Ting; Ning, Na; Wen, Yin-Yuan; Dong, Shu-Qi; Song, Xi-E; Wang, Hong-Fu; Guo, Ping-Yi

2017-09-11

To explore the role of Brassinolide (BR) in improving the tolerance of Sigma Broad in foxtail millet (Setaria italica L.), effects of 0.1 mg/L of BR foliar application 24 h before 3.37 g/ha of Sigma Broad treatment at five-leaf stage of foxtail millet on growth parameters, antioxidant enzymes, malondialdehyde (MDA), chlorophyll, net photosynthetic rate (P N ), chlorophyll fluorescence and P 700 parameters were studied 7 and 15 d after herbicide treatment, respectively. Results showed that Sigma Broad significantly decreased plant height, activities of superoxide dismutase (SOD), chlorophyll content, P N , PS II effective quantum yield (Y (II)), PS II electron transport rate (ETR (II)), photochemical quantum yield of PSI(Y (I)) and PS I electron transport rate ETR (I), but significantly increased MDA. Compared to herbicide treatment, BR dramatically increased plant height, activities of SOD, Y (II), ETR (II), Y (I) and ETR (I). This study showed BR pretreatment could improve the tolerance of Sigma Broad in foxtail millet through improving the activity of antioxidant enzymes, keeping electron transport smooth, and enhancing actual photochemical efficiency of PS II and PSI.

Discrimination and quantification of autofluorescence spectra of human lung cells

NASA Astrophysics Data System (ADS)

Rahmani, Mahya; Khani, Mohammad Mehdi; Khazaei Koohpar, Zeinab; Molik, Paria

2016-10-01

To study laser-induced autofluorescence spectroscopy of the human lung cell line, we evaluated the native fluorescence properties of cancer QU-DB and normal MRC-5 human lung cells during continuous exposure to 405 nm laser light. Two emission bands centered at ~470 nm and ~560 nm were observed. These peaks are most likely attributable to mitochondrial fluorescent reduced nicotinamide adenine dinucleotide and riboflavin fluorophores, respectively. This article highlights lung cell autofluorescence characterization and signal discrimination by collective investigation of different spectral features. The absolute intensity, the spectral shape factor or redox ratio, the full width of half-maximum and the full width of quarter maximum was evaluated. Moreover, the intensity ratio, the area under the peak and the area ratio as a contrast factor for normal and cancerous cells were also calculated. Among all these features it seems that the contrast factor precisely and significantly discriminates the spectral differences of normal and cancerous lung cells. On the other hand, the relative quantum yield for both cell types were found by comparing the quantum yield of an unknown compound with known fluorescein sodium as a reference solution.

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

Yang, Lu; Zhang, Sheng; Qu, Xiaoni

Lanthanide MOFs, [Eu(TCA)(NDC)·H{sub 2}O]{sub n} (1) and [Tb(TCA)(NDC)·H{sub 2}O]{sub n} (2), have been prepared with the mixed aromatic carboxylate ligands, namely, 4,4′,4″-tricarboxytriphenylamine (H{sub 3}TCA) and 1,4-naphthalenedicarboxylate (H{sub 2}NDC). Single-crystal X-ray diffraction analysis reveals that isomorphic 1 and 2 present pillar-layered 3D framework that Eu/Tb(III) bond with carboxylate in various coordination fashions. Optical investigation indicates that the as-prepared compounds feature characteristic luminescence emission bands of Eu/Tb ions in the visible regions at room temperature. Moreover, compound 2 shows a relatively longer luminescence lifetime (τ=0.342 ms) and significantly enhanced quantum yield (Φ{sub overall}=11%) comparing with those of 1 (τ=0.335 ms, Φ{sub overall}=0.06%).more » - Graphical abstract: Synoptic: Two Ln-MOFs (Ln=Eu{sup III}, Tb{sup III}) with mixed polycarboxylate ligands present different luminescent properties. - Highlights: • Two Eu/Tb-MOFs with H{sub 3}TCA and H{sub 2}NDC ligands have been obtained. • The ancillary ligand is employed to decrease water molecule coordinate numbers. • 2displays superior quantum yield and lifetime than those of 1.« less

Spectroscopic investigation of alloyed quantum dot-based FRET to cresyl violet dye.

PubMed

Kotresh, M G; Adarsh, K S; Shivkumar, M A; Mulimani, B G; Savadatti, M I; Inamdar, S R

2016-05-01

Quantum dots (QDs), bright luminescent semiconductor nanoparticles, have found numerous applications ranging from optoelectronics to bioimaging. Here, we present a systematic investigation of fluorescence resonance energy transfer (FRET) from hydrophilic ternary alloyed quantum dots (CdSeS/ZnS) to cresyl violet dye with a view to explore the effect of composition of QD donors on FRET efficiency. Fluorescence emission of QD is controlled by varying the composition of QD without altering the particle size. The results show that quantum yield of the QDs increases with increase in the emission wavelength. The FRET parameters such as spectral overlap J(λ), Förster distance R0, intermolecular distance (r), rate of energy transfer k(T)(r), and transfer efficiency (E) are determined by employing both steady-state and time-resolved fluorescence spectroscopy. Additionally, dynamic quenching is noticed to occur in the present FRET system. Stern-Volmer (K(D)) and bimolecular quenching constants (k(q)) are determined from the Stern-Volmer plot. It is observed that the transfer efficiency follows a linear dependence on the spectral overlap and the quantum yield of the donor as predicted by the Förster theory upon changing the composition of the QD. Copyright © 2015 John Wiley & Sons, Ltd.

High Quantum Yield Blue Emission from Lead-Free Inorganic Antimony Halide Perovskite Colloidal Quantum Dots.

PubMed

Zhang, Jian; Yang, Ying; Deng, Hui; Farooq, Umar; Yang, Xiaokun; Khan, Jahangeer; Tang, Jiang; Song, Haisheng

2017-09-26

Colloidal quantum dots (QDs) of lead halide perovskite have recently received great attention owing to their remarkable performances in optoelectronic applications. However, their wide applications are hindered from toxic lead element, which is not environment- and consumer-friendly. Herein, we utilized heterovalent substitution of divalent lead (Pb 2+ ) with trivalent antimony (Sb 3+ ) to synthesize stable and brightly luminescent Cs 3 Sb 2 Br 9 QDs. The lead-free, full-inorganic QDs were fabricated by a modified ligand-assisted reprecipitation strategy. A photoluminescence quantum yield (PLQY) was determined to be 46% at 410 nm, which was superior to that of other reported halide perovskite QDs. The PL enhancement mechanism was unraveled by surface composition derived quantum-well band structure and their large exciton binding energy. The Br-rich surface and the observed 530 meV exciton binding energy were proposed to guarantee the efficient radiative recombination. In addition, we can also tune the inorganic perovskite QD (Cs 3 Sb 2 X 9 ) emission wavelength from 370 to 560 nm via anion exchange reactions. The developed full-inorganic lead-free Sb-perovskite QDs with high PLQY and stable emission promise great potential for efficient emission candidates.

Perovskite Quantum Dots with Near Unity Solution and Neat-Film Photoluminescent Quantum Yield by Novel Spray Synthesis.

PubMed

Dai, Shu-Wen; Hsu, Bo-Wei; Chen, Chien-Yu; Lee, Chia-An; Liu, Hsiao-Yun; Wang, Hsiao-Fang; Huang, Yu-Ching; Wu, Tien-Lin; Manikandan, Arumugam; Ho, Rong-Ming; Tsao, Cheng-Si; Cheng, Chien-Hong; Chueh, Yu-Lun; Lin, Hao-Wu

2018-02-01

In this study, a novel perovskite quantum dot (QD) spray-synthesis method is developed by combining traditional perovskite QD synthesis with the technique of spray pyrolysis. By utilizing this new technique, the synthesis of cubic-shaped perovskite QDs with a homogeneous size of 14 nm is demonstrated, which shows an unprecedented stable absolute photoluminescence quantum yield ≈100% in the solution and even in the solid-state neat film. The highly emissive thin films are integrated with light emission devices (LEDs) and organic light emission displays (OLEDs). The color conversion type QD-LED (ccQD-LED) hybrid devices exhibit an extremely saturated green emission, excellent external quantum efficiency of 28.1%, power efficiency of 121 lm W -1 , and extraordinary forward-direction luminescence of 8 500 000 cd m -2 . The conceptual ccQD-OLED hybrid display also successfully demonstrates high-definition still images and moving pictures with a 119% National Television System Committee 1931 color gamut and 123% Digital Cinema Initiatives-P3 color gamut. These very-stable, ultra-bright perovskite QDs have the properties necessary for a variety of useful applications in optoelectronics. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Green, Rapid, and Universal Preparation Approach of Graphene Quantum Dots under Ultraviolet Irradiation.

PubMed

Zhu, Jinli; Tang, Yanfeng; Wang, Gang; Mao, Jiarong; Liu, Zhiduo; Sun, Tongming; Wang, Miao; Chen, Da; Yang, Yucheng; Li, Jipeng; Deng, Yuan; Yang, Siwei

2017-04-26

It is of great significance and importance to explore a mild, clean, and highly efficient universal approach for the synthesis of graphene quantum dots. Herein, we introduced a new green, rapid, and universal preparation approach for graphene quantum dots via the free-radical polymerization of oxygen-containing aromatic compounds under ultraviolet irradiation. This approach had a high yield (86%), and the byproducts are only H 2 O and CO 2 . The obtained graphene quantum dots were well-crystallized and showed remarkable optical and biological properties. The colorful, different-sized graphene quantum dots can be used in fluorescent bioimaging in vitro and in vivo. This approach is suitable not only for the preparation of graphene quantum dots but also for heteroatom-doped graphene quantum dots.

Quantum-capacity-approaching codes for the detected-jump channel

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

Grassl, Markus; Wei Zhaohui; Ji Zhengfeng

2010-12-15

The quantum-channel capacity gives the ultimate limit for the rate at which quantum data can be reliably transmitted through a noisy quantum channel. Degradable quantum channels are among the few channels whose quantum capacities are known. Given the quantum capacity of a degradable channel, it remains challenging to find a practical coding scheme which approaches capacity. Here we discuss code designs for the detected-jump channel, a degradable channel with practical relevance describing the physics of spontaneous decay of atoms with detected photon emission. We show that this channel can be used to simulate a binary classical channel with both erasuresmore » and bit flips. The capacity of the simulated classical channel gives a lower bound on the quantum capacity of the detected-jump channel. When the jump probability is small, it almost equals the quantum capacity. Hence using a classical capacity-approaching code for the simulated classical channel yields a quantum code which approaches the quantum capacity of the detected-jump channel.« less

Design and Synthesis of Antiblinking and Antibleaching Quantum Dots in Multiple Colors via Wave Function Confinement.

PubMed

Cao, Hujia; Ma, Junliang; Huang, Lin; Qin, Haiyan; Meng, Renyang; Li, Yang; Peng, Xiaogang

2016-12-07

Single-molecular spectroscopy reveals that photoluminescence (PL) of a single quantum dot blinks, randomly switching between bright and dim/dark states under constant photoexcitation, and quantum dots photobleach readily. These facts cast great doubts on potential applications of these promising emitters. After ∼20 years of efforts, synthesis of nonblinking quantum dots is still challenging, with nonblinking quantum dots only available in red-emitting window. Here we report synthesis of nonblinking quantum dots covering most part of the visible window using a new synthetic strategy, i.e., confining the excited-state wave functions of the core/shell quantum dots within the core quantum dot and its inner shells (≤ ∼5 monolayers). For the red-emitting ones, the new synthetic strategy yields nonblinking quantum dots with small sizes (∼8 nm in diameter) and improved nonblinking properties. These new nonblinking quantum dots are found to be antibleaching. Results further imply that the PL blinking and photobleaching of quantum dots are likely related to each other.

Unraveling the Mechanism of the Photodeprotection Reaction of 8-Bromo- and 8-Chloro-7-hydroxyquinoline Caged Acetates

PubMed Central

Ma, Jiani; Rea, Adam C; An, Huiying; Ma, Chensheng; Guan, Xiangguo; Li, Ming-De; Su, Tao; Yeung, Chi Shun; Harris, Kyle T; Zhu, Yue; Nganga, Jameil L; Fedoryak, Olesya D; Dore, Timothy M; Phillips, David Lee

2012-01-01

Abstract Photoremovable protecting groups (PPGs) when conjugated to biological effectors forming “caged compounds” are a powerful means to regulate the action of physiologically active messengers in vivo through 1-photon excitation (1PE) and 2-photon excitation (2PE). Understanding the photodeprotection mechanism is important for their physiological use. We compared the quantum efficiencies and product outcomes in different solvent and pH conditions for the photolysis reactions of (8-chloro-7-hydroxyquinolin-2-yl)methyl acetate (CHQ-OAc) and (8-bromo-7-hydroxyquinolin-2-yl)methyl acetate (BHQ-OAc), representatives of the quinoline class of phototriggers for biological use, and conducted nanosecond time-resolved spectroscopic studies using transient emission (ns-EM), transient absorption (ns-TA), transient resonance Raman (ns-TR2), and time-resolved resonance Raman (ns-TR3) spectroscopies. The results indicate differences in the photochemical mechanisms and product outcomes, and reveal that the triplet excited state is most likely on the pathway to the product and that dehalogenation competes with release of acetate from BHQ-OAc, but not CHQ-OAc. A high fluorescence quantum yield and a more efficient excited-state proton transfer (ESPT) in CHQ-OAc compared to BHQ-OAc explain the lower quantum efficiency of CHQ-OAc relative to BHQ-OAc. PMID:22511356

A semi-classical approach to the calculation of highly excited rotational energies for asymmetric-top molecules

PubMed Central

Schmiedt, Hanno; Schlemmer, Stephan; Yurchenko, Sergey N.; Yachmenev, Andrey

2017-01-01

We report a new semi-classical method to compute highly excited rotational energy levels of an asymmetric-top molecule. The method forgoes the idea of a full quantum mechanical treatment of the ro-vibrational motion of the molecule. Instead, it employs a semi-classical Green's function approach to describe the rotational motion, while retaining a quantum mechanical description of the vibrations. Similar approaches have existed for some time, but the method proposed here has two novel features. First, inspired by the path integral method, periodic orbits in the phase space and tunneling paths are naturally obtained by means of molecular symmetry analysis. Second, the rigorous variational method is employed for the first time to describe the molecular vibrations. In addition, we present a new robust approach to generating rotational energy surfaces for vibrationally excited states; this is done in a fully quantum-mechanical, variational manner. The semi-classical approach of the present work is applied to calculating the energies of very highly excited rotational states and it reduces dramatically the computing time as well as the storage and memory requirements when compared to the fullly quantum-mechanical variational approach. Test calculations for excited states of SO2 yield semi-classical energies in very good agreement with the available experimental data and the results of fully quantum-mechanical calculations. PMID:28000807

Efficient quantum computing using coherent photon conversion.

PubMed

Langford, N K; Ramelow, S; Prevedel, R; Munro, W J; Milburn, G J; Zeilinger, A

2011-10-12

Single photons are excellent quantum information carriers: they were used in the earliest demonstrations of entanglement and in the production of the highest-quality entanglement reported so far. However, current schemes for preparing, processing and measuring them are inefficient. For example, down-conversion provides heralded, but randomly timed, single photons, and linear optics gates are inherently probabilistic. Here we introduce a deterministic process--coherent photon conversion (CPC)--that provides a new way to generate and process complex, multiquanta states for photonic quantum information applications. The technique uses classically pumped nonlinearities to induce coherent oscillations between orthogonal states of multiple quantum excitations. One example of CPC, based on a pumped four-wave-mixing interaction, is shown to yield a single, versatile process that provides a full set of photonic quantum processing tools. This set satisfies the DiVincenzo criteria for a scalable quantum computing architecture, including deterministic multiqubit entanglement gates (based on a novel form of photon-photon interaction), high-quality heralded single- and multiphoton states free from higher-order imperfections, and robust, high-efficiency detection. It can also be used to produce heralded multiphoton entanglement, create optically switchable quantum circuits and implement an improved form of down-conversion with reduced higher-order effects. Such tools are valuable building blocks for many quantum-enabled technologies. Finally, using photonic crystal fibres we experimentally demonstrate quantum correlations arising from a four-colour nonlinear process suitable for CPC and use these measurements to study the feasibility of reaching the deterministic regime with current technology. Our scheme, which is based on interacting bosonic fields, is not restricted to optical systems but could also be implemented in optomechanical, electromechanical and superconducting systems with extremely strong intrinsic nonlinearities. Furthermore, exploiting higher-order nonlinearities with multiple pump fields yields a mechanism for multiparty mediation of the complex, coherent dynamics.

Comparing the acute sensitivity of growth and photosynthetic endpoints in three Lemna species exposed to four herbicides.

PubMed

Park, Jihae; Brown, Murray T; Depuydt, Stephen; Kim, Jang K; Won, Dam-Soo; Han, Taejun

2017-01-01

An ecological impact assessment of four herbicides (atrazine, diuron, paraquat and simazine) was assessed using the aquatic floating vascular plants, Lemna gibba, Lemna minor and Lemna paucicostata as test organisms. The sensitivity of several ecologically relevant parameters (increase in frond area, root length after regrowth, maximum and effective quantum yield of PSII and maximum electron transport rate (ETR max ), were compared after a 72 h exposure to herbicides. The present test methods require relatively small sample volume (3 mL), shorter exposure times (72 h), simple and quick analytical procedures as compared with standard Lemna assays. Sensitivity ranking of endpoints, based on EC 50 values, differed depending on the herbicide. The most toxic herbicides were diuron and paraquat and the most sensitive endpoints were root length (6.0-12.3 μg L -1 ) and ETR max (4.7-10.3 μg L -1 ) for paraquat and effective quantum yield (6.8-10.4 μg L -1 ) for diuron. Growth and chlorophyll a fluorescence parameters in all three Lemna species were sensitive enough to detect toxic levels of diuron and paraquat in water samples in excess of allowable concentrations set by international standards. CV values of all EC 50 s obtained from the Lemna tests were in the range of 2.8-24.33%, indicating a high level of repeatability comparable to the desirable level of <30% for adoption of toxicity test methods as international standards. Our new Lemna methods may provide useful information for the assessment of toxicity risk of residual herbicides in aquatic ecosystems. Copyright © 2016 Elsevier Ltd. All rights reserved.

A molecular-field approximation for quantum crystals. Ph.D. Thesis; [considering ground state properties

NASA Technical Reports Server (NTRS)

Danilowicz, R.

1973-01-01

Ground-state properties of quantum crystals have received considerable attention from both theorists and experimentalists. The theoretical results have varied widely with the Monte Carlo calculations being the most successful. The molecular field approximation yields ground-state properties which agree closely with the Monte Carlo results. This approach evaluates the dynamical behavior of each pair of molecules in the molecular field of the other N-2 molecules. In addition to predicting ground-state properties that agree well with experiment, this approach yields data on the relative importance of interactions of different nearest neighbor pairs.

Optical study of HgCdTe infrared photodetectors using internal photoemission spectroscopy

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

Lao, Yan-Feng; Unil Perera, A. G., E-mail: uperera@gsu.edu; Wijewarnasuriya, Priyalal S.

2014-03-31

We report a study of internal photoemission spectroscopy (IPE) applied to a n-type Hg{sub 1−x}Cd{sub x}Te/Hg{sub 1−y}Cd{sub y}Te heterojunction. An exponential line-shape of the absorption tail in HgCdTe is identified by IPE fittings of the near-threshold quantum yield spectra. The reduction of quantum yield (at higher photon energy) below the fitting value is explained as a result of carrier-phonon scatterings. In addition, the obtained bias independence of the IPE threshold indicates a negligible electron barrier at the heterojunction interface.

pHP-Tethered N-Acyl Carbamate: A Photocage for Nicotinamide.

PubMed

Salahi, Farbod; Purohit, Vatsal; Ferraudi, Guillermo; Stauffacher, Cynthia; Wiest, Olaf; Helquist, Paul

2018-05-04

The synthesis of a new photocaged nicotinamide having an N-acyl carbamate linker and a p-hydroxyphenacyl (pHP) chromophore is described. The photophysical and photochemical studies showed an absorption maximum at λ = 330 nm and a quantum yield for release of 11% that are dependent upon both pH and solvent. While the acyl carbamate releases nicotinamide efficiently, a simpler amide linker was inert to photocleavage. This photocaged nicotinamide has significant advantages with respect to quantum yield, absorbance wavelength, rate of release, and solubility that make it the first practical example of a photocaged amide.

Determination of absolute chemiluminescence quantum yields for reactions of bis-(pentachlorophenyl) oxalate, hydrogen peroxide and fluorescent compounds.

PubMed

Catherall, C L; Palmer, T F; Cundall, R B

1989-01-01

Absolute chemiluminescence quantum yields (phi CL) for reactions of bis-(pentachlorophenyl) oxalate (PCPO), hydrogen peroxide (H2O2) and 9:10 diphenyl anthracene (DPA) have been determined. A fully corrected chemiluminescence monitoring spectrometer was calibrated for spectral sensitivity using the chemiluminescence of the bis-(pentachlorophenyl) oxalate system as a liquid light source, the total photon output of which had previously been determined by chemical actinometry. At high (PCPO)/(H2O2) ratios phi CL was found to be independent of PCPO and H2O2 concentrations.

Dilepton production from hot hadronic matter in nonequilibrium

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

Schenke, B.; Greiner, C.

2006-03-15

The influence of time-dependent medium modifications of low-mass vector mesons on dilepton production is investigated within a nonequilibrium quantum field-theoretical description on the basis of the Kadanoff-Baym equations. Time scales for the adaption of the spectral properties to changing self-energies are given, and, under use of a model for the fireball evolution, nonequilibrium dilepton yields from the decay of {rho} and {omega} mesons are calculated. In a comparison of these yields, those from calculations that assume instantaneous (Markovian) adaption to the changing-medium quantum-mechanical memory effects turn out to be important.

Do genotypic differences in thermotolerance plasticity correspond with water-induced differences in yield and photosynthetic stability for field-grown upland cotton?

USDA-ARS?s Scientific Manuscript database

To determine if cultivar differences in thermotolerance plasticity of photosystem II promote yield or photosynthetic stability when variability in both parameters is water-induced, the temperature response of maximum quantum yield of photosystem II (Fv/Fm) was evaluated for two cotton cultivars (FM ...

The photochemistry and kinetics of chlorine compounds important to stratospheric mid-latitude ozone destruction

NASA Astrophysics Data System (ADS)

Goldfarb, Leah

1997-09-01

The catalytic destruction of stratospheric ozone via chlorinated species was first proposed in the 1970's. Since that time a decline in column ozone abundance in the polar regions as well as at mid-latitudes has been observed. Much of this reduction has been attributed to the increases in anthropogenic chlorine compounds such as CFCs. This study summarizes experimental results obtained using pulsed-photolysis resonance fluorescence and pulsed- photolysis long-path absorption methods to study processes important to chlorine-catalyzed ozone destruction: the quantum yields of the products in the dissociation of ClONO2 and the reactions of free radicals with ClONO2 and ClO. The quantum yields for the production of O, Cl and ClO from ClONO2 were studied at specific laser wavelengths (193, 222, 248, and 308 nm). Cl and ClO yields were comparable at nearly all the wavelengths, expect for 193 nm, where the O atom yield was appreciable. The yields at 308 nm (a wavelength available in the stratosphere) were 0.64 ± 0.17 for Cl, 0.37 ± 0.18 for ClO and <0.05 for O. The rate coefficients of O and Cl atoms with ClONO2 were measured over a wide range of temperatures, and the NO3 product yield for the former reaction, previously unreported, was determined to be ~1. The kinetics of the reaction of O atoms with ClO were measured using a new experimental system built specifically to investigate such radical-radical reactions. A slight negative temperature dependence (E/B = -90 ± 30) was observed over the temperature range (227-363 K). From the measured Arrhenius equation the rate constant at 240 K is 4.1 × 10-11 cm3molecule-1s-1 which is in excellent agreement (l.4% greater) with the currently recommended value. This observation is significant, since this reaction is the rate limiting the dominate chlorine catalytic cycle that destroys O3 near 40 km. To analyze the implications of the kinetic and photochemical information from this work, a box model was constructed. The vertical profile of ozone concentrations and loss rates calculated by this simple model compare well with atmospheric measurements and calculations.

Revisiting the quantum Szilard engine with fully quantum considerations

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

Li, Hai; School of Information and Electronics Engineering, Shandong Institute of Business and Technology, Yantai 264000; Zou, Jian, E-mail: zoujian@bit.edu.cn

2012-12-15

By considering level shifting during the insertion process we revisit the quantum Szilard engine (QSZE) with fully quantum consideration. We derive the general expressions of the heat absorbed from thermal bath and the total work done to the environment by the system in a cycle with two different cyclic strategies. We find that only the quantum information contributes to the absorbed heat, and the classical information acts like a feedback controller and has no direct effect on the absorbed heat. This is the first demonstration of the different effects of quantum information and classical information for extracting heat from themore » bath in the QSZE. Moreover, when the well width L{yields}{infinity} or the temperature of the bath T{yields}{infinity} the QSZE reduces to the classical Szilard engine (CSZE), and the total work satisfies the relation W{sub tot}=k{sub B}Tln2 as obtained by Sang Wook Kim et al. [S.W. Kim, T. Sagawa, S. De Liberato, M. Ueda, Phys. Rev. Lett. 106 (2011) 070401] for one particle case. - Highlights: Black-Right-Pointing-Pointer For the first time analyze the QSZE by considering energy level shifts. Black-Right-Pointing-Pointer Find different roles played by classical and quantum information in the QSZE. Black-Right-Pointing-Pointer The amount of work extracted depends on the cyclic strategies of the QSZE. Black-Right-Pointing-Pointer Verify that the QSZE will reduce to the CSZE in the classical limits.« less

Markov chain Monte Carlo estimation of quantum states

NASA Astrophysics Data System (ADS)

Diguglielmo, James; Messenger, Chris; Fiurášek, Jaromír; Hage, Boris; Samblowski, Aiko; Schmidt, Tabea; Schnabel, Roman

2009-03-01

We apply a Bayesian data analysis scheme known as the Markov chain Monte Carlo to the tomographic reconstruction of quantum states. This method yields a vector, known as the Markov chain, which contains the full statistical information concerning all reconstruction parameters including their statistical correlations with no a priori assumptions as to the form of the distribution from which it has been obtained. From this vector we can derive, e.g., the marginal distributions and uncertainties of all model parameters, and also of other quantities such as the purity of the reconstructed state. We demonstrate the utility of this scheme by reconstructing the Wigner function of phase-diffused squeezed states. These states possess non-Gaussian statistics and therefore represent a nontrivial case of tomographic reconstruction. We compare our results to those obtained through pure maximum-likelihood and Fisher information approaches.

On the minimum quantum requirement of photosynthesis.

PubMed

Zeinalov, Yuzeir

2009-01-01

An analysis of the shape of photosynthetic light curves is presented and the existence of the initial non-linear part is shown as a consequence of the operation of the non-cooperative (Kok's) mechanism of oxygen evolution or the effect of dark respiration. The effect of nonlinearity on the quantum efficiency (yield) and quantum requirement is reconsidered. The essential conclusions are: 1) The non-linearity of the light curves cannot be compensated using suspensions of algae or chloroplasts with high (>1.0) optical density or absorbance. 2) The values of the maxima of the quantum efficiency curves or the values of the minima of the quantum requirement curves cannot be used for estimation of the exact value of the maximum quantum efficiency and the minimum quantum requirement. The estimation of the maximum quantum efficiency or the minimum quantum requirement should be performed only after extrapolation of the linear part at higher light intensities of the quantum requirement curves to "0" light intensity.

Realization of a Cascaded Quantum System: Heralded Absorption of a Single Photon Qubit by a Single-Electron Charged Quantum Dot.

PubMed

Delteil, Aymeric; Sun, Zhe; Fält, Stefan; Imamoğlu, Atac

2017-04-28

Photonic losses pose a major limitation for the implementation of a quantum state transfer between nodes of a quantum network. A measurement that heralds a successful transfer without revealing any information about the qubit may alleviate this limitation. Here, we demonstrate the heralded absorption of a single photonic qubit, generated by a single neutral quantum dot, by a single-electron charged quantum dot that is located 5 m away. The transfer of quantum information to the spin degree of freedom takes place upon the emission of a photon; for a properly chosen or prepared quantum dot, the detection of this photon yields no information about the qubit. We show that this process can be combined with local operations optically performed on the destination node by measuring classical correlations between the absorbed photon color and the final state of the electron spin. Our work suggests alternative avenues for the realization of quantum information protocols based on cascaded quantum systems.

Quantum and classical noise in practical quantum-cryptography systems based on polarization-entangled photons

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

Castelletto, S.; Degiovanni, I.P.; Rastello, M.L.

2003-02-01

Quantum-cryptography key distribution (QCKD) experiments have been recently reported using polarization-entangled photons. However, in any practical realization, quantum systems suffer from either unwanted or induced interactions with the environment and the quantum measurement system, showing up as quantum and, ultimately, statistical noise. In this paper, we investigate how an ideal polarization entanglement in spontaneous parametric down-conversion (SPDC) suffers quantum noise in its practical implementation as a secure quantum system, yielding errors in the transmitted bit sequence. Since all SPDC-based QCKD schemes rely on the measurement of coincidence to assert the bit transmission between the two parties, we bundle up themore » overall quantum and statistical noise in an exhaustive model to calculate the accidental coincidences. This model predicts the quantum-bit error rate and the sifted key and allows comparisons between different security criteria of the hitherto proposed QCKD protocols, resulting in an objective assessment of performances and advantages of different systems.« less

Quantum walled Brauer algebra: commuting families, Baxterization, and representations

NASA Astrophysics Data System (ADS)

Semikhatov, A. M.; Tipunin, I. Yu

2017-02-01

For the quantum walled Brauer algebra, we construct its Specht modules and (for generic parameters of the algebra) seminormal modules. The latter construction yields the spectrum of a commuting family of Jucys-Murphy elements. We also propose a Baxterization prescription; it involves representing the quantum walled Brauer algebra in terms of morphisms in a braided monoidal category and introducing parameters into these morphisms, which allows constructing a ‘universal transfer matrix’ that generates commuting elements of the algebra.

Quantum communication complexity using the quantum Zeno effect

NASA Astrophysics Data System (ADS)

Tavakoli, Armin; Anwer, Hammad; Hameedi, Alley; Bourennane, Mohamed

2015-07-01

The quantum Zeno effect (QZE) is the phenomenon in which the unitary evolution of a quantum state is suppressed, e.g., due to frequent measurements. Here, we investigate the use of the QZE in a class of communication complexity problems (CCPs). Quantum entanglement is known to solve certain CCPs beyond classical constraints. However, recent developments have yielded CCPs for which superclassical results can be obtained using only communication of a single d -level quantum state (qudit) as a resource. In the class of CCPs considered here, we show quantum reduction of complexity in three ways: using (i) entanglement and the QZE, (ii) a single qudit and the QZE, and (iii) a single qudit. We have performed a proof of concept experimental demonstrations of three party CCP protocol based on single-qubit communication with and without QZE.

Time-bin entangled photons from a quantum dot

PubMed Central

Jayakumar, Harishankar; Predojević, Ana; Kauten, Thomas; Huber, Tobias; Solomon, Glenn S.; Weihs, Gregor

2014-01-01

Long distance quantum communication is one of the prime goals in the field of quantum information science. With information encoded in the quantum state of photons, existing telecommunication fibre networks can be effectively used as a transport medium. To achieve this goal, a source of robust entangled single photon pairs is required. Here, we report the realization of a source of time-bin entangled photon pairs utilizing the biexciton-exciton cascade in a III/V self-assembled quantum dot. We analyse the generated photon pairs by an inherently phase-stable interferometry technique, facilitating uninterrupted long integration times. We confirm the entanglement by performing quantum state tomography of the emitted photons, which yields a fidelity of 0.69(3) and a concurrence of 0.41(6) for our realization of time-energy entanglement from a single quantum emitter. PMID:24968024

Time-bin entangled photons from a quantum dot.

PubMed

Jayakumar, Harishankar; Predojević, Ana; Kauten, Thomas; Huber, Tobias; Solomon, Glenn S; Weihs, Gregor

2014-06-26

Long-distance quantum communication is one of the prime goals in the field of quantum information science. With information encoded in the quantum state of photons, existing telecommunication fibre networks can be effectively used as a transport medium. To achieve this goal, a source of robust entangled single-photon pairs is required. Here we report the realization of a source of time-bin entangled photon pairs utilizing the biexciton-exciton cascade in a III/V self-assembled quantum dot. We analyse the generated photon pairs by an inherently phase-stable interferometry technique, facilitating uninterrupted long integration times. We confirm the entanglement by performing quantum state tomography of the emitted photons, which yields a fidelity of 0.69(3) and a concurrence of 0.41(6) for our realization of time-energy entanglement from a single quantum emitter.

Quantum versus classical dynamics in the optical centrifuge

NASA Astrophysics Data System (ADS)

Armon, Tsafrir; Friedland, Lazar

2017-09-01

The interplay between classical and quantum-mechanical evolution in the optical centrifuge (OC) is discussed. The analysis is based on the quantum-mechanical formalism starting from either the ground state or a thermal ensemble. Two resonant mechanisms are identified, i.e., the classical autoresonance and the quantum-mechanical ladder climbing, yielding different dynamics and rotational excitation efficiencies. The rotating-wave approximation is used to analyze the two resonant regimes in the associated dimensionless two-parameter space and calculate the OC excitation efficiency. The results show good agreement between numerical simulations and theory and are relevant to existing experimental setups.

Measurements of observables replaced by “evaluations” in Quantum Theory

NASA Astrophysics Data System (ADS)

Nisticò, Giuseppe; Sestito, Angela

2015-07-01

In quantum physics there are circumstances where the direct measurement of particular observables encounters difficulties; in some of these cases, however, its value can be evaluated, i.e. it can be inferred by measuring another observable characterized by perfect correlation with the observable of interest. Though an evaluation is often interpreted as a measurement of the evaluated observable, we prove that the two concepts cannot be identified in quantum physics, because the identification yields contradictions. Then, we establish the conceptual status of evaluations in Quantum Theory and the role can be ascribed to them.

Fluorescent porous silicon biological probes with high quantum efficiency and stability.

PubMed

Tu, Chang-Ching; Chou, Ying-Nien; Hung, Hsiang-Chieh; Wu, Jingda; Jiang, Shaoyi; Lin, Lih Y

2014-12-01

We demonstrate porous silicon biological probes as a stable and non-toxic alternative to organic dyes or cadmium-containing quantum dots for imaging and sensing applications. The fluorescent silicon quantum dots which are embedded on the porous silicon surface are passivated with carboxyl-terminated ligands through stable Si-C covalent bonds. The porous silicon bio-probes have shown photoluminescence quantum yield around 50% under near-UV excitation, with high photochemical and thermal stability. The bio-probes can be efficiently conjugated with antibodies, which is confirmed by a standard enzyme-linked immunosorbent assay (ELISA) method.

Excited-State Proton-Transfer-Induced Trapping Enhances the Fluorescence Emission of a Locked GFP Chromophore

PubMed Central

2016-01-01

The chemical locking of the central single bond in core chromophores of green fluorescent proteins (GFPs) influences their excited-state behavior in a distinct manner. Experimentally, it significantly enhances the fluorescence quantum yield of GFP chromophores with an ortho-hydroxyl group, while it has almost no effect on the photophysics of GFP chromophores with a para-hydroxyl group. To unravel the underlying physical reasons for this different behavior, we report static electronic structure calculations and nonadiabatic dynamics simulations on excited-state intramolecular proton transfer, cis–trans isomerization, and excited-state deactivation in a locked ortho-substituted GFP model chromophore (o-LHBI). On the basis of our previous and present results, we find that the S1 keto species is responsible for the fluorescence emission of the unlocked o-HBI and the locked o-LHBI species. Chemical locking does not change the parts of the S1 and S0 potential energy surfaces relevant to enol–keto tautomerization; hence, in both chromophores, there is an ultrafast excited-state intramolecular proton transfer that takes only 35 fs on average. However, the locking effectively hinders the S1 keto species from approaching the keto S1/S0 conical intersections so that most of trajectories are trapped in the S1 keto region for the entire 2 ps simulation time. Therefore, the fluorescence quantum yield of o-LHBI is enhanced compared with that of unlocked o-HBI, in which the S1 excited-state decay is efficient and ultrafast. In the case of the para-substituted GFP model chromophores p-HBI and p-LHBI, chemical locking hardly affects their efficient excited-state deactivation via cis–trans isomerization; thus, the fluorescence quantum yields in these chromophores remain very low. The insights gained from the present work may help to guide the design of new GFP chromophores with improved fluorescence emission and brightness. PMID:26744782

Multi-functional quantum router using hybrid opto-electromechanics

NASA Astrophysics Data System (ADS)

Ma, Peng-Cheng; Yan, Lei-Lei; Chen, Gui-Bin; Li, Xiao-Wei; Liu, Shu-Jing; Zhan, You-Bang

2018-03-01

Quantum routers engineered with multiple frequency bands play a key role in quantum networks. We propose an experimentally accessible scheme for a multi-functional quantum router, using photon-phonon conversion in a hybrid opto-electromechanical system. Our proposed device functions as a bidirectional, tunable multi-channel quantum router, and demonstrates the possibility to route single optical photons bidirectionally and simultaneously to three different output ports, by adjusting the microwave power. Further, the device also behaves as an interswitching unit for microwave and optical photons, yielding probabilistic routing of microwave (optical) signals to optical (microwave) outports. With respect to potential application, we verify the insignificant influence from vacuum and thermal noises in the performance of the router under cryogenic conditions.

Complex Chemical Reaction Networks from Heuristics-Aided Quantum Chemistry.

PubMed

Rappoport, Dmitrij; Galvin, Cooper J; Zubarev, Dmitry Yu; Aspuru-Guzik, Alán

2014-03-11

While structures and reactivities of many small molecules can be computed efficiently and accurately using quantum chemical methods, heuristic approaches remain essential for modeling complex structures and large-scale chemical systems. Here, we present a heuristics-aided quantum chemical methodology applicable to complex chemical reaction networks such as those arising in cell metabolism and prebiotic chemistry. Chemical heuristics offer an expedient way of traversing high-dimensional reactive potential energy surfaces and are combined here with quantum chemical structure optimizations, which yield the structures and energies of the reaction intermediates and products. Application of heuristics-aided quantum chemical methodology to the formose reaction reproduces the experimentally observed reaction products, major reaction pathways, and autocatalytic cycles.

Six-dimensional quantum dynamics study for the dissociative adsorption of DCl on Au(111) surface

NASA Astrophysics Data System (ADS)

Liu, Tianhui; Fu, Bina; Zhang, Dong H.

2014-04-01

We carried out six-dimensional quantum dynamics calculations for the dissociative adsorption of deuterium chloride (DCl) on Au(111) surface using the initial state-selected time-dependent wave packet approach. The four-dimensional dissociation probabilities are also obtained with the center of mass of DCl fixed at various sites. These calculations were all performed based on an accurate potential energy surface recently constructed by neural network fitting to density function theory energy points. The origin of the extremely small dissociation probability for DCl/HCl (v = 0, j = 0) fixed at the top site compared to other fixed sites is elucidated in this study. The influence of vibrational excitation and rotational orientation of DCl on the reactivity was investigated by calculating six-dimensional dissociation probabilities. The vibrational excitation of DCl enhances the reactivity substantially and the helicopter orientation yields higher dissociation probability than the cartwheel orientation. The site-averaged dissociation probability over 25 fixed sites obtained from four-dimensional quantum dynamics calculations can accurately reproduce the six-dimensional dissociation probability.

Six-dimensional quantum dynamics study for the dissociative adsorption of DCl on Au(111) surface

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

Liu, Tianhui; Fu, Bina, E-mail: bina@dicp.ac.cn, E-mail: zhangdh@dicp.ac.cn; Zhang, Dong H., E-mail: bina@dicp.ac.cn, E-mail: zhangdh@dicp.ac.cn

We carried out six-dimensional quantum dynamics calculations for the dissociative adsorption of deuterium chloride (DCl) on Au(111) surface using the initial state-selected time-dependent wave packet approach. The four-dimensional dissociation probabilities are also obtained with the center of mass of DCl fixed at various sites. These calculations were all performed based on an accurate potential energy surface recently constructed by neural network fitting to density function theory energy points. The origin of the extremely small dissociation probability for DCl/HCl (v = 0, j = 0) fixed at the top site compared to other fixed sites is elucidated in this study. The influence of vibrational excitationmore » and rotational orientation of DCl on the reactivity was investigated by calculating six-dimensional dissociation probabilities. The vibrational excitation of DCl enhances the reactivity substantially and the helicopter orientation yields higher dissociation probability than the cartwheel orientation. The site-averaged dissociation probability over 25 fixed sites obtained from four-dimensional quantum dynamics calculations can accurately reproduce the six-dimensional dissociation probability.« less

Ligand-surface interactions and surface oxidation of colloidal PbSe quantum dots revealed by thin-film positron annihilation methods

NASA Astrophysics Data System (ADS)

Shi, Wenqin; Eijt, Stephan W. H.; Suchand Sandeep, C. S.; Siebbeles, Laurens D. A.; Houtepen, Arjan J.; Kinge, Sachin; Brück, Ekkes; Barbiellini, Bernardo; Bansil, Arun

2016-02-01

Positron Two Dimensional Angular Correlation of Annihilation Radiation (2D-ACAR) measurements reveal modifications of the electronic structure and composition at the surfaces of PbSe quantum dots (QDs), deposited as thin films, produced by various ligands containing either oxygen or nitrogen atoms. In particular, the 2D-ACAR measurements on thin films of colloidal PbSe QDs capped with oleic acid ligands yield an increased intensity in the electron momentum density (EMD) at high momenta compared to PbSe quantum dots capped with oleylamine. Moreover, the EMD of PbSe QDs is strongly affected by the small ethylenediamine ligands, since these molecules lead to small distances between QDs and favor neck formation between near neighbor QDs, inducing electronic coupling between neighboring QDs. The high sensitivity to the presence of oxygen atoms at the surface can be also exploited to monitor the surface oxidation of PbSe QDs upon exposure to air. Our study clearly demonstrates that positron annihilation spectroscopy applied to thin films can probe surface transformations of colloidal semiconductor QDs embedded in functional layers.

Numerical simulations in stochastic mechanics

NASA Astrophysics Data System (ADS)

McClendon, Marvin; Rabitz, Herschel

1988-05-01

The stochastic differential equation of Nelson's stochastic mechanics is integrated numerically for several simple quantum systems. The calculations are performed with use of Helfand and Greenside's method and pseudorandom numbers. The resulting trajectories are analyzed both individually and collectively to yield insight into momentum, uncertainty principles, interference, tunneling, quantum chaos, and common models of diatomic molecules from the stochastic quantization point of view. In addition to confirming Shucker's momentum theorem, these simulations illustrate, within the context of stochastic mechanics, the position-momentum and time-energy uncertainty relations, the two-slit diffraction pattern, exponential decay of an unstable system, and the greater degree of anticorrelation in a valence-bond model as compared with a molecular-orbital model of H2. The attempt to find exponential divergence of initially nearby trajectories, potentially useful as a criterion for quantum chaos, in a periodically forced oscillator is inconclusive. A way of computing excited energies from the ground-state motion is presented. In all of these studies the use of particle trajectories allows a more insightful interpretation of physical phenomena than is possible within traditional wave mechanics.

One-pot and ultrafast synthesis of nitrogen and phosphorus co-doped carbon dots possessing bright dual wavelength fluorescence emission

NASA Astrophysics Data System (ADS)

Sun, Xiangcheng; Brückner, Christian; Lei, Yu

2015-10-01

Very brief microwave heating of aniline, ethylene diamine, and phosphoric acid in water at ambient pressure generated nitrogen and phosphorus co-doped carbon dots (N,P-CDs) that exhibit bright dual blue (centred at 450 nm; 51% quantum yield) and green (centred at 510 nm, 38% quantum yield) fluorescence emission bands. The N,P-CDs were characterized using TEM, XRD, XPS, IR, UV-vis, and fluorescence spectroscopy, demonstrating their partially crystalline carbon, partially amorphous structures, and the incorporation of O, N, and P into the carbogenic scaffold. The N,P-CDs demonstrated excitation-dependent and nearly pH-independent emission properties. The unique dual emission properties lay the foundation for the use of N,P-CDs in ratiometric sensing applications.Very brief microwave heating of aniline, ethylene diamine, and phosphoric acid in water at ambient pressure generated nitrogen and phosphorus co-doped carbon dots (N,P-CDs) that exhibit bright dual blue (centred at 450 nm; 51% quantum yield) and green (centred at 510 nm, 38% quantum yield) fluorescence emission bands. The N,P-CDs were characterized using TEM, XRD, XPS, IR, UV-vis, and fluorescence spectroscopy, demonstrating their partially crystalline carbon, partially amorphous structures, and the incorporation of O, N, and P into the carbogenic scaffold. The N,P-CDs demonstrated excitation-dependent and nearly pH-independent emission properties. The unique dual emission properties lay the foundation for the use of N,P-CDs in ratiometric sensing applications. Electronic supplementary information (ESI) available: Detailed experimental section, XRD, FTIR, explosive sensing and the applications results. See DOI: 10.1039/c5nr05549k

Mapping quantum yield for (Fe-Zn-Sn-Ti)Ox photoabsorbers using a high throughput photoelectrochemical screening system.

PubMed

Xiang, Chengxiang; Haber, Joel; Marcin, Martin; Mitrovic, Slobodan; Jin, Jian; Gregoire, John M

2014-03-10

Combinatorial synthesis and screening of light absorbers are critical to material discoveries for photovoltaic and photoelectrochemical applications. One of the most effective ways to evaluate the energy-conversion properties of a semiconducting light absorber is to form an asymmetric junction and investigate the photogeneration, transport and recombination processes at the semiconductor interface. This standard photoelectrochemical measurement is readily made on a semiconductor sample with a back-side metallic contact (working electrode) and front-side solution contact. In a typical combinatorial material library, each sample shares a common back contact, requiring novel instrumentation to provide spatially resolved and thus sample-resolved measurements. We developed a multiplexing counter electrode with a thin layer assembly, in which a rectifying semiconductor/liquid junction was formed and the short-circuit photocurrent was measured under chopped illumination for each sample in a material library. The multiplexing counter electrode assembly demonstrated a photocurrent sensitivity of sub-10 μA cm(-2) with an external quantum yield sensitivity of 0.5% for each semiconductor sample under a monochromatic ultraviolet illumination source. The combination of cell architecture and multiplexing allows high-throughput modes of operation, including both fast-serial and parallel measurements. To demonstrate the performance of the instrument, the external quantum yields of 1819 different compositions from a pseudoquaternary metal oxide library, (Fe-Zn-Sn-Ti)Ox, at 385 nm were collected in scanning serial mode with a throughput of as fast as 1 s per sample. Preliminary screening results identified a promising ternary composition region centered at Fe0.894Sn0.103Ti0.0034Ox, with an external quantum yield of 6.7% at 385 nm.

Photochemical properties of squarylium cyanine dyes.

PubMed

Ferreira, D P; Conceição, D S; Ferreira, V R A; Graça, V C; Santos, P F; Vieira Ferreira, L F

2013-11-01

This study presents several new squarylium dyes derived from benzothiazole and benzoselenazole with several structural variations, namely the nature of the heteroaromatic ring and the length of the N,N'-dialkyl groups. Before being investigated in connection with their effect on living cells and/or tissues, these novel compounds were characterized, namely with respect to the determination of their main photophysical parameters. Therefore, a study of the ground state absorption, fluorescence emission (quantum yields and lifetimes) and singlet oxygen generation quantum yields was performed for all the compounds synthesized in order to evaluate their efficiency as photosensitizers. An increase of the alkyl chain length from ethyl to hexyl did not produce a clear change in the fluorescence quantum yields, showing no influence on the photoisomerization process. Heavy atom inclusion (Se instead of S) enhanced the singlet oxygen generation efficiency and decreased the intensity of the fluorescence emission. The external heavy atom effect (I(-) as a counterion instead of CF3SO3(-)) produced a significant increase in the singlet oxygen formation quantum yield (about 20%). Transient absorption studies in aerated and oxygen free samples revealed that the photoisomerization process, which could compete with the triplet state formation for all dyes in solution, is a negligible pathway for the excited state deactivation, in accordance with the rigidity introduced by the squaric ring into the polymethine chain of the dye, both in chloroform and ethanol. However, in the case of the chloroform solution a new transient was detected in air equilibrated solutions, resulting from a reaction of the excited squarylium dye in the singlet state with CHCl3˙, and assigned to the radical cation (SQ(+)˙) of the dye.

Single photon emission from plasma treated 2D hexagonal boron nitride.

PubMed

Xu, Zai-Quan; Elbadawi, Christopher; Tran, Toan Trong; Kianinia, Mehran; Li, Xiuling; Liu, Daobin; Hoffman, Timothy B; Nguyen, Minh; Kim, Sejeong; Edgar, James H; Wu, Xiaojun; Song, Li; Ali, Sajid; Ford, Mike; Toth, Milos; Aharonovich, Igor

2018-05-03

Artificial atomic systems in solids are becoming increasingly important building blocks in quantum information processing and scalable quantum nanophotonic networks. Amongst numerous candidates, 2D hexagonal boron nitride has recently emerged as a promising platform hosting single photon emitters. Here, we report a number of robust plasma and thermal annealing methods for fabrication of emitters in tape-exfoliated hexagonal boron nitride (hBN) crystals. A two-step process comprising Ar plasma etching and subsequent annealing in Ar is highly robust, and yields an eight-fold increase in the concentration of emitters in hBN. The initial plasma-etching step generates emitters that suffer from blinking and bleaching, whereas the two-step process yields emitters that are photostable at room temperature with emission wavelengths greater than ∼700 nm. Density functional theory modeling suggests that the emitters might be associated with defect complexes that contain oxygen. This is further confirmed by generating the emitters via annealing hBN in air. Our findings advance the present understanding of the structure of quantum emitters in hBN and enhance the nanofabrication toolkit needed to realize integrated quantum nanophotonic circuits.

Room temperature synthesis of pH-switchable polyaniline quantum dots as a turn-on fluorescent probe for acidic biotarget labeling.

PubMed

Liu, Yanfeng; Ding, Yin; Gou, Huilin; Huang, Xin; Zhang, Guiyang; Zhang, Qi; Liu, Yunzhong; Meng, Zhen; Xi, Kai; Jia, Xudong

2018-04-05

The synthesis of well-defined light-element-derived quantum dots (LEQDs) with advanced optical properties under mild conditions is highly desirable yet challenging. Here, a polyaniline (PANI) structure is introduced into carbon-rich LEQDs to yield well-defined, fluorescent polyaniline quantum dots (PAQDs), PAQD24, through a one-pot room temperature reaction. The mild synthetic conditions effectively minimize the defects introduced during the conventional synthesis and endow PAQD24 with desirable optical properties, including a narrow emission band (full width at half maximum = 55 nm), an optimal quantum yield of 32.5% and two-photon fluorescence. Furthermore, the bandgap of PAQD24 is highly sensitive toward pH variations in the near-neutral region, due to the proton doping and dedoping of the PANI structure. Such unique properties together with its fine bio-compatibility enable the application of this material as a turn-on fluorescent probe for the labeling of acidic biotargets from sub-cellular to organ levels, providing potential applications in diagnosis and surgery guidance for certain diseases.

Full spectral optical modeling of quantum-dot-converted elements for light-emitting diodes considering reabsorption and reemission effect.

PubMed

Li, Jia-Sheng; Tang, Yong; Li, Zong-Tao; Cao, Kai; Yan, Cai-Man; Ding, Xin-Rui

2018-07-20

Quantum dots (QDs) have attracted significant attention in light-emitting diode (LED) illumination and display applications, owing to their high quantum yield and unique spectral properties. However, an effective optical model of quantum-dot-converted elements (QDCEs) for (LEDs) that entirely considers the reabsorption and reemission effect is lacking. This suppresses the design of QDCE structures and further investigation of light-extraction/conversion mechanisms in QDCEs. In this paper, we proposed a full spectral optical modeling method for QDCEs packaged in LEDs, entirely considering the reabsorption and reemission effect, and its results are compared with traditional models without reabsorption or reemission. The comparisons indicate that the QDCE absorption loss of QD emission light is a major factor decreasing the radiant efficacy of LEDs, which should be considered when designing QDCE structures. According to the measurements of fabricated LEDs, only calculation results that entirely consider reabsorption and reemission show good agreement with experimental radiant efficacy, spectra, and peak wavelength at the same down-conversion efficiency. Consequently, it is highly expected that QDCE will be modeled considering the reabsorption and reemission events. This study provides a simple and effective modeling method for QDCEs, which shows great potential for their structure designs and fundamental investigations.

Full spectral optical modeling of quantum-dot-converted elements for light-emitting diodes considering reabsorption and reemission effect

NASA Astrophysics Data System (ADS)

Li, Jia-Sheng; Tang, Yong; Li, Zong-Tao; Cao, Kai; Yan, Cai-Man; Ding, Xin-Rui

2018-07-01

Quantum dots (QDs) have attracted significant attention in light-emitting diode (LED) illumination and display applications, owing to their high quantum yield and unique spectral properties. However, an effective optical model of quantum-dot-converted elements (QDCEs) for (LEDs) that entirely considers the reabsorption and reemission effect is lacking. This suppresses the design of QDCE structures and further investigation of light-extraction/conversion mechanisms in QDCEs. In this paper, we proposed a full spectral optical modeling method for QDCEs packaged in LEDs, entirely considering the reabsorption and reemission effect, and its results are compared with traditional models without reabsorption or reemission. The comparisons indicate that the QDCE absorption loss of QD emission light is a major factor decreasing the radiant efficacy of LEDs, which should be considered when designing QDCE structures. According to the measurements of fabricated LEDs, only calculation results that entirely consider reabsorption and reemission show good agreement with experimental radiant efficacy, spectra, and peak wavelength at the same down-conversion efficiency. Consequently, it is highly expected that QDCE will be modeled considering the reabsorption and reemission events. This study provides a simple and effective modeling method for QDCEs, which shows great potential for their structure designs and fundamental investigations.

Estimation of the quantum efficiency of the photodissociation of HbO2 and HbCO

NASA Astrophysics Data System (ADS)

Gisbrecht, A. I.; Mamilov, S. A.; Esman, S. S.; Asimov, M. M.

2016-01-01

The paper presents our results on the study of the efficiency of inter-fractional changes in hemoglobin molecules depending on the laser radiation parameters. The evaluation of the quantum efficiency of light interaction in vivo with oxyhemoglobin (HbO2) and carboxyhemoglobin (HbCO) in the blood at wavelengths for 525 and 605 nm is presented. The photodissociation yield of 11% for HbO2 and 79% for HbCO are measured at the wavelength of 525 nm and 10 % for HbO2 and 76 % for HbCO at a wavelength of 605 nm. Thus, the quantum yield of photodissociation of the HbCO is considerably higher, which ensures high efficiency of photodecomposition of the HbCO in the blood. The obtained results can be used in the clinical phototherapy practice for effective treatment of CO poisoning.

An insight into non-emissive excited states in conjugated polymers

NASA Astrophysics Data System (ADS)

Hu, Zhongjian; Willard, Adam P.; Ono, Robert J.; Bielawski, Christopher W.; Rossky, Peter J.; vanden Bout, David A.

2015-09-01

Conjugated polymers in the solid state usually exhibit low fluorescence quantum yields, which limit their applications in many areas such as light-emitting diodes. Despite considerable research efforts, the underlying mechanism still remains controversial and elusive. Here, the nature and properties of excited states in the archetypal polythiophene are investigated via aggregates suspended in solvents with different dielectric constants (ε). In relatively polar solvents (ε>~ 3), the aggregates exhibit a low fluorescence quantum yield (QY) of 2-5%, similar to bulk films, however, in relatively nonpolar solvents (ε<~ 3) they demonstrate much higher fluorescence QY up to 20-30%. A series of mixed quantum-classical atomistic simulations illustrate that dielectric induced stabilization of nonradiative charge-transfer (CT) type states can lead to similar drastic reduction in fluorescence QY as seen experimentally. Fluorescence lifetime measurement reveals that the CT-type states exist as a competitive channel of the formation of emissive exciton-type states.

Near-threshold harmonics from a femtosecond enhancement cavity-based EUV source: effects of multiple quantum pathways on spatial profile and yield.

PubMed

Hammond, T J; Mills, Arthur K; Jones, David J

2011-12-05

We investigate the photon flux and far-field spatial profiles for near-threshold harmonics produced with a 66 MHz femtosecond enhancement cavity-based EUV source operating in the tight-focus regime. The effects of multiple quantum pathways in the far-field spatial profile and harmonic yield show a strong dependence on gas jet dynamics, particularly nozzle diameter and position. This simple system, consisting of only a 700 mW Ti:Sapphire oscillator and an enhancement cavity produces harmonics up to 20 eV with an estimated 30-100 μW of power (intracavity) and > 1μW (measured) of power spectrally-resolved and out-coupled from the cavity. While this power is already suitable for applications, a quantum mechanical model of the system indicates substantial improvements should be possible with technical upgrades.

Variation in canopy duration in the perennial biofuel crop Miscanthus reveals complex associations with yield.

PubMed

Robson, Paul R H; Farrar, Kerrie; Gay, Alan P; Jensen, Elaine F; Clifton-Brown, John C; Donnison, Iain S

2013-05-01

Energy crops can provide a sustainable source of power and fuels, and mitigate the negative effects of CO2 emissions associated with fossil fuel use. Miscanthus is a perennial C4 energy crop capable of producing large biomass yields whilst requiring low levels of input. Miscanthus is largely unimproved and therefore there could be significant opportunities to increase yield. Further increases in yield will improve the economics, energy balance, and carbon mitigation of the crop, as well as reducing land-take. One strategy to increase yield in Miscanthus is to maximize the light captured through an extension of canopy duration. In this study, canopy duration was compared among a diverse collection of 244 Miscanthus genotypes. Canopy duration was determined by calculating the number of days between canopy establishment and senescence. Yield was positively correlated with canopy duration. Earlier establishment and later senescence were also both separately correlated with higher yield. However, although genotypes with short canopy durations were low yielding, not all genotypes with long canopy durations were high yielding. Differences of yield between genotypes with long canopy durations were associated with variation in stem and leaf traits. Different methodologies to assess canopy duration traits were investigated, including visual assessment, image analysis, light interception, and different trait thresholds. The highest correlation coefficients were associated with later assessments of traits and the use of quantum sensors for canopy establishment. A model for trait optimization to enable yield improvement in Miscanthus and other bioenergy crops is discussed.

Variation in canopy duration in the perennial biofuel crop Miscanthus reveals complex associations with yield

PubMed Central

Robson, Paul R.H.; Farrar, Kerrie; Gay, Alan P.; Jensen, Elaine F.; Clifton-Brown, John C.; Donnison, Iain S.

2013-01-01

Energy crops can provide a sustainable source of power and fuels, and mitigate the negative effects of CO2 emissions associated with fossil fuel use. Miscanthus is a perennial C4 energy crop capable of producing large biomass yields whilst requiring low levels of input. Miscanthus is largely unimproved and therefore there could be significant opportunities to increase yield. Further increases in yield will improve the economics, energy balance, and carbon mitigation of the crop, as well as reducing land-take. One strategy to increase yield in Miscanthus is to maximize the light captured through an extension of canopy duration. In this study, canopy duration was compared among a diverse collection of 244 Miscanthus genotypes. Canopy duration was determined by calculating the number of days between canopy establishment and senescence. Yield was positively correlated with canopy duration. Earlier establishment and later senescence were also both separately correlated with higher yield. However, although genotypes with short canopy durations were low yielding, not all genotypes with long canopy durations were high yielding. Differences of yield between genotypes with long canopy durations were associated with variation in stem and leaf traits. Different methodologies to assess canopy duration traits were investigated, including visual assessment, image analysis, light interception, and different trait thresholds. The highest correlation coefficients were associated with later assessments of traits and the use of quantum sensors for canopy establishment. A model for trait optimization to enable yield improvement in Miscanthus and other bioenergy crops is discussed. PMID:23599277

Achieving Optimal Quantum Acceleration of Frequency Estimation Using Adaptive Coherent Control.

PubMed

Naghiloo, M; Jordan, A N; Murch, K W

2017-11-03

Precision measurements of frequency are critical to accurate time keeping and are fundamentally limited by quantum measurement uncertainties. While for time-independent quantum Hamiltonians the uncertainty of any parameter scales at best as 1/T, where T is the duration of the experiment, recent theoretical works have predicted that explicitly time-dependent Hamiltonians can yield a 1/T^{2} scaling of the uncertainty for an oscillation frequency. This quantum acceleration in precision requires coherent control, which is generally adaptive. We experimentally realize this quantum improvement in frequency sensitivity with superconducting circuits, using a single transmon qubit. With optimal control pulses, the theoretically ideal frequency precision scaling is reached for times shorter than the decoherence time. This result demonstrates a fundamental quantum advantage for frequency estimation.

Coined quantum walks on weighted graphs

NASA Astrophysics Data System (ADS)

Wong, Thomas G.

2017-11-01

We define a discrete-time, coined quantum walk on weighted graphs that is inspired by Szegedy’s quantum walk. Using this, we prove that many lackadaisical quantum walks, where each vertex has l integer self-loops, can be generalized to a quantum walk where each vertex has a single self-loop of real-valued weight l. We apply this real-valued lackadaisical quantum walk to two problems. First, we analyze it on the line or one-dimensional lattice, showing that it is exactly equivalent to a continuous deformation of the three-state Grover walk with faster ballistic dispersion. Second, we generalize Grover’s algorithm, or search on the complete graph, to have a weighted self-loop at each vertex, yielding an improved success probability when l < 3 + 2\\sqrt{2} ≈ 5.828 .

Heisenberg-Langevin versus quantum master equation

NASA Astrophysics Data System (ADS)

Boyanovsky, Daniel; Jasnow, David

2017-12-01

The quantum master equation is an important tool in the study of quantum open systems. It is often derived under a set of approximations, chief among them the Born (factorization) and Markov (neglect of memory effects) approximations. In this article we study the paradigmatic model of quantum Brownian motion of a harmonic oscillator coupled to a bath of oscillators with a Drude-Ohmic spectral density. We obtain analytically the exact solution of the Heisenberg-Langevin equations, with which we study correlation functions in the asymptotic stationary state. We compare the exact correlation functions to those obtained in the asymptotic long time limit with the quantum master equation in the Born approximation with and without the Markov approximation. In the latter case we implement a systematic derivative expansion that yields the exact asymptotic limit under the factorization approximation only. We find discrepancies that could be significant when the bandwidth of the bath Λ is much larger than the typical scales of the system. We study the exact interaction energy as a proxy for the correlations missed by the Born approximation and find that its dependence on Λ is similar to the discrepancy between the exact solution and that of the quantum master equation in the Born approximation. We quantify the regime of validity of the quantum master equation in the Born approximation with or without the Markov approximation in terms of the system's relaxation rate γ , its unrenormalized natural frequency Ω and Λ : γ /Ω ≪1 and also γ Λ /Ω2≪1 . The reliability of the Born approximation is discussed within the context of recent experimental settings and more general environments.

Aryl-modified graphene quantum dots with enhanced photoluminescence and improved pH tolerance

NASA Astrophysics Data System (ADS)

Luo, Peihui; Ji, Zhe; Li, Chun; Shi, Gaoquan

2013-07-01

Chemical modification is an important technique to modulate the chemical and optical properties of graphene quantum dots (GQDs). In this paper, we report a versatile diazonium chemistry method to graft aryl groups including phenyl, 4-carboxyphenyl, 4-sulfophenyl and 5-sulfonaphthyl to GQDs via Gomberg-Bachmann reaction. The aryl-modified GQDs are nanocrystals with lateral dimensions in the range of 2-4 nm and an average thickness lower than 1 nm. Upon chemical modification with aryl groups, the photoluminescence (PL) bands of GQDs were tuned in the range of 418 and 447 nm, and their fluorescence quantum yields (QYs) were increased for up to about 6 times. Furthermore, the aryl-modified GQDs exhibited stable PL (both intensity and peak position) in a wide pH window of 1-11. The mechanism of improving the PL properties of GQDs by aryl-modification was also discussed.Chemical modification is an important technique to modulate the chemical and optical properties of graphene quantum dots (GQDs). In this paper, we report a versatile diazonium chemistry method to graft aryl groups including phenyl, 4-carboxyphenyl, 4-sulfophenyl and 5-sulfonaphthyl to GQDs via Gomberg-Bachmann reaction. The aryl-modified GQDs are nanocrystals with lateral dimensions in the range of 2-4 nm and an average thickness lower than 1 nm. Upon chemical modification with aryl groups, the photoluminescence (PL) bands of GQDs were tuned in the range of 418 and 447 nm, and their fluorescence quantum yields (QYs) were increased for up to about 6 times. Furthermore, the aryl-modified GQDs exhibited stable PL (both intensity and peak position) in a wide pH window of 1-11. The mechanism of improving the PL properties of GQDs by aryl-modification was also discussed. Electronic supplementary information (ESI) available: Fluorescence quantum yield measurements, estimation of grafting ratio, TEM images, FTIR spectra, PL spectra and zeta potentials. See DOI: 10.1039/c3nr02156d

Ultrafast endothermic transfer of non-radiative exciplex state to radiative excitons in polyfluorene random copolymer for blue electroluminescence

NASA Astrophysics Data System (ADS)

Moghe, Dhanashree A.; Dey, Amrita; Johnson, Kerr; Lu, L.-P.; Friend, Richard H.; Kabra, Dinesh

2018-04-01

We report a blue-emitting random copolymer (termed modified Aryl-F8) consisting of three repeat units of polydioctylfluorene (F8), Aryl-polydioctylfluorene (Aryl-F8), and an aromatic amine comonomer unit, poly(bis-N,Ν'-(4-butylphenyl)-bis-N,N'-phenyl-1,4 phenylenediamine) chemically linked to get an improved charge carrier balance without compromising on the photoluminescence (PL) quantum yield with respect to the Aryl-F8 homo-polymer. The measured photoluminescence quantum efficiency (˜70%) of the blue-emitting polymer is comparable to or greater than the individual monomer units. The time resolved PL spectra from the modified Aryl-F8 are similar to those of Arylated-poly(9,9'-dioctylfluorene-co-bis-N,N'-(4-butylphenyl)-bis-N,N'-phenyl-1,4 phenylenediamine) (PFB) even at a time scale of 100-250 ps, indicating an ultrafast energy transfer from the (Aryl-F8 or F8):Arylated-PFB interface to Arylated-PFB, i.e., endothermic transfer of non-radiative exciplex to a radiative molecular exciton. Furthermore, the presence of non-radiative exciplex is confirmed by the photoluminescence decay profile and temperature dependent PL spectra. The luminance efficiency achieved for the modified Aryl-F8 polymer light-emitting diodes is ˜11 cd A-1 with an external quantum efficiency (EQE) of ˜4.5%, whereas it is 0.05 cd/A with an EQE of ˜0.025% for Aryl-F8. Almost two orders of higher efficiency is achieved due to the improved charge carrier balance from the random copolymer without compromising on the photoluminescence yield.

Synthesis and spectroscopic behavior of highly luminescent Eu 3+-dibenzoylmethanate (DBM) complexes with sulfoxide ligands

NASA Astrophysics Data System (ADS)

Niyama, E.; Brito, H. F.; Cremona, M.; Teotonio, E. E. S.; Reyes, R.; Brito, G. E. S.; Felinto, M. C. F. C.

2005-09-01

In this paper the synthesis, characterization and photoluminescent behavior of the [RE(DBM) 3L 2] complexes (RE = Gd and Eu) with a variety of sulfoxide ligands; L = benzyl sulfoxide (DBSO), methyl sulfoxide (DMSO), phenyl sulfoxide (DPSO) and p-tolyl sulfoxide (PTSO) have been investigated in solid state. The emission spectra of the Eu 3+-β-diketonate complexes show characteristics narrow bands arising from the 5D 0 → 7F J ( J = 0-4) transitions, which are split according to the selection rule for C n, C nv or C s site symmetries. The experimental Judd-Ofelt intensity parameters ( Ω2 and Ω4), radiative ( Arad) and non-radiative ( Anrad) decay rates, and R02 for the europium complexes have been determined and compared. The highest value of Ω2 (61.9 × 10 -20 cm 2) was obtained to the complex with PTSO ligand, indicating that Eu 3+ ion is in the highly polarizable chemical environment. The higher values of the experimental quantum yield ( q) and emission quantum efficiency of the emitter 5D 0 level ( η) for the Eu-complexes with DMSO, DBSO and PTSO sulfoxides suggest that these complexes are promising Light Conversion Molecular Devices (LCMDs). The lower value of quantum yield ( q = 1%), for the hydrated complex [Eu(DBM) 3(H 2O)], indicates that the luminescence quenching occurs via multiphonon relaxation by coupling with the OH-oscillators from water molecule coordinated to rare earth ion. The pure red emission of the Eu-complexes has been confirmed by ( x, y) color coordinates.

Principle of minimal work fluctuations.

PubMed

Xiao, Gaoyang; Gong, Jiangbin

2015-08-01

Understanding and manipulating work fluctuations in microscale and nanoscale systems are of both fundamental and practical interest. For example, in considering the Jarzynski equality 〈e-βW〉=e-βΔF, a change in the fluctuations of e-βW may impact how rapidly the statistical average of e-βW converges towards the theoretical value e-βΔF, where W is the work, β is the inverse temperature, and ΔF is the free energy difference between two equilibrium states. Motivated by our previous study aiming at the suppression of work fluctuations, here we obtain a principle of minimal work fluctuations. In brief, adiabatic processes as treated in quantum and classical adiabatic theorems yield the minimal fluctuations in e-βW. In the quantum domain, if a system initially prepared at thermal equilibrium is subjected to a work protocol but isolated from a bath during the time evolution, then a quantum adiabatic process without energy level crossing (or an assisted adiabatic process reaching the same final states as in a conventional adiabatic process) yields the minimal fluctuations in e-βW, where W is the quantum work defined by two energy measurements at the beginning and at the end of the process. In the classical domain where the classical work protocol is realizable by an adiabatic process, then the classical adiabatic process also yields the minimal fluctuations in e-βW. Numerical experiments based on a Landau-Zener process confirm our theory in the quantum domain, and our theory in the classical domain explains our previous numerical findings regarding the suppression of classical work fluctuations [G. Y. Xiao and J. B. Gong, Phys. Rev. E 90, 052132 (2014)].

Impact of Mono-Fluorination on the Photophysics of the Flavin Chromophore.

PubMed

Reiffers, Anna; Torres Ziegenbein, Christian; Engelhardt, Alyn; Kühnemuth, Ralf; Gilch, Peter; Czekelius, Constantin

2018-03-31

Three mono-fluorinated derivatives of the flavin core system 10-methyl-isoalloxazine (MIA) were synthesized. Aqueous solutions of these compounds were characterized by steady-state and time-resolved spectroscopy. The positions for the fluorination (6, 7 and 8) were motivated by the nodal structure of the frontier orbitals of MIA. In comparison with MIA, the fluorination results in bathochromic (6F- and 7F-MIA) and hypsochromic (8F-MIA) shifts of the adiabatic excitation energy of the lowest allowed transition. Shifts of up to ~500 cm -1 were observed. These spectroscopic shifts go along with changes in fluorescence quantum yields and lifetimes. In addition, triplet yields are affected. For 7F-MIA, a 50% increase in the fluorescence quantum yield as well as a 50% decrease in triplet yield is observed rendering the compound interesting for fluorescence applications. The measured effects are discussed in terms of qualitative perturbation theory. © 2018 The American Society of Photobiology.

Luminescence and luminescence quenching of highly efficient Y2Mo4O15:Eu3+ phosphors and ceramics

PubMed Central

Janulevicius, Matas; Marmokas, Paulius; Misevicius, Martynas; Grigorjevaite, Julija; Mikoliunaite, Lina; Sakirzanovas, Simas; Katelnikovas, Arturas

2016-01-01

A good LED phosphor must possess strong enough absorption, high quantum yields, colour purity, and quenching temperatures. Our synthesized Y2Mo4O15:Eu3+ phosphors possess all of these properties. Excitation of these materials with near-UV or blue radiation yields bright red emission and the colour coordinates are relatively stable upon temperature increase. Furthermore, samples doped with 50% Eu3+ showed quantum yields up to 85%, what is suitable for commercial application. Temperature dependent emission spectra revealed that heavily Eu3+ doped phosphors possess stable emission up to 400 K and lose half of the efficiency only at 515 K. In addition, ceramic disks of Y2Mo4O15:75%Eu3+ phosphor with thickness of 0.71 and 0.98 mm were prepared and it turned out that they efficiently convert radiation of 375 and 400 nm LEDs to the red light, whereas combination with 455 nm LED yields purple colour. PMID:27180941

Luminescence and luminescence quenching of highly efficient Y2Mo4O15:Eu(3+) phosphors and ceramics.

PubMed

Janulevicius, Matas; Marmokas, Paulius; Misevicius, Martynas; Grigorjevaite, Julija; Mikoliunaite, Lina; Sakirzanovas, Simas; Katelnikovas, Arturas

2016-05-16

A good LED phosphor must possess strong enough absorption, high quantum yields, colour purity, and quenching temperatures. Our synthesized Y2Mo4O15:Eu(3+) phosphors possess all of these properties. Excitation of these materials with near-UV or blue radiation yields bright red emission and the colour coordinates are relatively stable upon temperature increase. Furthermore, samples doped with 50% Eu(3+) showed quantum yields up to 85%, what is suitable for commercial application. Temperature dependent emission spectra revealed that heavily Eu(3+) doped phosphors possess stable emission up to 400 K and lose half of the efficiency only at 515 K. In addition, ceramic disks of Y2Mo4O15:75%Eu(3+) phosphor with thickness of 0.71 and 0.98 mm were prepared and it turned out that they efficiently convert radiation of 375 and 400 nm LEDs to the red light, whereas combination with 455 nm LED yields purple colour.

Efficient hybrid-symbolic methods for quantum mechanical calculations

NASA Astrophysics Data System (ADS)

Scott, T. C.; Zhang, Wenxing

2015-06-01

We present hybrid symbolic-numerical tools to generate optimized numerical code for rapid prototyping and fast numerical computation starting from a computer algebra system (CAS) and tailored to any given quantum mechanical problem. Although a major focus concerns the quantum chemistry methods of H. Nakatsuji which has yielded successful and very accurate eigensolutions for small atoms and molecules, the tools are general and may be applied to any basis set calculation with a variational principle applied to its linear and non-linear parameters.

Orbital Picture of Ionization and Its Breakdown in Nanoarrays of Quantum Dots

NASA Astrophysics Data System (ADS)

Bâldea, Ioan; Cederbaum, Lorenz S.

2002-09-01

We present exact numerical results indicating that ionization could be a useful tool to study electron correlations in artificial molecules and nanoarrays of metallic quantum dots. For nanorings consisting of Ag quantum dots of the type already fabricated, we demonstrate that the molecular orbital picture breaks down even for lowest energy ionization processes, in contrast to ordinary molecules. Our ionization results yield a transition point between localization and delocalization regimes in good agreement with various experimental data.

Significant Quantum Effects in Hydrogen Activation

DOE PAGES

Kyriakou, Georgios; Davidson, Erlend R. M.; Peng, Guowen; ...

2014-03-31

Dissociation of molecular hydrogen is an important step in a wide variety of chemical, biological, and physical processes. Due to the light mass of hydrogen, it is recognized that quantum effects are often important to its reactivity. However, understanding how quantum effects impact the reactivity of hydrogen is still in its infancy. Here, we examine this issue using a well-defined Pd/Cu(111) alloy that allows the activation of hydrogen and deuterium molecules to be examined at individual Pd atom surface sites over a wide range of temperatures. Experiments comparing the uptake of hydrogen and deuterium as a function of temperature revealmore » completely different behavior of the two species. The rate of hydrogen activation increases at lower sample temperature, whereas deuterium activation slows as the temperature is lowered. Density functional theory simulations in which quantum nuclear effects are accounted for reveal that tunneling through the dissociation barrier is prevalent for H 2 up to ~190 K and for D 2 up to ~140 K. Kinetic Monte Carlo simulations indicate that the effective barrier to H 2 dissociation is so low that hydrogen uptake on the surface is limited merely by thermodynamics, whereas the D 2 dissociation process is controlled by kinetics. These data illustrate the complexity and inherent quantum nature of this ubiquitous and seemingly simple chemical process. Here, examining these effects in other systems with a similar range of approaches may uncover temperature regimes where quantum effects can be harnessed, yielding greater control of bond-breaking processes at surfaces and uncovering useful chemistries such as selective bond activation or isotope separation.« less

Quantum trajectories for high-order-harmonic generation from multiple rescattering events in the long-wavelength regime

NASA Astrophysics Data System (ADS)

He, Lixin; Li, Yang; Wang, Zhe; Zhang, Qingbin; Lan, Pengfei; Lu, Peixiang

2014-05-01

We have performed the quantum trajectory analysis for high-order-harmonic generation (HHG) with different driving laser wavelengths. By defining the ratio of HHG yields of the Nth and first rescattering events (YN/Y1), we quantitatively evaluate the HHG contributions from multiple rescatterings. The results show that the HHG yield ratio increases gradually with the increase of the laser wavelength, which demonstrates that high-order rescatterings provide ascendent contributions to HHG at longer wavelength. By calculating the classical electron trajectories, we find significant differences exist in the electron behaviors between the first and high-order rescatterings. Further investigations have demonstrated that the increasing HHG yield ratio is mainly attributed to the relatively smaller contributions from the short path of the first electron rescattering at longer laser wavelength.

pH-Induced transformation of ligated Au25 to brighter Au23 nanoclusters.

PubMed

Waszkielewicz, Magdalena; Olesiak-Banska, Joanna; Comby-Zerbino, Clothilde; Bertorelle, Franck; Dagany, Xavier; Bansal, Ashu K; Sajjad, Muhammad T; Samuel, Ifor D W; Sanader, Zeljka; Rozycka, Miroslawa; Wojtas, Magdalena; Matczyszyn, Katarzyna; Bonacic-Koutecky, Vlasta; Antoine, Rodolphe; Ozyhar, Andrzej; Samoc, Marek

2018-05-01

Thiolate-protected gold nanoclusters have recently attracted considerable attention due to their size-dependent luminescence characterized by a long lifetime and large Stokes shift. However, the optimization of nanocluster properties such as the luminescence quantum yield is still a challenge. We report here the transformation of Au25Capt18 (Capt labels captopril) nanoclusters occurring at low pH and yielding a product with a much increased luminescence quantum yield which we have identified as Au23Capt17. We applied a simple method of treatment with HCl to accomplish this transformation and we characterized the absorption and emission of the newly created ligated nanoclusters as well as their morphology. Based on DFT calculations we show which Au nanocluster size transformations can lead to highly luminescent species such as Au23Capt17.

Mysteries of TOPSe revealed: insights into quantum dot nucleation.

PubMed

Evans, Christopher M; Evans, Meagan E; Krauss, Todd D

2010-08-18

We have investigated the reaction mechanism responsible for QD nucleation using optical absorption and nuclear magnetic resonance spectroscopies. For typical II-VI and IV-VI quantum dot (QD) syntheses, pure tertiary phosphine selenide sources (e.g., trioctylphosphine selenide (TOPSe)) were surprisingly found to be unreactive with metal carboxylates and incapable of yielding QDs. Rather, small quantities of secondary phosphines, which are impurities in tertiary phosphines, are entirely responsible for the nucleation of QDs; their low concentrations account for poor synthetic conversion yields. QD yields increase to nearly quantitative levels when replacing TOPSe with a stoiciometric amount of a secondary phosphine chalcogenide such as diphenylphosphine selenide. Based on our observations, we have proposed potential monomer identities, reaction pathways, and transition states and believe this mechanism to be universal to all II-VI and IV-VI QDs synthesized using phosphine based methods.

Mysteries of TOPSe Revealed: Insights into Quantum Dot Nucleation

PubMed Central

Evans, Christopher M.; Evans, Meagan E.

2010-01-01

We have investigated the reaction mechanism responsible for QD nucleation using optical absorption and nuclear magnetic resonance spectroscopies. For typical II-VI and IV-VI quantum dot (QD) syntheses, pure tertiary phosphine selenide sources (e.g. trioctylphosphine selenide (TOPSe)) were surprisingly found to be unreactive with metal carboxylates and incapable of yielding QDs. Rather, small quantities of secondary phosphines, which are impurities in tertiary phosphines, are entirely responsible for the nucleation of QDs; their low concentrations account for poor synthetic conversion yields. QD yields increase to nearly quantitative levels when replacing TOPSe with a stoiciometric amount of a secondary phosphine chalcogenide such as diphenylphosphine selenide. Based on our observations, we have proposed potential monomer identities, reaction pathways and transition states, and believe this mechanism to be universal to all II-VI and IV-VI QDs synthesized using phosphine based methods. PMID:20698646

The Chameleonic Nature of Platinum(II) Imidazopyridine Complexes.

PubMed

Pinter, Piermaria; Pittkowski, Rebecca; Soellner, Johannes; Strassner, Thomas

2017-10-12

The synthesis and characterization of cyclometalated C^C* platinum(II) complexes with unique photophysical properties, aggregation induced enhancement of the quantum yields with a simultaneous decrease of phosphorescence lifetimes, is reported. Additionally, a change of emission color is induced by variation of the excitation wavelength. The aggregation behavior of these complexes is controlled by the steric demand of the substituents. The photophysical properties of these complexes are investigated through emission-excitation matrix analysis (EEM). The monomeric complexes are excellent room temperature phosphorescent blue emitters with emission maxima below 470 nm and quantum yields of up to 93 %. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Interaction of light with dye-doped calcium phosphate nanoparticles

NASA Astrophysics Data System (ADS)

Russin, Timothy John

In this work we present work on a novel amorphous calcium phosphate nanoparticle system for use in bioimaging and drug delivery applications. The system, by virtue of its synthesis, can be made to encapsulate and protect any number of molecules that are not suitable for biological applications on their own; for example, medication that is poorly soluble in aqueous solution can be encapsulated for delivery, or fragile optical molecules can be encapsulated to protect them from the local environment. We have encapsulated the near-infrared dye indocyanine green, which has beneficial properties for optical imaging (low biotoxicity, absorption and emission at a minimum of tissue absorption). There are two original works presented in this thesis. The first describes the measurement of the quantum yield of the indocyanine green-doped nanoparticles, as well as the development of a theoretical method to extract the molecular quantum yield of a fluorophore encapsulated in a dielectric sphere from effective quantum yield measurements of nanoparticle dispersions in solution. The second work is an application of diffuse scattering theory to the problem of light propagation in biological tissue; specifically, the limits on penetration depth for photodynamic therapy and bioimaging.

Montelukast photodegradation: elucidation of Ф-order kinetics, determination of quantum yields and application to actinometry.

PubMed

Maafi, Mounir; Maafi, Wassila

2014-08-25

A recently developed Ф-order semi-emperical integrated rate-law for photoreversible AB(2Ф) reactions has been successfully applied to investigate Montelukast sodium (Monte) photodegradation kinetics in ethanol. The model equations also served to propose a new stepwise kinetic elucidation method valid for any AB(2Ф) system and its application to the determination of Monte's forward (Ф(λ(irr))(A-->B)) and reverse (Ф(λ(irr))(B-->A)) quantum yields at various irradiation wavelengths. It has been found that Ф(λ(irr))(A-->B) undergoes a 15-fold increase with wavelength between 220 and 360 nm, with the spectral section 250-360 nm representing Monte effective photodegradation causative range. The reverse quantum yield values were generally between 12 and 54% lower than those recorded for Ф(λ(irr))(A-->B), with the trans-isomer (Monte) converting almost completely to its cis-counterpart at high irradiation wavelengths. Furthermore, the potential use of Monte as an actinometer has been investigated, and an actinometric method was proposed. This study demonstrated the usefulness of Monte for monochromatic light actinometry for the dynamic range 258-380 nm. Copyright © 2014 Elsevier B.V. All rights reserved.

The influence of the Tbeta level upon fluorescence and laser properties of aromatic compounds.

PubMed

Nijegorodov, N; Winkoun, D P; Nkoma, J S

2004-07-01

The fluorescence and laser properties of seven specially chosen aromatic compounds are studied at 293 degrees C. The quantum yield of fluorescence, gamma, decay times, tauf, of the deaerated and non-deaerated solutions are measured. The oscillator strength, fe, fluorescence rate constants, kf, natural lifetimes, tauT0, and intersystem crossing rate constants, kST, are calculated. Some laser parameters are calculated or measured experimentally. It is found that the position of the Tbeta level plays an important role in the fluorescence and laser properties of aromatic compounds. If the Tbeta level is situated below the Sp level, it decreases the quantum yield of fluorescence and the decay time and increases the threshold of laser action. If, due to some structural changes of a molecule, the Tbeta level is situated higher than the Sp level, then the quantum yield of fluorescence and the decay times are increasing and the threshold of laser action is decreasing. Such influence of the position of the Tbeta level upon fluorescence and laser properties of aromatic compound is explained by the fact that the Sp level mixes with the Tbeta level more readily than with other taupipi* levels.

Synthesis and photophysical characterizations of thermal-stable naphthalene benzimidazoles.

PubMed

Erten-Ela, Sule; Ozcelik, Serdar; Eren, Esin

2011-07-01

Microwave-assisted synthesis, photophysical and electrochemical properties of thermal-stable naphthalene benzimidazoles and naphthalimides are studied in this paper. Microwave-assisted synthesis of naphthalene benzimidazoles provide higher yields than the conventional thermal synthesis. Comparative photophysical properties of naphthalene benzimidazoles and naphthalimides are revealed that conjugation of electron-donating group onto naphthalimide moiety increases fluorescence quantum yields. Fluorophore-solvent interactions are also investigated using Lippert-Mataga equation for naphthalimides and naphthalene benzimidazoles. Thermal stabilities of naphthalene benzimidazoles are better than naphthalimides due to increased aromaticity. The experimental E(LUMO) levels of naphthalene benzimidazoles are found to be between 3.15 and 3.28 eV. Therefore, naphthalene benzimidazole derivatives consisting of anchoring groups are promising materials in organic dye sensitized solar cells. © Springer Science+Business Media, LLC 2011

Proline puckering parameters for collagen structure simulations

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

Wu, Di, E-mail: diwu@fudan.edu.cn

Collagen is made of triple helices rich in proline residues, and hence is influenced by the conformational motions of prolines. Because the backbone motions of prolines are restricted by the helical structures, the only side chain motion—proline puckering—becomes an influential factor that may affect the stability of collagen structures. In molecular simulations, a proper proline puckering population is desired so to yield valid results of the collagen properties. Here we design the proline puckering parameters in order to yield suitable proline puckering populations as demonstrated in the experimental results. We test these parameters in collagen and the proline dipeptide simulations.more » Compared with the results of the PDB and the quantum calculations, we propose the proline puckering parameters for the selected collagen model simulations.« less

Hole Transfer from Low Band Gap Quantum Dots to Conjugated Polymers in Organic/Inorganic Hybrid Photovoltaics.

PubMed

Colbert, Adam E; Janke, Eric M; Hsieh, Stephen T; Subramaniyan, Selvam; Schlenker, Cody W; Jenekhe, Samson A; Ginger, David S

2013-01-17

We use photoinduced absorption (PIA) spectroscopy to investigate pathways for photocurrent generation in hybrid organic/inorganic quantum dot bulk heterojunction solar cells. We study blends of the conjugated polymer poly(2,3-bis(2-(hexyldecyl)quinoxaline-5,8-diyl-alt-N-(2-hexyldecyl)dithieno[3,2-b:2',3'-d]pyrrole) (PDTPQx-HD) with PbS quantum dots and find that positively charged polarons are formed on the conjugated polymer following selective photoexcitation of the PbS quantum dots. This result provides a direct spectroscopic fingerprint demonstrating that photoinduced hole transfer occurs from the photoexcited quantum dots to the host polymer. We compute the relative yields of long-lived holes following photoexcitation of both the polymer and quantum dot phases and estimate that more long-lived polarons are produced per photon absorbed by the polymer phase than by the quantum dot phase.

Noninformative prior in the quantum statistical model of pure states

NASA Astrophysics Data System (ADS)

Tanaka, Fuyuhiko

2012-06-01

In the present paper, we consider a suitable definition of a noninformative prior on the quantum statistical model of pure states. While the full pure-states model is invariant under unitary rotation and admits the Haar measure, restricted models, which we often see in quantum channel estimation and quantum process tomography, have less symmetry and no compelling rationale for any choice. We adopt a game-theoretic approach that is applicable to classical Bayesian statistics and yields a noninformative prior for a general class of probability distributions. We define the quantum detection game and show that there exist noninformative priors for a general class of a pure-states model. Theoretically, it gives one of the ways that we represent ignorance on the given quantum system with partial information. Practically, our method proposes a default distribution on the model in order to use the Bayesian technique in the quantum-state tomography with a small sample.

Physics Meets Philosophy at the Planck Scale

NASA Astrophysics Data System (ADS)

Callender, Craig; Huggett, Nick

2001-04-01

Preface; 1. Introduction Craig Callendar and Nick Huggett; Part I. Theories of Quantum Gravity and their Philosophical Dimensions: 2. Spacetime and the philosophical challenge of quantum gravity Jeremy Butterfield and Christopher Isham; 3. Naive quantum gravity Steven Weinstein; 4. Quantum spacetime: what do we know? Carlo Rovelli; Part II. Strings: 5. Reflections on the fate of spacetime Edward Witten; 6. A philosopher looks at string theory Robert Weingard; 7. Black holes, dumb holes, and entropy William G. Unruh; Part III. Topological Quantum Field Theory: 8. Higher-dimensional algebra and Planck scale physics John C. Baez; Part IV. Quantum Gravity and the Interpretation of General Relativity: 9. On general covariance and best matching Julian B. Barbour; 10. Pre-Socratic quantum gravity Gordon Belot and John Earman; 11. The origin of the spacetime metric: Bell's 'Lorentzian Pedagogy' and its significance in general relativity Harvey R. Brown and Oliver Pooley; Part IV. Quantum Gravity and the Interpretation of Quantum Mechanics: 12. Quantum spacetime without observers: ontological clarity and the conceptual foundations of quantum gravity Sheldon Goldstein and Stefan Teufel; 13. On gravity's role in quantum state reduction Roger Penrose; 14. Why the quantum must yield to gravity Joy Christian.

Quantum logic using correlated one-dimensional quantum walks

NASA Astrophysics Data System (ADS)

Lahini, Yoav; Steinbrecher, Gregory R.; Bookatz, Adam D.; Englund, Dirk

2018-01-01

Quantum Walks are unitary processes describing the evolution of an initially localized wavefunction on a lattice potential. The complexity of the dynamics increases significantly when several indistinguishable quantum walkers propagate on the same lattice simultaneously, as these develop non-trivial spatial correlations that depend on the particle's quantum statistics, mutual interactions, initial positions, and the lattice potential. We show that even in the simplest case of a quantum walk on a one dimensional graph, these correlations can be shaped to yield a complete set of compact quantum logic operations. We provide detailed recipes for implementing quantum logic on one-dimensional quantum walks in two general cases. For non-interacting bosons—such as photons in waveguide lattices—we find high-fidelity probabilistic quantum gates that could be integrated into linear optics quantum computation schemes. For interacting quantum-walkers on a one-dimensional lattice—a situation that has recently been demonstrated using ultra-cold atoms—we find deterministic logic operations that are universal for quantum information processing. The suggested implementation requires minimal resources and a level of control that is within reach using recently demonstrated techniques. Further work is required to address error-correction.

Efficient energy transfer in light-harvesting systems: Quantum-classical comparison, flux network, and robustness analysis

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

Wu Jianlan; Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Ave., Cambridge, Massachusetts 02139; Liu Fan

2012-11-07

Following the calculation of optimal energy transfer in thermal environment in our first paper [J. L. Wu, F. Liu, Y. Shen, J. S. Cao, and R. J. Silbey, New J. Phys. 12, 105012 (2010)], full quantum dynamics and leading-order 'classical' hopping kinetics are compared in the seven-site Fenna-Matthews-Olson (FMO) protein complex. The difference between these two dynamic descriptions is due to higher-order quantum corrections. Two thermal bath models, classical white noise (the Haken-Strobl-Reineker (HSR) model) and quantum Debye model, are considered. In the seven-site FMO model, we observe that higher-order corrections lead to negligible changes in the trapping time ormore » in energy transfer efficiency around the optimal and physiological conditions (2% in the HSR model and 0.1% in the quantum Debye model for the initial site at BChl 1). However, using the concept of integrated flux, we can identify significant differences in branching probabilities of the energy transfer network between hopping kinetics and quantum dynamics (26% in the HSR model and 32% in the quantum Debye model for the initial site at BChl 1). This observation indicates that the quantum coherence can significantly change the distribution of energy transfer pathways in the flux network with the efficiency nearly the same. The quantum-classical comparison of the average trapping time with the removal of the bottleneck site, BChl 4, demonstrates the robustness of the efficient energy transfer by the mechanism of multi-site quantum coherence. To reconcile with the latest eight-site FMO model which is also investigated in the third paper [J. Moix, J. L. Wu, P. F. Huo, D. F. Coker, and J. S. Cao, J. Phys. Chem. Lett. 2, 3045 (2011)], the quantum-classical comparison with the flux network analysis is summarized in Appendix C. The eight-site FMO model yields similar trapping time and network structure as the seven-site FMO model but leads to a more disperse distribution of energy transfer pathways.« less

Introduction to dissociative recombination

NASA Technical Reports Server (NTRS)

Guberman, Steven L.; Mitchell, J. Brian A.

1989-01-01

Dissociative recombination (DR) of molecular ions with electrons has important consequences in many areas of physical science. Ab-initio calculations coupled with resonant scattering theory and multichannel quantum defect studies have produced detailed results illuminating the role of ion vibrational excitation, the quantum yields of the DR products, and the role of Rydberg states. The theoretical and experimental results are discussed.

Quantum Mechanics in Insulators

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

Aeppli, G.; Department of Physics and Astronomy, University College of London, London

Atomic physics is undergoing a large revival because of the possibility of trapping and cooling ions and atoms both for individual quantum control as well as collective quantum states, such as Bose-Einstein condensates. The present lectures start from the 'atomic' physics of isolated atoms in semiconductors and insulators and proceed to coupling them together to yield magnets undergoing quantum phase transitions as well as displaying novel quantum states with no classical analogs. The lectures are based on: G.-Y. Xu et al., Science 317, 1049-1052 (2007); G. Aeppli, P. Warburton, C. Renner, BT Technology Journal, 24, 163-169 (2006); H. M. Ronnowmore » et al., Science 308, 392-395 (2005) and N. Q. Vinh et al., PNAS 105, 10649-10653 (2008).« less

Multipolar Ewald methods, 1: theory, accuracy, and performance.

PubMed

Giese, Timothy J; Panteva, Maria T; Chen, Haoyuan; York, Darrin M

2015-02-10

The Ewald, Particle Mesh Ewald (PME), and Fast Fourier–Poisson (FFP) methods are developed for systems composed of spherical multipole moment expansions. A unified set of equations is derived that takes advantage of a spherical tensor gradient operator formalism in both real space and reciprocal space to allow extension to arbitrary multipole order. The implementation of these methods into a novel linear-scaling modified “divide-and-conquer” (mDC) quantum mechanical force field is discussed. The evaluation times and relative force errors are compared between the three methods, as a function of multipole expansion order. Timings and errors are also compared within the context of the quantum mechanical force field, which encounters primary errors related to the quality of reproducing electrostatic forces for a given density matrix and secondary errors resulting from the propagation of the approximate electrostatics into the self-consistent field procedure, which yields a converged, variational, but nonetheless approximate density matrix. Condensed-phase simulations of an mDC water model are performed with the multipolar PME method and compared to an electrostatic cutoff method, which is shown to artificially increase the density of water and heat of vaporization relative to full electrostatic treatment.

Probing structure and dynamics of DNA with 2-aminopurine: effects of local environment on fluorescence.

PubMed

Rachofsky, E L; Osman, R; Ross, J B

2001-01-30

2-Aminopurine (2AP) is an analogue of adenine that has been utilized widely as a fluorescence probe of protein-induced local conformational changes in DNA. Within a DNA strand, this fluorophore demonstrates characteristic decreases in quantum yield and emission decay lifetime that vary sensitively with base sequence, temperature, and helix conformation but that are accompanied by only small changes in emission wavelength. However, the molecular interactions that give rise to these spectroscopic changes have not been established. To develop a molecular model for interpreting the fluorescence measurements, we have investigated the effects of environmental polarity, hydrogen bonding, and the purine and pyrimidine bases of DNA on the emission energy, quantum yield, and intensity decay kinetics of 2AP in simple model systems. The effects of environmental polarity were examined in a series of solvents of varying dielectric constant, and hydrogen bonding was investigated in binary mixtures of water with 1,4-dioxane or N,N-dimethylformamide (DMF). The effects of the purine and pyrimidine bases were studied by titrating 2AP deoxyriboside (d2AP) with the nucleosides adenosine (rA), cytidine (rC), guanosine (rG), and deoxythymidine (dT), and the nucleoside triphosphates ATP and GTP in neutral aqueous solution. The nucleosides and NTPs each quench the fluorescence of d2AP by a combination of static (affecting only the quantum yield) and dynamic (affecting both the quantum yield and the lifetime, proportionately) mechanisms. The peak wavelength and shape of the emission spectrum are not altered by either of these effects. The static quenching is saturable and has half-maximal effect at approximately 20 mM nucleoside or NTP, consistent with an aromatic stacking interaction. The rate constant for dynamic quenching is near the diffusion limit for collisional interaction (k(q) approximately 2 x 10(9) M(-1) s(-1)). Neither of these effects varies significantly between the various nucleosides and NTPs studied. In contrast, hydrogen bonding with water was observed to have a negligible effect on the emission wavelength, fluorescence quantum yield, or lifetime of 2AP in either dioxane or DMF. In nonpolar solvents, the fluorescence lifetime and quantum yield decrease dramatically, accompanied by significant shifts in the emission spectrum to shorter wavelengths. However, these effects of polarity do not coincide with the observed emission wavelength-independent quenching of 2AP fluorescence in DNA. Therefore, we conclude that the fluorescence quenching of 2AP in DNA arises from base stacking and collisions with neighboring bases only but is insensitive to base-pairing or other hydrogen bonding interactions. These results implicate both structural and dynamic properties of DNA in quenching of 2AP and constitute a simple model within which the fluorescence changes induced by protein-DNA binding or other perturbations may be interpreted.

Quantum key distribution with 1.25 Gbps clock synchronization.

PubMed

Bienfang, J; Gross, A; Mink, A; Hershman, B; Nakassis, A; Tang, X; Lu, R; Su, D; Clark, Charles; Williams, Carl; Hagley, E; Wen, Jesse

2004-05-03

We have demonstrated the exchange of sifted quantum cryptographic key over a 730 meter free-space link at rates of up to 1.0 Mbps, two orders of magnitude faster than previously reported results. A classical channel at 1550 nm operates in parallel with a quantum channel at 845 nm. Clock recovery techniques on the classical channel at 1.25 Gbps enable quantum transmission at up to the clock rate. System performance is currently limited by the timing resolution of our silicon avalanche photodiode detectors. With improved detector resolution, our technique will yield another order of magnitude increase in performance, with existing technology.

Facile synthesis of fluorescent polymer nanoparticles by covalent modification-nanoprecipitation of amine-reactive ester polymers.

PubMed

Lee, Yeonju; Hanif, Sadaf; Theato, Patrick; Zentel, Rudolf; Lim, Jeewoo; Char, Kookheon

2015-06-01

Emission wavelength control in fluorescent nanoparticles (NPs) is crucial for their applications. In the case of inorganic quantum dots or dye-impregnated silica NPs, such a control is readily achieved by changing the size of the particles or choosing appropriate fluorescent dyes, respectively. A similar modular approach for controlling the emission wavelength of fluo-rescent polymer NPs, however, is difficult. This article reports on fluorescent polymer NPs, the synthesis of which provides a platform for a modular approach towards the preparation of fluorescent NPs of desired emission wavelength. Atom-transfer radical polymerization (ATRP) is employed to synthesize reactive ester polymers, which are then easily modified with a commercially available dye and subsequently subjected to nanoprecipitation. The resulting NPs, with low size polydispersity, show an enhanced emission quantum yield when compared with the same dye molecules in solution. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Atomic level characterization of cadmium selenide nanocrystal systems using atomic number contrast scanning transmission electron microscopy and Rutherford backscattering spectroscopy

NASA Astrophysics Data System (ADS)

McBride, James R.

This project involved the characterization of CdSe nanocrystals. Through the use of Atomic Number Contrast Scanning Transmission Electron Microscopy (Z-STEM) and Rutherford Backscattering Spectroscopy (RBS), atomic level structure and chemical information was obtained. Specifically, CdSe nanocrystals produced using a mixture of hexadecylamine (HDA) and trioctylphosphine oxide (TOPO) were determined to be spherical compared to nanocrystals produced in TOPO only, which had elongated (101) facets. Additionally, the first Z-STEM images of CdSe/ZnS core/shell nanocrystals were obtained. From these images, the growth mechanism of the ZnS shell was determined and the existence of non-fluorescent ZnS particles was confirmed. Through collaboration with Quantum Dot Corp., core/shell nanocrystals with near unity quantum yield were developed. These core/shell nanocrystals included a US intermediate layer to improve shell coverage.

Quantum molecular dynamics and multistep-direct analyses of multiple preequilibrium emission

NASA Astrophysics Data System (ADS)

Chadwick, M. B.; Chiba, S.; Niita, K.; Maruyama, T.; Iwamoto, A.

1995-11-01

We study multiple preequilibrium emission in nucleon induced reactions at intermediate energies, and compare quantum molecular dynamics (QMD) calculations with multistep-direct Feshbach-Kerman-Koonin results [M. B. Chadwick, P. G. Young, D. C. George, and Y. Watanabe, Phys. Rev. C 50, 996 (1994)]. When the theoretical expressions of this reference are reformulated so that the definitions of primary and multiple emission correspond to those used in QMD, the two theories yield similar results for primary and multiple preequilibrium emission. We use QMD as a tool to determine the multiplicities of fast preequilibrium nucleons as a function of incident energy. For fast particle cross sections to exceed 5% of the inclusive preequilibrium emission cross sections we find that two particles should be included in reactions above 50 MeV, three above about 180 MeV, and four are only needed when the incident energy exceeds about 400 MeV.

Continuous-variable quantum teleportation with non-Gaussian resources

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

Dell'Anno, F.; Dipartimento di Fisica, Universita degli Studi di Salerno, Via S. Allende, I-84081 Baronissi; CNR-INFM Coherentia, Napoli, Italy and CNISM Unita di Salerno and INFN Sezione di Napoli, Gruppo Collegato di Salerno, Baronissi

2007-08-15

We investigate continuous variable quantum teleportation using non-Gaussian states of the radiation field as entangled resources. We compare the performance of different classes of degaussified resources, including two-mode photon-added and two-mode photon-subtracted squeezed states. We then introduce a class of two-mode squeezed Bell-like states with one-parameter dependence for optimization. These states interpolate between and include as subcases different classes of degaussified resources. We show that optimized squeezed Bell-like resources yield a remarkable improvement in the fidelity of teleportation both for coherent and nonclassical input states. The investigation reveals that the optimal non-Gaussian resources for continuous variable teleportation are those thatmore » most closely realize the simultaneous maximization of the content of entanglement, the degree of affinity with the two-mode squeezed vacuum, and the, suitably measured, amount of non-Gaussianity.« less

230 s room-temperature storage time and 1.14 eV hole localization energy in In{sub 0.5}Ga{sub 0.5}As quantum dots on a GaAs interlayer in GaP with an AlP barrier

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

Bonato, Leo, E-mail: leo.bonato@tu-berlin.de; Sala, Elisa M.; Stracke, Gernot

2015-01-26

A GaP n{sup +}p-diode containing In{sub 0.5}Ga{sub 0.5}As quantum dots (QDs) and an AlP barrier is characterized electrically, together with two reference samples: a simple n{sup +}p-diode and an n{sup +}p-diode with AlP barrier. Localization energy, capture cross-section, and storage time for holes in the QDs are determined using deep-level transient spectroscopy. The localization energy is 1.14(±0.04) eV, yielding a storage time at room temperature of 230(±60) s, which marks an improvement of 2 orders of magnitude compared to the former record value in QDs. Alternative material systems are proposed for still higher localization energies and longer storage times.

Comparison of the iterated equation of motion approach and the density matrix formalism for the quantum Rabi model

NASA Astrophysics Data System (ADS)

Kalthoff, Mona; Keim, Frederik; Krull, Holger; Uhrig, Götz S.

2017-05-01

The density matrix formalism and the equation of motion approach are two semi-analytical methods that can be used to compute the non-equilibrium dynamics of correlated systems. While for a bilinear Hamiltonian both formalisms yield the exact result, for any non-bilinear Hamiltonian a truncation is necessary. Due to the fact that the commonly used truncation schemes differ for these two methods, the accuracy of the obtained results depends significantly on the chosen approach. In this paper, both formalisms are applied to the quantum Rabi model. This allows us to compare the approximate results and the exact dynamics of the system and enables us to discuss the accuracy of the approximations as well as the advantages and the disadvantages of both methods. It is shown to which extent the results fulfill physical requirements for the observables and which properties of the methods lead to unphysical results.

Investigation of degradation mechanisms in composite matrices

NASA Technical Reports Server (NTRS)

Giori, C.; Yamauchi, T.

1982-01-01

Degradation mechanisms were investigated for graphite/polysulfone and graphite/epoxy laminates exposed to ultraviolet and high-energy electron radiations in vacuum up to 960 equivalent sun hours and 10 to the ninth power rads respectively. Based on GC and combined GC/MS analysis of volatile by-products evolved during irradiation, several free radical mechanisms of composite degradation were identified. The radiation resistance of different matrices was compared in terms of G values and quantum yields for gas formation. All the composite materials evaluated show high electron radiation stability and relatively low ultraviolet stability as indicated by low G values and high quantum for gas formation. Mechanical property measurements of irradiated samples did not reveal significant changes, with the possible exception of UV exposed polysulfone laminates. Hydrogen and methane were identified as the main by-products of irradiation, along with unexpectedly high levels of CO and CO2.

Noise induced quantum effects in photosynthetic complexes

NASA Astrophysics Data System (ADS)

Dorfman, Konstantin; Voronine, Dmitri; Mukamel, Shaul; Scully, Marlan

2012-02-01

Recent progress in coherent multidimensional optical spectroscopy revealed effects of quantum coherence coupled to population leading to population oscillations as evidence of quantum transport. Their description requires reevaluation of the currently used methods and approximations. We identify couplings between coherences and populations as the noise-induced cross-terms in the master equation generated via Agarwal-Fano interference that have been shown earlier to enhance the quantum yield in a photocell. We investigated a broad range of typical parameter regimes, which may be applied to a variety of photosynthetic complexes. We demonstrate that quantum coherence may be induced in photosynthetic complexes under natural conditions of incoherent light from the sun. This demonstrates that a photosynthetic reaction center may be viewed as a biological quantum heat engine that transforms high-energy thermal photon radiation into low entropy electron flux.

Reactive ground-state pathways are not ubiquitous in red/green cyanobacteriochromes.

PubMed

Chang, Che-Wei; Gottlieb, Sean M; Kim, Peter W; Rockwell, Nathan C; Lagarias, J Clark; Larsen, Delmar S

2013-09-26

Recent characterization of the red/green cyanobacteriochrome (CBCR) NpR6012g4 revealed a high quantum yield for its forward photoreaction [J. Am. Chem. Soc. 2012, 134, 130-133] that was ascribed to the activity of hidden, productive ground-state intermediates. The dynamics of the pathways involving these ground-state intermediates was resolved with femtosecond dispersed pump-dump-probe spectroscopy, the first such study reported for any CBCR. To address the ubiquity of such second-chance initiation dynamics (SCID) in CBCRs, we examined the closely related red/green CBCR NpF2164g6 from Nostoc punctiforme. Both NpF2164g6 and NpR6012g4 use phycocyanobilin as the chromophore precursor and exhibit similar excited-state dynamics. However, NpF2164g6 exhibits a lower quantum yield of 32% for the generation of the isomerized Lumi-R primary photoproduct, compared to 40% for NpR6012g4. This difference arises from significantly different ground-state dynamics between the two proteins, with the SCID mechanism deactivated in NpF2164g6. We present an integrated inhomogeneous target model that self-consistently fits the pump-probe and pump-dump-probe signals for both forward and reverse photoreactions in both proteins. This work demonstrates that reactive ground-state intermediates are not ubiquitous phenomena in CBCRs.

Large transient nonproton ion movements in purple membrane suspensions are abolished by solubilization in Triton X-100.

PubMed Central

Marinetti, T; Mauzerall, D

1986-01-01

Light-induced release/uptake of both protons and other ions cause transient changes in conductivity in suspensions of purple membrane (PM) fragments (Marinetti, Tim, and David Mauzerall, 1983, Proc. Natl. Acad. Sci. USA, 80:178-180). We find that the release/uptake of nonproton ions with quantum yield greater than 1 is observed at most pHs and ionic strengths. Only at both low pH and low ionic strength is the conductivity transient mostly due to protons. Our hypothesis is that during the photocycle, changes occur in the PM's dense surface charge distribution that result in changes in the number of counterions bound or condensed at the membrane surface. To test this, the PM structure was perturbed with the nonionic detergent Triton X-100. Immediately after addition, Triton does not abolish the nonproton ion movements; in fact at low detergent concentrations (0.02% vol/vol) the signal amplitudes increased considerably. However, when PM is completely solubilized into monomers in Triton, the conductivity transients are due to protons alone, though at lower quantum yield compared with native PM. These results suggest that changes in the surface charge distribution in native PM's photocycle could contribute to proton transfer between the aqueous phase and bR itself. PMID:3019444

Efficient Carrier-to-Exciton Conversion in Field Emission Tunnel Diodes Based on MIS-Type van der Waals Heterostack.

PubMed

Wang, Shunfeng; Wang, Junyong; Zhao, Weijie; Giustiniano, Francesco; Chu, Leiqiang; Verzhbitskiy, Ivan; Zhou Yong, Justin; Eda, Goki

2017-08-09

We report on efficient carrier-to-exciton conversion and planar electroluminescence from tunnel diodes based on a metal-insulator-semiconductor (MIS) van der Waals heterostack consisting of few-layer graphene (FLG), hexagonal boron nitride (hBN), and monolayer tungsten disulfide (WS 2 ). These devices exhibit excitonic electroluminescence with extremely low threshold current density of a few pA·μm -2 , which is several orders of magnitude lower compared to the previously reported values for the best planar EL devices. Using a reference dye, we estimate the EL quantum efficiency to be ∼1% at low current density limit, which is of the same order of magnitude as photoluminescence quantum yield at the equivalent excitation rate. Our observations reveal that the efficiency of our devices is not limited by carrier-to-exciton conversion efficiency but by the inherent exciton-to-photon yield of the material. The device characteristics indicate that the light emission is triggered by injection of hot minority carriers (holes) to n-doped WS 2 by Fowler-Nordheim tunneling and that hBN serves as an efficient hole-transport and electron-blocking layer. Our findings offer insight into the intelligent design of van der Waals heterostructures and avenues for realizing efficient excitonic devices.

Energy-Cascaded Upconversion in an Organic Dye-Sensitized Core/Shell Fluoride Nanocrystal.

PubMed

Chen, Guanying; Damasco, Jossana; Qiu, Hailong; Shao, Wei; Ohulchanskyy, Tymish Y; Valiev, Rashid R; Wu, Xiang; Han, Gang; Wang, Yan; Yang, Chunhui; Ågren, Hans; Prasad, Paras N

2015-11-11

Lanthanide-doped upconversion nanoparticles hold promises for bioimaging, solar cells, and volumetric displays. However, their emission brightness and excitation wavelength range are limited by the weak and narrowband absorption of lanthanide ions. Here, we introduce a concept of multistep cascade energy transfer, from broadly infrared-harvesting organic dyes to sensitizer ions in the shell of an epitaxially designed core/shell inorganic nanostructure, with a sequential nonradiative energy transfer to upconverting ion pairs in the core. We show that this concept, when implemented in a core-shell architecture with suppressed surface-related luminescence quenching, yields multiphoton (three-, four-, and five-photon) upconversion quantum efficiency as high as 19% (upconversion energy conversion efficiency of 9.3%, upconversion quantum yield of 4.8%), which is about ~100 times higher than typically reported efficiency of upconversion at 800 nm in lanthanide-based nanostructures, along with a broad spectral range (over 150 nm) of infrared excitation and a large absorption cross-section of 1.47 × 10(-14) cm(2) per single nanoparticle. These features enable unprecedented three-photon upconversion (visible by naked eye as blue light) of an incoherent infrared light excitation with a power density comparable to that of solar irradiation at the Earth surface, having implications for broad applications of these organic-inorganic core/shell nanostructures with energy-cascaded upconversion.

Is the flower fluorescence relevant in biocommunication?

PubMed

Iriel, Analía; Lagorio, María Gabriela

2010-10-01

Flower fluorescence has been previously proposed as a potential visual signal to attract pollinators. In this work, this point was addressed by quantitatively measuring the fluorescence quantum yield (Φ(f)) for flowers of Bellis perennis (white, yellow, pink, and purple), Ornithogalum thyrsoides (petals and ovaries), Limonium sinuatum (white and yellow), Lampranthus productus (yellow), Petunia nyctaginiflora (white), Bougainvillea spectabilis (white and yellow), Antirrhinum majus (white and yellow), Eustoma grandiflorum (white and blue), Citrus aurantium (petals and stigma), and Portulaca grandiflora (yellow). The highest values were obtained for the ovaries of O. thyrsoides (Φ(f) = 0.030) and for Citrus aurantium petals (Φ(f) = 0.014) and stigma (Φ(f) = 0.013). Emitted photons as fluorescence were compared with reflected photons. It was concluded that the fluorescence emission is negligible compared to the reflected light, even for the most fluorescent samples, and it may not be considered as an optical signal in biocommunication. The work was complemented with the calculation of quantum catches for each studied flower species to describe the visual sensitization of eye photoreceptors.

Quantum Entanglement and the Topological Order of Fractional Hall States

NASA Astrophysics Data System (ADS)

Rezayi, Edward

2015-03-01

Fractional quantum Hall states or, more generally, topological phases of matter defy Landau classification based on order parameter and broken symmetry. Instead they have been characterized by their topological order. Quantum information concepts, such as quantum entanglement, appear to provide the most efficient method of detecting topological order solely from the knowledge of the ground state wave function. This talk will focus on real-space bi-partitioning of quantum Hall states and will present both exact diagonalization and quantum Monte Carlo studies of topological entanglement entropy in various geometries. Results on the torus for non-contractible cuts are quite rich and, through the use of minimum entropy states, yield the modular S-matrix and hence uniquely determine the topological order, as shown in recent literature. Concrete examples of minimum entropy states from known quantum Hall wave functions and their corresponding quantum numbers, used in exact diagonalizations, will be given. In collaboration with Clare Abreu and Raul Herrera. Supported by DOE Grant DE-SC0002140.

CW-pumped telecom band polarization entangled photon pair generation in a Sagnac interferometer.

PubMed

Li, Yan; Zhou, Zhi-Yuan; Ding, Dong-Sheng; Shi, Bao-Sen

2015-11-02

Polarization entangled photon pair source is widely used in many quantum information processing applications such as teleportation, quantum communications, quantum computation and high precision quantum metrology. We report on the generation of a continuous-wave pumped 1550 nm polarization entangled photon pair source at telecom wavelength using a type-II periodically poled KTiOPO(4) (PPKTP) crystal in a Sagnac interferometer. Hong-Ou-Mandel (HOM) interference measurement yields signal and idler photon bandwidth of 2.4 nm. High quality of entanglement is verified by various kinds of measurements, for example two-photon interference fringes, Bell inequality and quantum states tomography. The source can be tuned over a broad range against temperature or pump power without loss of visibilities. This source will be used in our future experiments such as generation of orbital angular momentum entangled source at telecom wavelength for quantum frequency up-conversion, entanglement based quantum key distributions and many other quantum optics experiments at telecom wavelengths.

Absorption and emission behaviour of trans- p-coumaric acid in aqueous solutions and some organic solvents

NASA Astrophysics Data System (ADS)

Putschögl, M.; Zirak, P.; Penzkofer, A.

2008-01-01

The absorption and fluorescence behaviour of trans- p-coumaric acid ( trans-4-hydroxycinnamic acid) is investigated in buffered aqueous solution over a wide range from pH 1 to pH 12, in un-buffered water, and in some organic solvents. Absorption cross-section spectra, fluorescence quantum distributions, fluorescence quantum yields, and degrees of fluorescence polarisation are measured. p-Coumaric acid exists in different ionic forms in aqueous solution depending on the pH. There is an equilibrium between the neutral form ( p-CAH 2) and the single anionic form ( p-CAH -) at low pH (p Kna ≈ 4.9), and between the single anionic and the double anionic form ( p-CA 2-) at high pH (p Kaa ≈ 9.35). In the organic solvents studied trans- p-coumaric acid is dissolved in its neutral form. The fluorescence quantum yield of trans- p-coumaric acid in aqueous solution is ϕF ≈ 1.4 × 10 -4 for the neutral and the single anionic form, while it is ϕF ≈ 1.3 × 10 -3 for the double anionic form. For trans- p-coumaric acid in organic solvents fluorescence quantum yields in the range from 4.8 × 10 -5 (acetonitrile) to 1.5 × 10 -4 (glycerol) were measured. The fluorescence spectra are 7700-10,000 cm -1 Stokes shifted in aqueous solution, and 5400-8200 cm -1 Stokes shifted in the studied organic solvents. Decay paths responsible for the low fluorescence quantum yields are discussed (photo-isomerisation and internal conversion for p-CA 2-, solvent-assisted intra-molecular charge-transfer or ππ ∗ to nπ ∗ transfer and internal conversion for p-CAH 2 and p-CAH -). The solvent dependence of the first ππ ∗ electronic transition frequency and of the fluorescence Stokes shift of p-CAH 2 is discussed in terms of polar solute-solvent interaction effects. Thereby the ground-state and excite-state molecular dipole moments are extracted.

Photodissociation of CO2 and quenching of metastables

NASA Technical Reports Server (NTRS)

Slanger, T. G.

1978-01-01

Investigations in four different areas were carried out to further our understanding of the chemistry of the atmospheres of Mars and Venus. CO2 photodissociation quantum yields were determined in the 1300-1500 A spectral region by measuring both CO and oxygen atoms. The O(1S) quantum yield was determined for CO2 photodissociation in the 1060-1175 A spectral region. The measurement resolves the differences between two earlier experiments, and demonstrates that the O(1S) yield is unity throughout most of the measured region. The pathways for the quenching of O(1S) by N2O, CO2, H2O and NO were investigated and the source of the Venus nightglow, detected by Venera 9 and 10, was investigated. What appears to be a new O2 band system, was detected although the identity of the transition is not yet evident.

Viscosity and medium effects on the fluorescence and photochemical behaviour of some aryl chalcones

NASA Astrophysics Data System (ADS)

Ebeid, El-Zeiny M.; Abdel-Kader, Mahmood H.; Issa, Raafat M.; El-Daly, Samy A.

1988-05-01

The emission, excitation and absorption spectra toghether with the fluorescence and photochemical quantum yields of some chalcone derivatives have been studied in organic solvents and micellar and microemulsion media. Both 4-[2-(2-pyridyl)ethenyl] ( I) and 4-[2-(4-pyridyl)ethenyl ( II) chalcones show large positive solvatochromic effects. The fluorescence quantum yields increase substantially as the medium viscosity increases with a subsequent decrease in the photochemical quatum yield. Compounds I and II undergo excited-state molecular aggregation in concentrated solutions giving excimer-like emission that coincides with emission from crystalline samples. The enthalpies of photoassociation have been estimated. The chalcone derivative I acts as an efficient quencher of the fluorescence of the laser dye 1,4-bis (β-pyridyl-2-vinyl)benzene via a long-range mechanism. The excited-state lifetimes of both I and II are short and at 20°C their τ values are less than 800 ps.

The Radical Pair Mechanism and the Avian Chemical Compass: Quantum Coherence and Entanglement

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

Zhang, Yiteng; Kais, Sabre; Berman, Gennady Petrovich

2015-02-02

We review the spin radical pair mechanism which is a promising explanation of avian navigation. This mechanism is based on the dependence of product yields on 1) the hyperfine interaction involving electron spins and neighboring nuclear spins and 2) the intensity and orientation of the geomagnetic field. One surprising result is that even at ambient conditions quantum entanglement of electron spins can play an important role in avian magnetoreception. This review describes the general scheme of chemical reactions involving radical pairs generated from singlet and triplet precursors; the spin dynamics of the radical pairs; and the magnetic field dependence ofmore » product yields caused by the radical pair mechanism. The main part of the review includes a description of the chemical compass in birds. We review: the general properties of the avian compass; the basic scheme of the radical pair mechanism; the reaction kinetics in cryptochrome; quantum coherence and entanglement in the avian compass; and the effects of noise. We believe that the quantum avian compass can play an important role in avian navigation and can also provide the foundation for a new generation of sensitive and selective magnetic-sensing nano-devices.« less

Near-Unity Internal Quantum Efficiency of Luminescent Silicon Nanocrystals with Ligand Passivation.

PubMed

Sangghaleh, Fatemeh; Sychugov, Ilya; Yang, Zhenyu; Veinot, Jonathan G C; Linnros, Jan

2015-07-28

Spectrally resolved photoluminescence (PL) decays were measured for samples of colloidal, ligand-passivated silicon nanocrystals. These samples have PL emission energies with peak positions in the range ∼1.4-1.8 eV and quantum yields of ∼30-70%. Their ensemble PL decays are characterized by a stretched-exponential decay with a dispersion factor of ∼0.8, which changes to an almost monoexponential character at fixed detection energies. The dispersion factors and decay rates for various detection energies were extracted from spectrally resolved curves using a mathematical approach that excluded the effect of homogeneous line width broadening. Since nonradiative recombination would introduce a random lifetime variation, leading to a stretched-exponential decay for an ensemble, we conclude that the observed monoexponential decay in size-selected ensembles signifies negligible nonradiative transitions of a similar strength to the radiative one. This conjecture is further supported as extracted decay rates agree with radiative rates reported in the literature, suggesting 100% internal quantum efficiency over a broad range of emission wavelengths. The apparent differences in the quantum yields can then be explained by a varying fraction of "dark" or blinking nanocrystals.

Generic framework for the secure Yuen 2000 quantum-encryption protocol employing the wire-tap channel approach

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

Mihaljevic, Miodrag J.

2007-05-15

It is shown that the security, against known-plaintext attacks, of the Yuen 2000 (Y00) quantum-encryption protocol can be considered via the wire-tap channel model assuming that the heterodyne measurement yields the sample for security evaluation. Employing the results reported on the wire-tap channel, a generic framework is proposed for developing secure Y00 instantiations. The proposed framework employs a dedicated encoding which together with inherent quantum noise at the attacker's side provides Y00 security.

Mechanism for the Green Glow of the Upper Ionosphere

NASA Technical Reports Server (NTRS)

Guberman, Steven L.

1997-01-01

The generation of the green line of atomic oxygen by dissociative recombination of 02 plus occurs by the capture of an electron into a repulsive state of 02 followed by dissociation along another state of a different electronic symmetry. The two states are coupled together by mixed symmetry Rydberg states. Quantum chemical calculations give a rate coefficient at room temperature of (0.39 (+ 0.31 or -0.19)) x 10 exp -8 cubic centimeters per second. The quantum yield of excited oxygen is within the range deduced from ground, rocket, and satellite observations. The rate coefficients and yields are needed in models of the optical emission, chemistry, and energy balance of planetary ionospheres.

Photosensitized electron transport across lipid vesicle walls: quantum yield dependence on sensitizer concentration.

PubMed Central

Ford, W E; Otvos, J W; Calvin, M

1979-01-01

An amphiphilic tris(2,2'-bipyridine)ruthenium(2+) derivative that is incorporated into the walls of phosphatidylcholine vesicles photosensitizes the irreversible oxidation of ethylenediaminetetraacetate(3-) dissolved in the inner aqueous compartments of the vesicle suspension and the one-electron reduction of heptylviologen(2+) dissolved in the continuous aqueous phase. The quantum yield of viologen radical production depends on the phospholipid-to-ruthenium complex mole ratios. A kinetic model is used to derive an order-of-magnitude estimate for the rate constant of electron transport across the vesicle walls. The results are inconsistent with a diffusional mechanism for electron transport and are interpreted in terms of electron exchange. PMID:291027

An Environmentally Sensitive Fluorescent Dye as a Multidimensional Probe of Amyloid Formation

PubMed Central

2016-01-01

We have explored amyloid formation using poly(amino acid) model systems in which differences in peptide secondary structure and hydrophobicity can be introduced in a controlled manner. We show that an environmentally sensitive fluorescent dye, dapoxyl, is able to identify β-sheet structure and hydrophobic surfaces, structural features likely to be related to toxicity, as a result of changes in its excitation and emission profiles and its relative quantum yield. These results show that dapoxyl is a multidimensional probe of the time dependence of amyloid aggregation, which provides information about the presence and nature of metastable aggregation intermediates that is inaccessible to the conventional probes that rely on changes in quantum yield alone. PMID:26865546

Free volume dependence of an ionic molecular rotor in Fluoroalkylphosphate (FAP) based ionic liquids

NASA Astrophysics Data System (ADS)

Singh, Prabhat K.; Mora, Aruna K.; Nath, Sukhendu

2016-01-01

The emission properties of Thioflavin-T (ThT), a cationic molecular rotor, have been investigated in two fluoroalkylphosphate ([FAP]) anion based ionic liquids, namely, 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate and 1-(2-hydroxyethyl)-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate, over a wide temperature range. The micro-viscosities of ionic liquids around ThT, measured from the emission quantum yield, are found to be quite different from their bulk viscosities. The temperature dependence of the viscosity and the emission quantum yield reveals that, despite the very low shear viscosity of these ILs, the non-radiative torsional relaxation has a strong dependence on the free volume of these [FAP] anion based ILs.

Arginine-glycine-aspartic acid-conjugated dendrimer-modified quantum dots for targeting and imaging melanoma.

PubMed

Li, Zhiming; Huang, Peng; Lin, Jing; He, Rong; Liu, Bing; Zhang, Xiaomin; Yang, Sen; Xi, Peng; Zhang, Xuejun; Ren, Qiushi; Cui, Daxiang

2010-08-01

Angiogenesis is essential for the development of malignant tumors and provides important targets for tumor diagnosis and therapy. Quantum dots have been broadly investigated for their potential application in cancer molecular imaging. In present work, CdSe quantum dots were synthesized, polyamidoamine dendrimers were used to modify surface of quantum dots and improve their solubility in water solution. Then, dendrimer-modified CdSe quantum dots were conjugated with arginine-glycine-aspartic acid (RGD) peptides. These prepared nanoprobes were injected into nude mice loaded with melanoma (A375) tumor xenografts via tail vessels, IVIS imaging system was used to image the targeting and bio-distribution of as-prepared nanoprobes. The dendrimer-modified quantum dots exhibit water-soluble, high quantum yield, and good biocompatibility. RGD-conjugated quantum dots can specifically target human umbilical vein endothelial cells (HUVEC) and A375 melanoma cells, as well as nude mice loaded with A735 melanoma cells. High-performance RGD-conjugated dendrimers modified quantum dot-based nanoprobes have great potential in application such as tumor diagnosis and therapy.

Relativistic quantum Darwinism in Dirac fermion and graphene systems

NASA Astrophysics Data System (ADS)

Ni, Xuan; Huang, Liang; Lai, Ying-Cheng; Pecora, Louis

2012-02-01

We solve the Dirac equation in two spatial dimensions in the setting of resonant tunneling, where the system consists of two symmetric cavities connected by a finite potential barrier. The shape of the cavities can be chosen to yield both regular and chaotic dynamics in the classical limit. We find that certain pointer states about classical periodic orbits can exist, which are signatures of relativistic quantum Darwinism (RQD). These localized states suppress quantum tunneling, and the effect becomes less severe as the underlying classical dynamics in the cavity is chaotic, leading to regularization of quantum tunneling. Qualitatively similar phenomena have been observed in graphene. A physical theory is developed to explain relativistic quantum Darwinism and its effects based on the spectrum of complex eigenenergies of the non-Hermitian Hamiltonian describing the open cavity system.

Josephson junction microwave amplifier in self-organized noise compression mode

PubMed Central

Lähteenmäki, Pasi; Vesterinen, Visa; Hassel, Juha; Seppä, Heikki; Hakonen, Pertti

2012-01-01

The fundamental noise limit of a phase-preserving amplifier at frequency is the standard quantum limit . In the microwave range, the best candidates have been amplifiers based on superconducting quantum interference devices (reaching the noise temperature at 700 MHz), and non-degenerate parametric amplifiers (reaching noise levels close to the quantum limit at 8 GHz). We introduce a new type of an amplifier based on the negative resistance of a selectively damped Josephson junction. Noise performance of our amplifier is limited by mixing of quantum noise from Josephson oscillation regime down to the signal frequency. Measurements yield nearly quantum-limited operation, at 2.8 GHz, owing to self-organization of the working point. Simulations describe the characteristics of our device well and indicate potential for wide bandwidth operation. PMID:22355788

Compact and highly stable quantum dots through optimized aqueous phase transfer

NASA Astrophysics Data System (ADS)

Tamang, Sudarsan; Beaune, Grégory; Poillot, Cathy; De Waard, Michel; Texier-Nogues, Isabelle; Reiss, Peter

2011-03-01

A large number of different approaches for the aqueous phase transfer of quantum dots have been proposed. Surface ligand exchange with small hydrophilic thiols, such as L-cysteine, yields the lowest particle hydrodynamic diameter. However, cysteine is prone to dimer formation, which limits colloidal stability. We demonstrate that precise pH control during aqueous phase transfer dramatically increases the colloidal stability of InP/ZnS quantum dots. Various bifunctional thiols have been applied. The formation of disulfides, strongly diminishing the fluorescence QY has been prevented through addition of appropriate reducing agents. Bright InP/ZnS quantum dots with a hydrodynamic diameter <10 nm and long-term stability have been obtained. Finally we present in vitro studies of the quantum dots functionalized with the cell-penetrating peptide maurocalcine.

Highly Luminescent Phase-Stable CsPbI3 Perovskite Quantum Dots Achieving Near 100% Absolute Photoluminescence Quantum Yield.

PubMed

Liu, Feng; Zhang, Yaohong; Ding, Chao; Kobayashi, Syuusuke; Izuishi, Takuya; Nakazawa, Naoki; Toyoda, Taro; Ohta, Tsuyoshi; Hayase, Shuzi; Minemoto, Takashi; Yoshino, Kenji; Dai, Songyuan; Shen, Qing

2017-10-24

Perovskite quantum dots (QDs) as a new type of colloidal nanocrystals have gained significant attention for both fundamental research and commercial applications owing to their appealing optoelectronic properties and excellent chemical processability. For their wide range of potential applications, synthesizing colloidal QDs with high crystal quality is of crucial importance. However, like most common QD systems such as CdSe and PbS, those reported perovskite QDs still suffer from a certain density of trapping defects, giving rise to detrimental nonradiative recombination centers and thus quenching luminescence. In this paper, we show that a high room-temperature photoluminescence quantum yield of up to 100% can be obtained in CsPbI 3 perovskite QDs, signifying the achievement of almost complete elimination of the trapping defects. This is realized with our improved synthetic protocol that involves introducing organolead compound trioctylphosphine-PbI 2 (TOP-PbI 2 ) as the reactive precursor, which also leads to a significantly improved stability for the resulting CsPbI 3 QD solutions. Ultrafast kinetic analysis with time-resolved transient absorption spectroscopy evidence the negligible electron or hole-trapping pathways in our QDs, which explains such a high quantum efficiency. We expect the successful synthesis of the "ideal" perovskite QDs will exert profound influence on their applications to both QD-based light-harvesting and -emitting devices.

Estimates on Functional Integrals of Quantum Mechanics and Non-relativistic Quantum Field Theory

NASA Astrophysics Data System (ADS)

Bley, Gonzalo A.; Thomas, Lawrence E.

2017-01-01

We provide a unified method for obtaining upper bounds for certain functional integrals appearing in quantum mechanics and non-relativistic quantum field theory, functionals of the form {E[{exp}(A_T)]} , the (effective) action {A_T} being a function of particle trajectories up to time T. The estimates in turn yield rigorous lower bounds for ground state energies, via the Feynman-Kac formula. The upper bounds are obtained by writing the action for these functional integrals in terms of stochastic integrals. The method is illustrated in familiar quantum mechanical settings: for the hydrogen atom, for a Schrödinger operator with {1/|x|^2} potential with small coupling, and, with a modest adaptation of the method, for the harmonic oscillator. We then present our principal applications of the method, in the settings of non-relativistic quantum field theories for particles moving in a quantized Bose field, including the optical polaron and Nelson models.

A quantum network of clocks

NASA Astrophysics Data System (ADS)

Komar, Peter; Kessler, Eric; Bishof, Michael; Jiang, Liang; Sorensen, Anders; Ye, Jun; Lukin, Mikhail

2014-05-01

Shared timing information constitutes a key resource for positioning and navigation with a direct correspondence between timing accuracy and precision in applications such as the Global Positioning System (GPS). By combining precision metrology and quantum networks, we propose here a quantum, cooperative protocol for the operation of a network consisting of geographically remote optical atomic clocks. Using non-local entangled states, we demonstrate an optimal utilization of the global network resources, and show that such a network can be operated near the fundamental limit set by quantum theory yielding an ultra-precise clock signal. Furthermore, the internal structure of the network, combined with basic techniques from quantum communication, guarantees security both from internal and external threats. Realization of such a global quantum network of clocks may allow construction of a real-time single international time scale (world clock) with unprecedented stability and accuracy. See also: Komar et al. arXiv:1310.6045 (2013) and Kessler et al. arXiv:1310.6043 (2013).

Converting multilevel nonclassicality into genuine multipartite entanglement

NASA Astrophysics Data System (ADS)

Regula, Bartosz; Piani, Marco; Cianciaruso, Marco; Bromley, Thomas R.; Streltsov, Alexander; Adesso, Gerardo

2018-03-01

Characterizing genuine quantum resources and determining operational rules for their manipulation are crucial steps to appraise possibilities and limitations of quantum technologies. Two such key resources are nonclassicality, manifested as quantum superposition between reference states of a single system, and entanglement, capturing quantum correlations among two or more subsystems. Here we present a general formalism for the conversion of nonclassicality into multipartite entanglement, showing that a faithful reversible transformation between the two resources is always possible within a precise resource-theoretic framework. Specializing to quantum coherence between the levels of a quantum system as an instance of nonclassicality, we introduce explicit protocols for such a mapping. We further show that the conversion relates multilevel coherence and multipartite entanglement not only qualitatively, but also quantitatively, restricting the amount of entanglement achievable in the process and in particular yielding an equality between the two resources when quantified by fidelity-based geometric measures.

Entropy generation in Gaussian quantum transformations: applying the replica method to continuous-variable quantum information theory

NASA Astrophysics Data System (ADS)

Gagatsos, Christos N.; Karanikas, Alexandros I.; Kordas, Georgios; Cerf, Nicolas J.

2016-02-01

In spite of their simple description in terms of rotations or symplectic transformations in phase space, quadratic Hamiltonians such as those modelling the most common Gaussian operations on bosonic modes remain poorly understood in terms of entropy production. For instance, determining the quantum entropy generated by a Bogoliubov transformation is notably a hard problem, with generally no known analytical solution, while it is vital to the characterisation of quantum communication via bosonic channels. Here we overcome this difficulty by adapting the replica method, a tool borrowed from statistical physics and quantum field theory. We exhibit a first application of this method to continuous-variable quantum information theory, where it enables accessing entropies in an optical parametric amplifier. As an illustration, we determine the entropy generated by amplifying a binary superposition of the vacuum and a Fock state, which yields a surprisingly simple, yet unknown analytical expression.

Historical remarks on exponential product and quantum analysis

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

Suzuki, Masuo

2015-03-10

The exponential product formula [1, 2] was substantially introduced in physics by the present author [2]. Its systematic applications to quantum Monte Carlo Methods [3] were preformed [4, 5] first in 1977. Many interesting applications [6] of the quantum-classical correspondence (namely S-T transformation) have been reported. Systematic higher-order decomposition formulae were also discovered by the present author [7-11], using the recursion scheme [7, 9]. Physically speaking, these exponential product formulae play a conceptual role of separation of procedures [3,14]. Mathematical aspects of these formulae have been integrated in quantum analysis [15], in which non-commutative differential calculus is formulated and amore » general quantum Taylor expansion formula is given. This yields many useful operator expansion formulae such as the Feynman expansion formula and the resolvent expansion. Irreversibility and entropy production are also studied using quantum analysis [15].« less

Quantum no-scale regimes in string theory

NASA Astrophysics Data System (ADS)

Coudarchet, Thibaut; Fleming, Claude; Partouche, Hervé

2018-05-01

We show that in generic no-scale models in string theory, the flat, expanding cosmological evolutions found at the quantum level can be attracted to a "quantum no-scale regime", where the no-scale structure is restored asymptotically. In this regime, the quantum effective potential is dominated by the classical kinetic energies of the no-scale modulus and dilaton. We find that this natural preservation of the classical no-scale structure at the quantum level occurs when the initial conditions of the evolutions sit in a subcritical region of their space. On the contrary, supercritical initial conditions yield solutions that have no analogue at the classical level. The associated intrinsically quantum universes are sentenced to collapse and their histories last finite cosmic times. Our analysis is done at 1-loop, in perturbative heterotic string compactified on tori, with spontaneous supersymmetry breaking implemented by a stringy version of the Scherk-Schwarz mechanism.

Radiative lifetimes of zincblende CdSe/CdS quantum dots

DOE PAGES

Gong, Ke; Martin, James E.; Shea-Rohwer, Lauren E.; ...

2015-01-02

Recent synthetic advances have made available very monodisperse zincblende CdSe/CdS quantum dots having near-unity photoluminescence quantum yields. Because of the absence of nonradiative decay pathways, accurate values of the radiative lifetimes can be obtained from time-resolved PL measurements. Radiative lifetimes can also be obtained from the Einstein relations, using the static absorption spectra and the relative thermal populations in the angular momentum sublevels. We found that one of the inputs into these calculations is the shell thickness, and it is useful to be able to determine shell thickness from spectroscopic measurements. We use an empirically corrected effective mass model tomore » produce a “map” of exciton wavelength as a function of core size and shell thickness. These calculations use an elastic continuum model and the known lattice and elastic constants to include the effect of lattice strain on the band gap energy. The map is in agreement with the known CdSe sizing curve and with the shell thicknesses of zincblende core/shell particles obtained from TEM images. Furthermore, if selenium–sulfur diffusion is included and lattice strain is omitted from the calculation then the resulting map is appropriate for wurtzite CdSe/CdS quantum dots synthesized at high temperatures, and this map is very similar to one previously reported (J. Am. Chem. Soc. 2009, 131, 14299). Radiative lifetimes determined from time-resolved measurements are compared to values obtained from the Einstein relations, and found to be in excellent agreement. For a specific core size (2.64 nm diameter, in the present case), radiative lifetimes are found to decrease with increasing shell thickness. Thus, this is similar to the size dependence of one-component CdSe quantum dots and in contrast to the size dependence in type-II quantum dots.« less

Regularized linearization for quantum nonlinear optical cavities: application to degenerate optical parametric oscillators.

PubMed

Navarrete-Benlloch, Carlos; Roldán, Eugenio; Chang, Yue; Shi, Tao

2014-10-06

Nonlinear optical cavities are crucial both in classical and quantum optics; in particular, nowadays optical parametric oscillators are one of the most versatile and tunable sources of coherent light, as well as the sources of the highest quality quantum-correlated light in the continuous variable regime. Being nonlinear systems, they can be driven through critical points in which a solution ceases to exist in favour of a new one, and it is close to these points where quantum correlations are the strongest. The simplest description of such systems consists in writing the quantum fields as the classical part plus some quantum fluctuations, linearizing then the dynamical equations with respect to the latter; however, such an approach breaks down close to critical points, where it provides unphysical predictions such as infinite photon numbers. On the other hand, techniques going beyond the simple linear description become too complicated especially regarding the evaluation of two-time correlators, which are of major importance to compute observables outside the cavity. In this article we provide a regularized linear description of nonlinear cavities, that is, a linearization procedure yielding physical results, taking the degenerate optical parametric oscillator as the guiding example. The method, which we call self-consistent linearization, is shown to be equivalent to a general Gaussian ansatz for the state of the system, and we compare its predictions with those obtained with available exact (or quasi-exact) methods. Apart from its operational value, we believe that our work is valuable also from a fundamental point of view, especially in connection to the question of how far linearized or Gaussian theories can be pushed to describe nonlinear dissipative systems which have access to non-Gaussian states.

Some applications of uncertainty relations in quantum information

NASA Astrophysics Data System (ADS)

Majumdar, A. S.; Pramanik, T.

2016-08-01

We discuss some applications of various versions of uncertainty relations for both discrete and continuous variables in the context of quantum information theory. The Heisenberg uncertainty relation enables demonstration of the Einstein, Podolsky and Rosen (EPR) paradox. Entropic uncertainty relations (EURs) are used to reveal quantum steering for non-Gaussian continuous variable states. EURs for discrete variables are studied in the context of quantum memory where fine-graining yields the optimum lower bound of uncertainty. The fine-grained uncertainty relation is used to obtain connections between uncertainty and the nonlocality of retrieval games for bipartite and tripartite systems. The Robertson-Schrödinger (RS) uncertainty relation is applied for distinguishing pure and mixed states of discrete variables.

Probability and Quantum Paradigms: the Interplay

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

Kracklauer, A. F.

Since the introduction of Born's interpretation of quantum wave functions as yielding the probability density of presence, Quantum Theory and Probability have lived in a troubled symbiosis. Problems arise with this interpretation because quantum probabilities exhibit features alien to usual probabilities, namely non Boolean structure and non positive-definite phase space probability densities. This has inspired research into both elaborate formulations of Probability Theory and alternate interpretations for wave functions. Herein the latter tactic is taken and a suggested variant interpretation of wave functions based on photo detection physics proposed, and some empirical consequences are considered. Although incomplete in a fewmore » details, this variant is appealing in its reliance on well tested concepts and technology.« less

Probability and Quantum Paradigms: the Interplay

NASA Astrophysics Data System (ADS)

Kracklauer, A. F.

2007-12-01

Since the introduction of Born's interpretation of quantum wave functions as yielding the probability density of presence, Quantum Theory and Probability have lived in a troubled symbiosis. Problems arise with this interpretation because quantum probabilities exhibit features alien to usual probabilities, namely non Boolean structure and non positive-definite phase space probability densities. This has inspired research into both elaborate formulations of Probability Theory and alternate interpretations for wave functions. Herein the latter tactic is taken and a suggested variant interpretation of wave functions based on photo detection physics proposed, and some empirical consequences are considered. Although incomplete in a few details, this variant is appealing in its reliance on well tested concepts and technology.

Entanglement as a signature of quantum chaos.

PubMed

Wang, Xiaoguang; Ghose, Shohini; Sanders, Barry C; Hu, Bambi

2004-01-01

We explore the dynamics of entanglement in classically chaotic systems by considering a multiqubit system that behaves collectively as a spin system obeying the dynamics of the quantum kicked top. In the classical limit, the kicked top exhibits both regular and chaotic dynamics depending on the strength of the chaoticity parameter kappa in the Hamiltonian. We show that the entanglement of the multiqubit system, considered for both the bipartite and the pairwise entanglement, yields a signature of quantum chaos. Whereas bipartite entanglement is enhanced in the chaotic region, pairwise entanglement is suppressed. Furthermore, we define a time-averaged entangling power and show that this entangling power changes markedly as kappa moves the system from being predominantly regular to being predominantly chaotic, thus sharply identifying the edge of chaos. When this entangling power is averaged over all states, it yields a signature of global chaos. The qualitative behavior of this global entangling power is similar to that of the classical Lyapunov exponent.

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

Luo, Yue; Ahmadi, Ehsaneh D.; Shayan, Kamran

Single-walled carbon nanotubes (SWCNTs) are promising absorbers and emitters to enable novel photonic applications and devices but are also known to suffer from low optical quantum yields. Here we demonstrate SWCNT excitons coupled to plasmonic nanocavity arrays reaching deeply into the Purcell regime with Purcell factors (F P) up to F P = 180 (average F P = 57), Purcell-enhanced quantum yields of 62% (average 42%), and a photon emission rate of 15 MHz into the first lens. The cavity coupling is quasi-deterministic since the photophysical properties of every SWCNT are enhanced by at least one order of magnitude. Furthermore,more » the measured ultra-narrow exciton linewidth (18 ueV) reaches the radiative lifetime limit, which is promising towards generation of transform-limited single photons. Furthermore, to demonstrate utility beyond quantum light sources we show that nanocavity-coupled SWCNTs perform as single-molecule thermometers detecting plasmonically induced heat at cryogenic temperatures in a unique interplay of excitons, phonons, and plasmons at the nanoscale.« less

Measurement of the photobleaching kinetics of semiconducting polymer films by the pump - probe method

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

Ozimova, A E; Bruevich, V V; Parashchuk, D Yu

2011-12-31

A phenomenological model of the laser photobleaching dynamics of a semiconducting polymer in a dual-beam scheme for different wavelengths of the burning and probe beams is developed. An experimental method is implemented based on this model, which allows one to investigate materials with significantly different photodegradation rates. The photodegradation quantum yield in mixtures of a semiconducting polymer belonging to polyparaphenylene vinylenes (MEH-PPV) with a low-molecular electron acceptor 2,4,7-trinitrofluorenone (TNF) is measured at burning wavelengths of 488 and 514 nm for different component ratios of MEHPPV : TNF. It is found that adding the acceptor decreases the polymer photodegradation quantum yieldmore » by at least four orders of magnitude in the MEH-PPV : TNF = 1 : 0.4 mixture; the photodegradation quantum yields are the same at both wavelengths. It is shown that the photodegradation rates of the MEH-PPV : TNF films measured by laser photobleaching and IR spectroscopy are in good agreement.« less

Temperature dependence of tris(2,2'-bipyridine) ruthenium (II) device characteristics

NASA Astrophysics Data System (ADS)

Slinker, Jason D.; Malliaras, George G.; Flores-Torres, Samuel; Abruña, Héctor D.; Chunwachirasiri, Withoon; Winokur, Michael J.

2004-04-01

We have investigated the temperature dependence of the current, radiance, and efficiency from electroluminescent devices based on [Ru(bpy)3]2+(PF6-)2, where bpy is 2,2'-bipyridine. We find that the current increases monotonically with temperature from 200 to 380 K, while the radiance reaches a maximum near room temperature. For temperatures greater than room temperature, an irreversible, current-induced degradation occurs with thermal cycling that diminishes both the radiance and the photoluminescence (PL) quantum yield, but does not affect the current. The temperature dependence of the external quantum efficiency is fully accounted for by the dependence of the PL quantum yield as measured from the emissive area of the device. This implies that the contacts remain ohmic throughout the temperature range investigated. The quenching of the PL with temperature was attributed to thermal activation to a nonradiative d-d transition. The temperature dependence of the current shows a complex behavior in which transport appears to be thermally activated, with distinct low-temperature and high-temperature regimes.

The use of dendrimers as high-performance shells for round-trip energy transfer: efficient trans-cis photoisomerization from an excited triplet state produced within a dendrimer shell.

PubMed

Miura, Yousuke; Momotake, Atsuya; Takeuchi, Keiichirou; Arai, Tatsuo

2011-01-01

A series of stilbene-cored poly(benzyl ether) dendrimers with benzophenone peripheries were synthesized and their photophysical and photochemical properties were studied. Fluorescence studies revealed that singlet-singlet energy transfer (SSET) from the stilbene core to the benzophenone units took place efficiently in dendrimers of all generations. Similarly, phosphorescence and time-resolved spectroscopic measurements indicated efficient triplet-triplet energy transfer (TTET) from the benzophenone periphery to the stilbene core. Upon excitation at 310 nm, the stilbene core isomerizes via an energy round trip within the dendrimer shell. The quantum yields for the energy round trip (Φ(ERT)), defined as the product of the quantum yields of SSET, intersystem crossing, and TTET (Φ(ERT) = Φ(SS)Φ(isc)Φ(TT)), were extremely high for all generations--99%, 95% and 94% for G1, G2, and G3, respectively--which means that the excitation energy of the dendrimer core was transferred to the dendrimer periphery and back to the core almost quantitatively. The quantum yield for photoisomerization of G1-G3 via an energy round trip was higher than for other stilbene-cored dendrimers, which mainly isomerize from the excited singlet state. Photostability in the dendrimers was also demonstrated and discussed.

Singlet Oxygen Generation by UVA Light Exposure of Endogenous Photosensitizers

PubMed Central

Baier, Jürgen; Maisch, Tim; Maier, Max; Engel, Eva; Landthaler, Michael; Bäumler, Wolfgang

2006-01-01

UVA light (320–400 nm) has been shown to produce deleterious biological effects in tissue due to the generation of singlet oxygen by substances like flavins or urocanic acid. Riboflavin, flavin mononucleotide (FMN), flavin adenine dinucleotide (FAD), β-nicotinamide adenine dinucleotide (NAD), and β-nicotinamide adenine dinucleotide phosphate (NADP), urocanic acid, or cholesterol in solution were excited at 355 nm. Singlet oxygen was directly detected by time-resolved measurement of its luminescence at 1270 nm. NAD, NADP, and cholesterol showed no luminescence signal possibly due to the very low absorption coefficient at 355 nm. Singlet oxygen luminescence of urocanic acid was clearly detected but the signal was too weak to quantify a quantum yield. The quantum yield of singlet oxygen was precisely determined for riboflavin (ΦΔ = 0.54 ± 0.07), FMN (ΦΔ = 0.51 ± 0.07), and FAD (ΦΔ = 0.07 ± 0.02). In aerated solution, riboflavin and FMN generate more singlet oxygen than exogenous photosensitizers such as Photofrin, which are applied in photodynamic therapy to kill cancer cells. With decreasing oxygen concentration, the quantum yield of singlet oxygen generation decreased, which must be considered when assessing the role of singlet oxygen at low oxygen concentrations (inside tissue). PMID:16751234

Phosphorescent binuclear iridium complexes based on terpyridine-carboxylate: an experimental and theoretical study.

PubMed

Andreiadis, Eugen S; Imbert, Daniel; Pécaut, Jacques; Calborean, Adrian; Ciofini, Ilaria; Adamo, Carlo; Demadrille, Renaud; Mazzanti, Marinella

2011-09-05

The phosphorescent binuclear iridium(III) complexes tetrakis(2-phenylpyridine)μ-(2,2':6',2''-terpyridine-6,6''-dicarboxylic acid)diiridium (Ir1) and tetrakis(2-(2,4-difluorophenyl) pyridine))μ-(2,2':6',2''-terpyridine-6,6''-dicarboxylic acid)diiridium (Ir2) were synthesized in a straightforward manner and characterized using X-ray diffraction, NMR, UV-vis absorption, and emission spectroscopy. The complexes have similar solution structures in which the two iridium centers are equivalent. This is further confirmed by the solid state structure of Ir2. The newly reported complexes display intense luminescence in dichloromethane solutions with maxima at 538 (Ir1) and 477 nm (Ir2) at 298 K (496 and 468 nm at 77 K, respectively) and emission quantum yields reaching ~18% for Ir1. The emission quantum yield for Ir1 is among the highest values reported for dinuclear iridium complexes. It shows only a 11% decrease with respect to the emission quantum yield reported for its mononuclear analogue, while the molar extinction coefficient is roughly doubled. This suggests that such architectures are of potential interest for the development of polymetallic assemblies showing improved optical properties. DFT and time-dependent-DFT calculations were performed on the ground and excited states of the complexes to provide insights into their structural, electronic, and photophysical properties.

Single-photon absorption by single photosynthetic light-harvesting complexes

NASA Astrophysics Data System (ADS)

Chan, Herman C. H.; Gamel, Omar E.; Fleming, Graham R.; Whaley, K. Birgitta

2018-03-01

We provide a unified theoretical approach to the quantum dynamics of absorption of single photons and subsequent excitonic energy transfer in photosynthetic light-harvesting complexes. Our analysis combines a continuous mode < n > -photon quantum optical master equation for the chromophoric system with the hierarchy of equations of motion describing excitonic dynamics in presence of non-Markovian coupling to vibrations of the chromophores and surrounding protein. We apply the approach to simulation of absorption of single-photon coherent states by pigment-protein complexes containing between one and seven chromophores, and compare with results obtained by excitation using a thermal radiation field. We show that the values of excitation probability obtained under single-photon absorption conditions can be consistently related to bulk absorption cross-sections. Analysis of the timescale and efficiency of single-photon absorption by light-harvesting systems within this full quantum description of pigment-protein dynamics coupled to a quantum radiation field reveals a non-trivial dependence of the excitation probability and the excited state dynamics induced by exciton-phonon coupling during and subsequent to the pulse, on the bandwidth of the incident photon pulse. For bandwidths equal to the spectral bandwidth of Chlorophyll a, our results yield an estimation of an average time of ˜0.09 s for a single chlorophyll chromophore to absorb the energy equivalent of one (single-polarization) photon under irradiation by single-photon states at the intensity of sunlight.

Large-scale progenitor cell expansion for multiple donors in a monitored hollow fibre bioreactor.

PubMed

Lambrechts, Toon; Papantoniou, Ioannis; Rice, Brent; Schrooten, Jan; Luyten, Frank P; Aerts, Jean-Marie

2016-09-01

With the increasing scale in stem cell production, a robust and controlled cell expansion process becomes essential for the clinical application of cell-based therapies. The objective of this work was the assessment of a hollow fiber bioreactor (Quantum Cell Expansion System from Terumo BCT) as a cell production unit for the clinical-scale production of human periosteum derived stem cells (hPDCs). We aimed to demonstrate comparability of bioreactor production to standard culture flask production based on a product characterization in line with the International Society of Cell Therapy in vitro benchmarks and supplemented with a compelling quantitative in vivo bone-forming potency assay. Multiple process read-outs were implemented to track process performance and deal with donor-to-donor-related variation in nutrient needs and harvest timing. The data show that the hollow fiber bioreactor is capable of robustly expanding autologous hPDCs on a clinical scale (yield between 316 million and 444 million cells starting from 20 million after ± 8 days of culture) while maintaining their in vitro quality attributes compared with the standard flask-based culture. The in vivo bone-forming assay on average resulted in 10.3 ± 3.7% and 11.0 ± 3.8% newly formed bone for the bioreactor and standard culture flask respectively. The analysis showed that the Quantum system provides a reproducible cell expansion process in terms of yields and culture conditions for multiple donors. Copyright © 2016 International Society for Cellular Therapy. Published by Elsevier Inc. All rights reserved.

Porous Silicon Nanoparticle Photosensitizers for Singlet Oxygen and Their Phototoxicity Against Cancer Cells

PubMed Central

Xiao, Ling; Gu, Luo; Howell, Stephen B.; Sailor, Michael J.

2011-01-01

Porous Si nanoparticles, prepared from electrochemically etched single crystal Si wafers, function as photosensitizers to generate 1O2 in ethanol and in aqueous media. The preparation conditions for the porous Si nanoparticles were optimized to maximize (1) the yield of material; (2) its quantum yield of 1O2 production; and (3) its in vitro degradation properties. The optimal formulation was determined to consist of nanoparticles 146 ± 7 nm in diameter, with nominal pore sizes of 12 ± 4 nm. The quantum yield for 1O2 production is 0.10 ± 0.02 in ethanol and 0.17 ± 0.01 in H2O. HeLa or NIH-3T3 cells treated with 100 µg/mL porous Si nanoparticles and exposed to 60 J/cm2 white light (infrared filtered, 100 mW/cm2 for 10 min) exhibit ~ 45% cell death, while controls containing no nanoparticles show 10% or 25% cell death, respectively. The dark control experiment yields < 10% cytotoxicity for either cell type. PMID:21452822

Tapping the potential of trioctylphosphine (TOP) in the realization of highly luminescent blue-emitting colloidal indium phosphide (InP) quantum dots

NASA Astrophysics Data System (ADS)

Singh, Akanksha; Chawla, Parul; Jain, Shefali; Sharma, Shailesh Narain

2017-06-01

In this work, extremely small blue emitting colloidal InP-based quantum dots (size 2-5 nm) have been synthesized using trioctylphosphine (TOP) as a source of phosphorus. The method reported here is unconventional, quite rapid ( 90 min), more viable, less expensive and relatively greener as compared to other conventional methods that employ tristrimethylsilyylphosphine(P(SiMe3)3) which is scarce, expensive, flammable, highly toxic and even banned in a few countries. Highly luminescent InP QDs having bluish-green emission (λ 490 nm) can be synthesized using this method without resorting to any post-synthesis etching to tune the emission to the blue region. Besides being the source of phosphorus and the particle size regulating agent, the efficacy of TOP is further realized during synthesis via its reduction of indium salt, which aids in the formation of indium metal and then subsequently in the development of InP QDs. The PL intensity of as-synthesized InP QDs is further enhanced by growing a shell of wide band gap material, i.e. ZnS resulting in a concurrent increment in quantum yield from 25% to 38% respectively.

On-demand generation of background-free single photons from a solid-state source

NASA Astrophysics Data System (ADS)

Schweickert, Lucas; Jöns, Klaus D.; Zeuner, Katharina D.; Covre da Silva, Saimon Filipe; Huang, Huiying; Lettner, Thomas; Reindl, Marcus; Zichi, Julien; Trotta, Rinaldo; Rastelli, Armando; Zwiller, Val

2018-02-01

True on-demand high-repetition-rate single-photon sources are highly sought after for quantum information processing applications. However, any coherently driven two-level quantum system suffers from a finite re-excitation probability under pulsed excitation, causing undesirable multi-photon emission. Here, we present a solid-state source of on-demand single photons yielding a raw second-order coherence of g(2 )(0 )=(7.5 ±1.6 )×10-5 without any background subtraction or data processing. To this date, this is the lowest value of g(2 )(0 ) reported for any single-photon source even compared to the previously reported best background subtracted values. We achieve this result on GaAs/AlGaAs quantum dots embedded in a low-Q planar cavity by employing (i) a two-photon excitation process and (ii) a filtering and detection setup featuring two superconducting single-photon detectors with ultralow dark-count rates of (0.0056 ±0.0007 ) s-1 and (0.017 ±0.001 ) s-1, respectively. Re-excitation processes are dramatically suppressed by (i), while (ii) removes false coincidences resulting in a negligibly low noise floor.

Quantum noise spectra for periodically driven cavity optomechanics

NASA Astrophysics Data System (ADS)

Aranas, E. B.; Akram, M. Javed; Malz, Daniel; Monteiro, T. S.

2017-12-01

A growing number of experimental setups in cavity optomechanics exploit periodically driven fields. However, such setups are not amenable to analysis by using simple, yet powerful, closed-form expressions of linearized optomechanics, which have provided so much of our present understanding of experimental optomechanics. In the present paper, we formulate a method to calculate quantum noise spectra in modulated optomechanical systems, which we analyze, compare, and discuss with two other recently proposed solutions: we term these (i) frequency-shifted operators, (ii) Floquet [Phys. Rev. A 94, 023803 (2016), 10.1103/PhysRevA.94.023803], and (iii) iterative analysis [New J. Phys. 18, 113021 (2016), 10.1088/1367-2630/18/11/113021]. We prove that (i) and (ii) yield equivalent noise spectra and find that (iii) is an analytical approximation to (i) for weak modulations. We calculate the noise spectra of a doubly modulated system describing experiments of levitated particles in hybrid electro-optical traps. We show excellent agreement with Langevin stochastic simulations in the thermal regime and predict squeezing in the quantum regime. Finally, we reveal how otherwise-inaccessible spectral components of a modulated system can be measured in heterodyne detection through an appropriate choice of modulation frequencies.

Synthesis of blue emitting InP/ZnS quantum dots through control of competition between etching and growth.

PubMed

Lim, Kipil; Jang, Ho Seong; Woo, Kyoungja

2012-12-07

Blue (<480 nm) emitting Cd-free quantum dots (QDs) are in great demand for various applications. However, their synthesis has been challenging. Here we present blue emitting InP/ZnS core/shell QDs with a band edge emission of 475 nm and a full width at half maximum of 39 nm (215 meV) from their quantum confined states. The drastic temperature drop immediately after mixing of the precursors and holding them at a temperature below 150 °C was the critical factor for the synthesis of blue emitting QDs, because the blue QDs are formed by the etching of ultra-small InP cores by residual acetic acid below 150 °C. Etching was dominant at temperatures below 150 °C, whereas growth was dominant at temperatures above 150 °C. ZnS shells were formed successfully at 150 °C, yielding blue emitting InP/ZnS QDs. The colour of the InP/ZnS QDs depicted on the CIE 1931 chromaticity diagram is located close to the edge, indicating a pure blue colour compared to other InP-based QDs.

Synthesis of blue emitting InP/ZnS quantum dots through control of competition between etching and growth

NASA Astrophysics Data System (ADS)

Lim, Kipil; Jang, Ho Seong; Woo, Kyoungja

2012-12-01

Blue (<480 nm) emitting Cd-free quantum dots (QDs) are in great demand for various applications. However, their synthesis has been challenging. Here we present blue emitting InP/ZnS core/shell QDs with a band edge emission of 475 nm and a full width at half maximum of 39 nm (215 meV) from their quantum confined states. The drastic temperature drop immediately after mixing of the precursors and holding them at a temperature below 150 °C was the critical factor for the synthesis of blue emitting QDs, because the blue QDs are formed by the etching of ultra-small InP cores by residual acetic acid below 150 °C. Etching was dominant at temperatures below 150 °C, whereas growth was dominant at temperatures above 150 °C. ZnS shells were formed successfully at 150 °C, yielding blue emitting InP/ZnS QDs. The colour of the InP/ZnS QDs depicted on the CIE 1931 chromaticity diagram is located close to the edge, indicating a pure blue colour compared to other InP-based QDs.

Tomographic imaging of flourescence resonance energy transfer in highly light scattering media

NASA Astrophysics Data System (ADS)

Soloviev, Vadim Y.; McGinty, James; Tahir, Khadija B.; Laine, Romain; Stuckey, Daniel W.; Mohan, P. Surya; Hajnal, Joseph V.; Sardini, Alessandro; French, Paul M. W.; Arridge, Simon R.

2010-02-01

Three-dimensional localization of protein conformation changes in turbid media using Förster Resonance Energy Transfer (FRET) was investigated by tomographic fluorescence lifetime imaging (FLIM). FRET occurs when a donor fluorophore, initially in its electronic excited state, transfers energy to an acceptor fluorophore in close proximity through non-radiative dipole-dipole coupling. An acceptor effectively behaves as a quencher of the donor's fluorescence. The quenching process is accompanied by a reduction in the quantum yield and lifetime of the donor fluorophore. Therefore, FRET can be localized by imaging changes in the quantum yield and the fluorescence lifetime of the donor fluorophore. Extending FRET to diffuse optical tomography has potentially important applications such as in vivo studies in small animal. We show that FRET can be localized by reconstructing the quantum yield and lifetime distribution from time-resolved non-invasive boundary measurements of fluorescence and transmitted excitation radiation. Image reconstruction was obtained by an inverse scattering algorithm. Thus we report, to the best of our knowledge, the first tomographic FLIM-FRET imaging in turbid media. The approach is demonstrated by imaging a highly scattering cylindrical phantom concealing two thin wells containing cytosol preparations of HEK293 cells expressing TN-L15, a cytosolic genetically-encoded calcium FRET sensor. A 10mM calcium chloride solution was added to one of the wells to induce a protein conformation change upon binding to TN-L15, resulting in FRET and a corresponding decrease in the donor fluorescence lifetime. The resulting fluorescence lifetime distribution, the quantum efficiency, absorption and scattering coefficients were reconstructed.