Synthesis and Exciton Dynamics of Triplet Sensitized Conjugated Polymers.

PubMed

Andernach, Rolf; Utzat, Hendrik; Dimitrov, Stoichko D; McCulloch, Iain; Heeney, Martin; Durrant, James R; Bronstein, Hugo

2015-08-19

We report the synthesis of a novel polythiophene-based host-guest copolymer incorporating a Pt-porphyrin complex (TTP-Pt) into the backbone for efficient singlet to triplet polymer exciton sensitization. We elucidated the exciton dynamics in thin films of the material by means of Transient Absorption Spectrosopcy (TAS) on multiple time scales and investigated the mechanism of triplet exciton formation. During sensitization, singlet exciton diffusion is followed by exciton transfer from the polymer backbone to the complex where it undergoes intersystem crossing to the triplet state of the complex. We directly monitored the triplet exciton back transfer from the Pt-porphyrin to the polymer and found that 60% of the complex triplet excitons were transferred with a time constant of 1087 ps. We propose an equilibrium between polymer and porphyrin triplet states as a result of the low triplet diffusion length in the polymer backbone and hence an increased local triplet population resulting in increased triplet-triplet annihilation. This novel system has significant implications for the design of novel materials for triplet sensitized solar cells and upconversion layers.

Fast and long-range triplet exciton diffusion in metal-organic frameworks for photon upconversion at ultralow excitation power.

PubMed

Mahato, Prasenjit; Monguzzi, Angelo; Yanai, Nobuhiro; Yamada, Teppei; Kimizuka, Nobuo

2015-09-01

The conversion of low-energy light into photons of higher energy based on sensitized triplet-triplet annihilation upconversion (TTA-UC) has emerged as a promising wavelength-shifting methodology because it permits UC at excitation powers as low as the solar irradiance. However, its application has been significantly hampered by the slow diffusion of excited molecules in solid matrices. Here, we introduce metal-organic frameworks (MOFs) that promote TTA-UC by taking advantage of triplet exciton migration among fluorophores that are regularly aligned with spatially controlled chromophore orientations. We synthesized anthracene-containing MOFs with different molecular orientations, and the analysis of TTA-UC emission kinetics unveiled a high triplet diffusion rate with a micrometre-scale diffusion length. Surface modification of MOF nanocrystals with donor molecules and their encapsulation in glassy poly(methyl methacrylate) (PMMA) allowed the construction of molecular-diffusion-free solid-state upconverters, which lead to an unprecedented maximization of overall UC quantum yield at excitation powers comparable to or well below the solar irradiance.

Development of Phase-Stable Photon Upconverters for Efficient Solar Energy Utilization

NASA Astrophysics Data System (ADS)

Murakami, Yoichi

Photon upconversion based on triplet-triplet annihilation (TTA) of excited triplet molecules is drawing attention due to its applicability for weak incident light, possessing a potential for improving efficiencies of solar energy conversion devices. Since energy transfer between triplet levels of different molecules and TTA are based on the Dexter mechanism, inter-molecular collision is necessary and hence the majority of previous studies have been done with organic solvents, which are volatile and flammable. This paper presents the development and characterization of phase-stable photon upconverters fabricated with ionic liquids, which are room temperature molten salts with negligible vapor pressure and high thermal stability. The employed aromatic molecules, which are carrier of photo-created energies and are non-polar (or weakly polar) molecules, are found to be stable in the polar environment of ionic liquids, contrary to expectation. The mechanism of the stable solvation is proposed. The upconversion quantum yields are found to rapidly saturate as the excitation light power increases. An analytical model was developed and compared with the experimental data. It is shown that ionic liquids are not viscous media for the purpose of TTA-based upconversion.

Methods and compositions for the upconversion of light

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

Baldo, Marc A.; Congreve, Daniel N.; Thompson, Nicholas John

The present invention generally relates to composition and methods for upconverting light. In some embodiments, the composition and methods comprise an organic material, a nanocrystal, and a ligand capable of facilitating energy transfer between the nanocrystal and the organic material. In certain embodiments, the nanocrystal has a first excited energy state with an energy greater than a triplet state of the organic material. The organic material, in some embodiments, may be aromatic and/or include one or more pi-conjugated carbon-carbon double bonds. In some cases, incident light may be absorbed by the nanocrystal to produce triplet excitons. The triplet excitons maymore » then transfer from the nanocrystal to the organic material and undergo triplet-triplet annihilation, creating a singlet state of approximately twice the energy of the triplet exciton. In certain embodiments, the singlet state fluoresces, resulting in the formation of a high energy photon.« less

Dual enhancement of electroluminescence efficiency and operational stability by rapid upconversion of triplet excitons in OLEDs

PubMed Central

Furukawa, Taro; Nakanotani, Hajime; Inoue, Munetomo; Adachi, Chihaya

2015-01-01

Recently, triplet harvesting via a thermally activated delayed fluorescence (TADF) process has been established as a realistic route for obtaining ultimate internal electroluminescence (EL) quantum efficiency in organic light-emitting diodes (OLEDs). However, the possibility that the rather long transient lifetime of the triplet excited states would reduce operational stability due to an increased chance for unwarranted chemical reactions has been a concern. Herein, we demonstrate dual enhancement of EL efficiency and operational stability in OLEDs by employing a TADF molecule as an assistant dopant and a fluorescent molecule as an end emitter. The proper combination of assistant dopant and emitter molecules realized a “one-way” rapid Förster energy transfer of singlet excitons from TADF molecules to fluorescent emitters, reducing the number of cycles of intersystem crossing (ISC) and reverse ISC in the TADF molecules and resulting in a significant enhancement of operational stability compared to OLEDs with a TADF molecule as the end emitter. In addition, we found that the presence of this rapid energy transfer significantly suppresses singlet-triplet annihilation. Using this finely-tuned rapid triplet-exciton upconversion scheme, OLED performance and lifetime was greatly improved. PMID:25673259

Long-lived room temperature deep-red/near-IR emissive intraligand triplet excited state (3IL) of naphthalimide in cyclometalated platinum(II) complexes and its application in upconversion.

PubMed

Wu, Wenting; Guo, Huimin; Wu, Wanhua; Ji, Shaomin; Zhao, Jianzhang

2011-11-21

[C(^)NPt(acac)] (C(^)N = cyclometalating ligand; acac = acetylacetonato) complexes in which the naphthalimide (NI) moiety is directly cyclometalated (NI as the C donor of the C-Pt bond) were synthesized. With 4-pyrazolylnaphthalimide, isomers with five-membered (Pt-2) and six-membered (Pt-3) chelate rings were obtained. With 4-pyridinylnaphthalimide, only the complex with a five-membered chelate ring (Pt-4) was isolated. A model complex with 1-phenylpyrazole as the C(^)N ligand was prepared (Pt-1). Strong absorption of visible light (ε = 21,900 M(-1) cm(-1) at 443 nm for Pt-3) and room temperature (RT) phosphorescence at 630 nm (Pt-2 and Pt-3) or 674 nm (Pt-4) were observed. Long-lived phosphorescences were observed for Pt-2 (τ(P) = 12.8 μs) and Pt-3 (τ(P) = 61.9 μs). Pt-1 is nonphosphorescent at RT in solution because of the acac-localized T(1) excited state [based on density functional theory (DFT) calculations and spin density analysis], but a structured emission band centered at 415 nm was observed at 77 K. Time-resolved transient absorption spectra and spin density analysis indicated a NI-localized intraligand triplet excited state ((3)IL) for complexes Pt-2, Pt-3, and Pt-4. DFT calculations on the transient absorption spectra (T(1) → T(n) transitions, n > 1) also support the (3)IL assignment of the T(1) excited states of Pt-2, Pt-3, and Pt-4. The complexes were used as triplet sensitizers for triplet-triplet-annihilation (TTA) based upconversion, and the results show that Pt-3 is an efficient sensitizer with an upconversion quantum yield of up to 14.1%, despite its low phosphorescence quantum yield of 5.2%. Thus, we propose that the sensitizer molecules at the triplet excited state that are otherwise nonphosphorescent were involved in the TTA upconversion process, indicating that weakly phosphorescent or nonphosphorescent transition-metal complexes can be used as triplet sensitizers for TTA upconversion.

The triplet excited state of Bodipy: formation, modulation and application.

PubMed

Zhao, Jianzhang; Xu, Kejing; Yang, Wenbo; Wang, Zhijia; Zhong, Fangfang

2015-12-21

Boron dipyrromethene (Bodipy) is one of the most extensively investigated organic chromophores. Most of the investigations are focused on the singlet excited state of Bodipy, such as fluorescence. In stark contrast, the study of the triplet excited state of Bodipy is limited, but it is an emerging area, since the triplet state of Bodipy is tremendously important for several areas, such as the fundamental photochemistry study, photodynamic therapy (PDT), photocatalysis and triplet-triplet annihilation (TTA) upconversion. The recent developments in the study of the production, modulation and application of the triplet excited state of Bodipy are discussed in this review article. The formation of the triplet state of Bodipy upon photoexcitation, via the well known approach such as the heavy atom effect (including I, Br, Ru, Ir, etc.), and the new methods, such as using a spin converter (e.g. C60), charge recombination, exciton coupling and the doubly substituted excited state, are summarized. All the Bodipy-based triplet photosensitizers show strong absorption of visible or near IR light and the long-lived triplet excited state, which are important for the application of the triplet excited state in PDT or photocatalysis. Moreover, the methods for switching (or modulation) of the triplet excited state of Bodipy were discussed, such as those based on the photo-induced electron transfer (PET), by controlling the competing Förster-resonance-energy-transfer (FRET), or the intermolecular charge transfer (ICT). Controlling the triplet excited state will give functional molecules such as activatable PDT reagents or molecular devices. It is worth noting that switching of the singlet excited state and the triplet state of Bodipy may follow different principles. Application of the triplet excited state of Bodipy in PDT, hydrogen (H2) production, photoredox catalytic organic reactions and TTA upconversion were discussed. The challenges and the opportunities in these areas were briefly discussed.

Ionic liquid dependence of triplet-sensitized photon upconversion.

PubMed

Murakami, Yoichi; Ito, Toshiyuki; Kawai, Akio

2014-12-11

Photon upconversion (UC) is a technology used to convert wasted lower energy photons to usable higher energy photons. Triplet-sensitized UC based on the triplet-triplet annihilation (TTA) of organic molecules has recently received attention because of its applicability to noncoherent sunlight. Among the various media proposed for this UC, ionic liquids (ILs) are practically advantageous because of their nonvolatility and nonflammability. However, from previous studies, the efficiency of UC (ΦUC) has been found to depend on the ILs employed. In this article, systematic investigations were carried out on samples made using more than 10 kinds of ILs, all of which were purified before sample fabrication to enhance data reliability. Several clear tendencies were found, and they were all related to the viscosity of the ILs. We also found that the magnitude of their solvatochromic shifts did not correlate to these trends. These results show that the dynamic aspects of the molecules influence the kinetics that govern the magnitude of ΦUC. Along with related discussions and interpretations, these results should provide a guideline toward increasing the ΦUC.

Solid-state infrared-to-visible upconversion sensitized by colloidal nanocrystals

NASA Astrophysics Data System (ADS)

Wu, Mengfei; Congreve, Daniel N.; Wilson, Mark W. B.; Jean, Joel; Geva, Nadav; Welborn, Matthew; van Voorhis, Troy; Bulović, Vladimir; Bawendi, Moungi G.; Baldo, Marc A.

2016-01-01

Optical upconversion via sensitized triplet-triplet exciton annihilation converts incoherent low-energy photons to shorter wavelengths under modest excitation intensities. Here, we report a solid-state thin film for infrared-to-visible upconversion that employs lead sulphide colloidal nanocrystals as a sensitizer. Upconversion is achieved from pump wavelengths beyond λ = 1 μm to emission at λ = 612 nm. When excited at λ = 808 nm, two excitons in the sensitizer are converted to one higher-energy state in the emitter at a yield of 1.2 ± 0.2%. Peak efficiency is attained at an absorbed intensity equivalent to less than one sun. We demonstrate that colloidal nanocrystals are an attractive alternative to existing molecular sensitizers, given their small exchange splitting, wide wavelength tunability, broadband infrared absorption, and our transient observations of efficient energy transfer. This solid-state architecture for upconversion may prove useful for enhancing the capabilities of solar cells and photodetectors.

Near-Infrared-to-Visible Photon Upconversion Enabled by Conjugated Porphyrinic Sensitizers under Low-Power Noncoherent Illumination.

PubMed

Olivier, Jean-Hubert; Bai, Yusong; Uh, Hyounsoo; Yoo, Hyejin; Therien, Michael J; Castellano, Felix N

2015-06-04

We report four supermolecular chromophores based on (porphinato)zinc(II) (PZn) and (polypyridyl)metal units bridged via ethyne connectivity (Pyr1RuPZn2, Pyr1RuPZnRuPyr1, Pyr1RuPZn2RuPyr1, and OsPZn2Os) that fulfill critical sensitizer requirements for NIR-to-vis triplet-triplet annihilation upconversion (TTA-UC) photochemistry. These NIR sensitizers feature: (i) broad, high oscillator strength NIR absorptivity (700 nm < λ(max(NIR)) < 770 nm; 6 × 10(4) M(-1) cm(-1) < extinction coefficient (λ(max(NIR))) < 1.6 × 10(5) M(-1) cm(-1); 820 cm(-1) < fwhm < 1700 cm(-1)); (ii) substantial intersystem crossing quantum yields; (iii) long, microsecond time scale T1 state lifetimes; and (iv) triplet states that are energetically poised for exergonic energy transfer to the molecular annihilator (rubrene). Using low-power noncoherent illumination at power densities (1-10 mW cm(-2)) similar to that of terrestrial solar photon illumination conditions, we demonstrate that Pyr1RuPZn2, Pyr1RuPZn2RuPyr1, and Pyr1RuPZnRuPyr1 sensitizers can be used in combination with the rubrene acceptor/annihilator to achieve TTA-UC: these studies represent the first examples whereby a low-power noncoherent NIR light source drives NIR-to-visible upconverted fluorescence centered in a spectral window within the bandgap of amorphous silicon.

The Role of Triplet Exciton Diffusion in Light-Upconverting Polymer Glasses.

PubMed

Raišys, Steponas; Kazlauskas, Karolis; Juršėnas, Saulius; Simon, Yoan C

2016-06-22

Light upconversion (UC) via triplet-triplet annihilation (TTA) by using noncoherent photoexcitation at subsolar irradiance power densities is extremely attractive, particularly for enhanced solar energy harvesting. Unfortunately, practical TTA-UC application is hampered by low UC efficiency of upconverting polymer glasses, which is commonly attributed to poor exciton diffusion of the triplet excitons across emitter molecules. The present study addresses this issue by systematically evaluating triplet exciton diffusion coefficients and diffusion lengths (LD) in a UC model system based on platinum-octaethylporphyrin-sensitized poly(methyl methacrylate)/diphenylanthracene (emitter) films as a function of emitter concentration (15-40 wt %). For this evaluation time-resolved photoluminescence bulk-quenching technique followed by Stern-Volmer-type quenching analysis of experimental data was employed. The key finding is that although increasing emitter concentration in the disordered PMMA/DPA/PtOEP films improves triplet exciton diffusion, and thus LD, this does not result in enhanced UC quantum yield. Conversely, improved LD accompanied by the accelerated decay of UC intensity on millisecond time scale degrades TTA-UC performance at high emitter loadings (>25 wt %) and suggests that diffusion-enhanced nonradiative decay of triplet excitons is the major limiting factor.

Photon Upconversion and Molecular Solar Energy Storage by Maximizing the Potential of Molecular Self-Assembly.

PubMed

Kimizuka, Nobuo; Yanai, Nobuhiro; Morikawa, Masa-Aki

2016-11-29

The self-assembly of functional molecules into ordered molecular assemblies and the fulfillment of potentials unique to their nanotomesoscopic structures have been one of the central challenges in chemistry. This Feature Article provides an overview of recent progress in the field of molecular self-assembly with the focus on the triplet-triplet annihilation-based photon upconversion (TTA-UC) and supramolecular storage of photon energy. On the basis of the integration of molecular self-assembly and photon energy harvesting, triplet energy migration-based TTA-UC has been achieved in varied molecular systems. Interestingly, some molecular self-assemblies dispersed in solution or organogels revealed oxygen barrier properties, which allowed TTA-UC even under aerated conditions. The elements of molecular self-assembly were also introduced to the field of molecular solar thermal fuel, where reversible photoliquefaction of ionic crystals to ionic liquids was found to double the molecular storage capacity with the simultaneous pursuit of switching ionic conductivity. A future prospect in terms of innovating molecular self-assembly toward molecular systems chemistry is also discussed.

Amplified Photon Upconversion by Photonic Shell of Cholesteric Liquid Crystals.

PubMed

Kang, Ji-Hwan; Kim, Shin-Hyun; Fernandez-Nieves, Alberto; Reichmanis, Elsa

2017-04-26

As an effective platform to exploit triplet-triplet-annihilation-based photon upconversion (TTA-UC), microcapsules composed of a fluidic UC core and photonic shell are microfluidically prepared using a triple emulsion as the template. The photonic shell consists of cholesteric liquid crystals (CLCs) with a periodic helical structure, exhibiting a photonic band gap. Combined with planar anchoring at the boundaries, the shell serves as a resonance cavity for TTA-UC emission and enables spectral tuning of the UC under low-power-density excitation. The CLC shell can be stabilized by introducing a polymerizable mesogen in the LC host. Because of the microcapsule spherical symmetry, spontaneous emission of the delayed fluorescence is omnidirectionally amplified at the edge of the stop band. These results demonstrate the range of opportunities provided by TTA-UC systems for the future design of low-threshold photonic devices.

Photocatalytic Water-Splitting Enhancement by Sub-Bandgap Photon Harvesting.

PubMed

Monguzzi, Angelo; Oertel, Amadeus; Braga, Daniele; Riedinger, Andreas; Kim, David K; Knüsel, Philippe N; Bianchi, Alberto; Mauri, Michele; Simonutti, Roberto; Norris, David J; Meinardi, Francesco

2017-11-22

Upconversion is a photon-management process especially suited to water-splitting cells that exploit wide-bandgap photocatalysts. Currently, such catalysts cannot utilize 95% of the available solar photons. We demonstrate here that the energy-conversion yield for a standard photocatalytic water-splitting device can be enhanced under solar irradiance by using a low-power upconversion system that recovers part of the unutilized incident sub-bandgap photons. The upconverter is based on a sensitized triplet-triplet annihilation mechanism (sTTA-UC) obtained in a dye-doped elastomer and boosted by a fluorescent nanocrystal/polymer composite that allows for broadband light harvesting. The complementary and tailored optical properties of these materials enable efficient upconversion at subsolar irradiance, allowing the realization of the first prototype water-splitting cell assisted by solid-state upconversion. In our proof-of concept device the increase of the performance is 3.5%, which grows to 6.3% if concentrated sunlight (10 sun) is used. Our experiments show how the sTTA-UC materials can be successfully implemented in technologically relevant devices while matching the strict requirements of clean-energy production.

New anthracene derivatives as triplet acceptors for efficient green-to-blue low-power upconversion.

PubMed

Liang, Zuo-Qin; Sun, Bin; Ye, Chang-Qing; Wang, Xiao-Mei; Tao, Xu-Tang; Wang, Qin-Hua; Ding, Ping; Wang, Bao; Wang, Jing-Jing

2013-10-21

Three new anthracene derivatives [2-chloro-9,10-dip-tolylanthracene (DTACl), 9,10-dip-tolylanthracene-2-carbonitrile (DTACN), and 9,10-di(naphthalen-1-yl)anthracene-2-carbonitrile (DNACN)] were synthesized as triplet acceptors for low-power upconversion. Their linear absorption, single-photon-excited fluorescence, and upconversion fluorescence properties were studied. The acceptors exhibit high fluorescence yields in DMF. Selective excitation of the sensitizer Pd(II)octaethylporphyrin (PdOEP) in solution containing DTACl, DTACN, or DNA-CN at 532 nm with an ultralow excitation power density of 0.5 W cm(-2) results in anti-Stokes blue emission. The maximum upconversion quantum yield (Φ(UC) =17.4%) was obtained for the couple PdOEP/DTACl. In addition, the efficiency of the triplet-triplet energy transfer process was quantitatively studied by quenching experiments. Experimental results revealed that a highly effective acceptor for upconversion should combine high fluorescence quantum yields with efficient quenching of the sensitizer triplet. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Triplet-sensitized photon upconversion in deep eutectic solvents.

PubMed

Murakami, Yoichi; Das, Sudhir Kumar; Himuro, Yuki; Maeda, Satoshi

2017-11-22

Photon upconversion (UC) is a technology that can increase solar utilization efficiencies in broad photoenergy conversion systems by converting lower-energy photons into usable higher-energy photons. Recently, UC using triplet-triplet annihilation (TTA) of organic molecules has drawn attention because it is presently the only method applicable to weak and noncoherent light. To date, many attempts have been made to realize this UC technology in forms suitable for applications, but they typically suffer from either high cost or insufficient stability and/or safety of materials. Recently, a new class of liquid called deep eutectic solvents (DESs) has emerged as low-cost green fluids that possess low toxicity and vapor pressure, biodegradability, and high thermal stability. DESs have been proposed as an alternative to ionic liquids. This article develops triplet-sensitized UC samples using DESs that are found to be suitable solvents for this purpose, attaining a new materials platform for UC with the aforementioned advantages. The high thermal stability of the samples is qualitatively confirmed and their UC quantum yields are determined to be 0.11-0.21 (based on the definition that the maximum quantum yield is 0.5) depending on the DES composition. The triplet lifetime of the emitter 9,10-diphenylanthracene increases with DES viscosity, resulting in unique kinetics. Analysis of photophysical experimental results allows the relevant physics governing the performance of this sample system to be determined and discussed. Overall, a novel UC platform that simultaneously achieves high thermal stability, low cost, and environmental friendliness is developed using DESs as the solvent.

Bodipy-C60 triple hydrogen bonding assemblies as heavy atom-free triplet photosensitizers: preparation and study of the singlet/triplet energy transfer.

PubMed

Guo, Song; Xu, Liang; Xu, Kejing; Zhao, Jianzhang; Küçüköz, Betül; Karatay, Ahmet; Yaglioglu, Halime Gul; Hayvali, Mustafa; Elmali, Ayhan

2015-07-01

Supramolecular triplet photosensitizers based on hydrogen bonding-mediated molecular assemblies were prepared. Three thymine-containing visible light-harvesting Bodipy derivatives ( B-1 , B-2 and B-3 , which show absorption at 505 nm, 630 nm and 593 nm, respectively) were used as H-bonding modules, and 1,6-diaminopyridine-appended C 60 was used as the complementary hydrogen bonding module ( C-1 ), in which the C 60 part acts as a spin converter for triplet formation. Visible light-harvesting antennae with methylated thymine were prepared as references ( B-1-Me , B-2-Me and B-3-Me ), which are unable to form strong H-bonds with C-1 . Triple H-bonds are formed between each Bodipy antenna ( B-1 , B-2 and B-3 ) and the C 60 module ( C-1 ). The photophysical properties of the H-bonding assemblies and the reference non-hydrogen bond-forming mixtures were studied using steady state UV/vis absorption spectroscopy, fluorescence emission spectroscopy, electrochemical characterization, and nanosecond transient absorption spectroscopy. Singlet energy transfer from the Bodipy antenna to the C 60 module was confirmed by fluorescence quenching studies. The intersystem crossing of the latter produced the triplet excited state. The nanosecond transient absorption spectroscopy showed that the triplet state is either localized on the C 60 module (for assembly B-1·C-1 ), or on the styryl-Bodipy antenna (for assemblies B-2·C-1 and B-3·C-1 ). Intra-assembly forward-backward (ping-pong) singlet/triplet energy transfer was proposed. In contrast to the H-bonding assemblies, slow triplet energy transfer was observed for the non-hydrogen bonding mixtures. As a proof of concept, these supramolecular assemblies were used as triplet photosensitizers for triplet-triplet annihilation upconversion.

Theory of triplet-triplet annihilation in optically detected magnetic resonance

NASA Astrophysics Data System (ADS)

Keevers, T. L.; McCamey, D. R.

2016-01-01

Triplet-triplet annihilation allows two low-energy photons to be upconverted into a single high-energy photon. By essentially engineering the solar spectrum, this allows solar cells to be made more efficient and even exceed the Shockley-Quiesser limit. Unfortunately, optimizing the reaction pathway is difficult, especially with limited access to the microscopic time scales and states involved in the process. Optical measurements can provide detailed information: triplet-triplet annihilation is intrinsically spin dependent and exhibits substantial magnetoluminescence in the presence of a static magnetic field. Pulsed optically detected magnetic resonance is especially suitable, since it combines high spin sensitivity with coherent manipulation. In this paper, we develop a time-domain theory of triplet-triplet annihilation for complexes with arbitrary spin-spin coupling. We identify unique "Rabi fingerprints" for each coupling regime and show that this can be used to characterize the microscopic Hamiltonian.

Triplet diffusion leads to triplet-triplet annihilation in organic phosphorescent emitters

NASA Astrophysics Data System (ADS)

Zhang, Yifan; Forrest, Stephen R.

2013-12-01

In organic materials, triplet-triplet annihilation (TTA) can be dominated by triplet diffusion or triplet-to-triplet energy transfer. Here, we discuss the diffusion and transfer dominated mechanisms in the context of photoluminescence (PL) transient measurements from thin films of archetype phosphorescent organic light emitters based on Ir and Pt complexes. We find that TTA in these emitters is controlled by diffusion due to a Dexter-type exchange interaction, suggesting triplet radiative decay and TTA are independent processes. Minimizing the PL and absorption spectral overlap in phosphorescent emitters can lead to a significantly decreased TTA rate, and thus suppressed efficiency roll-off in phosphorescent organic light emitting diodes at high brightness.

New Triplet Sensitization Routes for Photon Upconversion: Thermally Activated Delayed Fluorescence Molecules, Inorganic Nanocrystals, and Singlet-to-Triplet Absorption.

PubMed

Yanai, Nobuhiro; Kimizuka, Nobuo

2017-10-17

Photon upconversion based on triplet-triplet annihilation (TTA-UC) has attracted much interest because of its possible applications to renewable energy production and biological fields. In particular, the UC of near-infrared (NIR) light to visible (vis) light is imperative to overcome the Shockley-Queisser limit of single-junction photovoltaic cells, and the efficiency of photocatalytic hydrogen production from water can also be improved with the aid of vis-to-ultraviolet (UV) UC. However, both processes have met limitations in the wavelength range, efficiency, and sensitivity for weak incident light. This Account describes recent breakthroughs that solve these major problems, new triplet sensitization routes to significantly enlarge the range of conversion wavelength by minimizing the energy loss during intersystem crossing (ISC) of triplet sensitizers or bypassing the ISC process. The photochemical processes of TTA-UC in general start with the absorption of longer wavelength incident light by triplet sensitizers, which generate the triplet states via ISC. This ISC inevitably accompanies the energy loss of hundreds of millielectronvolts, which significantly limits the TTA-UC with large anti-Stokes shifts. The small S 1 -T 1 gap of molecules showing thermally activated delayed fluorescence (TADF) allows the sensitization of emitters with the highest T 1 and S 1 energy levels ever employed in TTA-UC, which results in efficient vis-to-UV UC. As alternatives to molecular sensitizers in the NIR region, inorganic nanocrystals with broad NIR absorption bands have recently been shown to work as effective sensitizers for NIR-to-vis TTA-UC. Their small exchange splitting minimizes the energy loss during triplet sensitization. The modification of nanocrystal surfaces with organic acceptors via coordination bonds allows efficient energy transfer between the components and succeeding TTA processes. To remove restrictions on the energy loss during ISC, molecules with direct singlet-to-triplet (S-T) excitation are employed as triplet sensitizers. Although the S-T absorption is spin forbidden, large spin-orbital coupling occurs for appropriately designed metal complexes, which allow S-T absorption in the NIR region with large absorption coefficients. While the triplet lifetime of such S-T absorption sensitizers is often short (less than microsecond), the integration of the molecular sensitizers with emitter assemblies allows facile Dexter energy transfer to the surrounding emitter molecules, leading to efficient NIR-to-vis UC emission through triplet energy migration (TEM) in the condensed state. By judicious modification of the chromophore structures, the first example of NIR-to-blue UC has also been achieved. It is essential to combine these new triplet sensitization routes with an upconverted energy collection (UPCON) approach in molecular assemblies to effectively populate emitter triplets and to overcome remaining issues including back energy transfer. We propose two overall materials designs for the TEM-UPCON strategy, core-shell-shell structures and trilayer structures composed of triplet donor, acceptor, and energy collector. The fusion between triplet science and chemistry of self-assembly would overcome previous difficulties of NIR-to-vis and vis-to-UV TTA-UC toward real-world applications ranging from energy to biology.

Bodipy–C60 triple hydrogen bonding assemblies as heavy atom-free triplet photosensitizers: preparation and study of the singlet/triplet energy transfer† †Electronic supplementary information (ESI) available: Syntheses, structure characterization data, and UV/vis absorption and emission spectra. See DOI: 10.1039/c4sc03865g

PubMed Central

Guo, Song; Xu, Liang; Xu, Kejing; Küçüköz, Betül; Karatay, Ahmet; Yaglioglu, Halime Gul; Hayvali, Mustafa; Elmali, Ayhan

2015-01-01

Supramolecular triplet photosensitizers based on hydrogen bonding-mediated molecular assemblies were prepared. Three thymine-containing visible light-harvesting Bodipy derivatives (B-1, B-2 and B-3, which show absorption at 505 nm, 630 nm and 593 nm, respectively) were used as H-bonding modules, and 1,6-diaminopyridine-appended C60 was used as the complementary hydrogen bonding module (C-1), in which the C60 part acts as a spin converter for triplet formation. Visible light-harvesting antennae with methylated thymine were prepared as references (B-1-Me, B-2-Me and B-3-Me), which are unable to form strong H-bonds with C-1. Triple H-bonds are formed between each Bodipy antenna (B-1, B-2 and B-3) and the C60 module (C-1). The photophysical properties of the H-bonding assemblies and the reference non-hydrogen bond-forming mixtures were studied using steady state UV/vis absorption spectroscopy, fluorescence emission spectroscopy, electrochemical characterization, and nanosecond transient absorption spectroscopy. Singlet energy transfer from the Bodipy antenna to the C60 module was confirmed by fluorescence quenching studies. The intersystem crossing of the latter produced the triplet excited state. The nanosecond transient absorption spectroscopy showed that the triplet state is either localized on the C60 module (for assembly B-1·C-1), or on the styryl-Bodipy antenna (for assemblies B-2·C-1 and B-3·C-1). Intra-assembly forward–backward (ping-pong) singlet/triplet energy transfer was proposed. In contrast to the H-bonding assemblies, slow triplet energy transfer was observed for the non-hydrogen bonding mixtures. As a proof of concept, these supramolecular assemblies were used as triplet photosensitizers for triplet–triplet annihilation upconversion. PMID:29218142

Ionoluminescence properties of polystyrene-hosted fluorophore films induced by helium ions of energy 50-350 keV

NASA Astrophysics Data System (ADS)

Chakraborty, Subha; Huang, Mengbing

2017-10-01

We report on measurements and analysis of ionoluminescence properties of pure polystyrene films and polystyrene films doped with four types of fluorophores in low kinetic energies (50-350 keV) of ion irradiation. We have developed a theoretical model to understand the experimentally observed ionoluminescence behaviors in terms of scintillation yield from individual ion tracks, photophysical energy transfer mechanisms, and irradiation-induced defects. A comparison of the model and experimental results suggests that singlet up-conversion resulting from triplet-triplet annihilation processes may be responsible for enhanced singlet emission of the fluorophores at high ion beam flux densities. Energy transfer from the polystyrene matrix to the fluorophore molecules has been identified as an effective pathway to increasing the fluorescence efficiency in the doped scintillator films.

Absolute measurements of the triplet-triplet annihilation rate and the charge-carrier recombination layer thickness in working polymer light-emitting diodes based on polyspirobifluorene

NASA Astrophysics Data System (ADS)

Rothe, C.; Al Attar, H. A.; Monkman, A. P.

2005-10-01

The triplet exciton densities in electroluminescent devices prepared from two polyspirobifluorene derivatives have been investigated by means of time-resolved transient triplet absorption as a function of optical and electrical excitation power at 20 K. Because of the low mobility of the triplet excitons at this temperature, the triplet generation profile within the active polymer layer is preserved throughout the triplet lifetime and as a consequence the absolute triplet-triplet annihilation efficiency is not homogeneously distributed but depends on position within the active layer. This then gives a method to measure the charge-carrier recombination layer after electrical excitation relative to the light penetration depth, which is identical to the triplet generation layer after optical excitation. With the latter being obtained from ellipsometry, an absolute value of 5 nm is found for the exciton formation layer in polyspirobifluorene devices. This layer increases to 11 nm if the balance between the electron and the hole mobility is improved by chemically modifying the polymer backbone. Also, and consistent with previous work, triplet diffusion is dispersive at low temperature. As a consequence of this, the triplet-triplet annihilation rate is not a constant in the classical sense but depends on the triplet excitation dose. At 20 K and for typical excitation doses, absolute values of the latter rate are of the order of 10-14cm3s-1 .

Photon energy upconverting nanopaper: a bioinspired oxygen protection strategy.

PubMed

Svagan, Anna J; Busko, Dmitry; Avlasevich, Yuri; Glasser, Gunnar; Baluschev, Stanislav; Landfester, Katharina

2014-08-26

The development of solid materials which are able to upconvert optical radiation into photons of higher energy is attractive for many applications such as photocatalytic cells and photovoltaic devices. However, to fully exploit triplet-triplet annihilation photon energy upconversion (TTA-UC), oxygen protection is imperative because molecular oxygen is an ultimate quencher of the photon upconversion process. So far, reported solid TTA-UC materials have focused mainly on elastomeric matrices with low barrier properties because the TTA-UC efficiency generally drops significantly in glassy and semicrystalline matrices. To overcome this limit, for example, combine effective and sustainable annihilation upconversion with exhaustive oxygen protection of dyes, we prepare a sustainable solid-state-like material based on nanocellulose. Inspired by the structural buildup of leaves in Nature, we compartmentalize the dyes in the liquid core of nanocellulose-based capsules which are then further embedded in a cellulose nanofibers (NFC) matrix. Using pristine cellulose nanofibers, a sustainable and environmentally friendly functional nanomaterial with ultrahigh barrier properties is achieved. Also, an ensemble of sensitizers and emitter compounds are encapsulated, which allow harvesting of the energy of the whole deep-red sunlight region. The films demonstrate excellent lifetime in synthetic air (20.5/79.5, O2/N2)-even after 1 h operation, the intensity of the TTA-UC signal decreased only 7.8% for the film with 8.8 μm thick NFC coating. The lifetime can be further modulated by the thickness of the protective NFC coating. For comparison, the lifetime of TTA-UC in liquids exposed to air is on the level of seconds to minutes due to fast oxygen quenching.

Interference-enhanced infrared-to-visible upconversion in solid-state thin films sensitized by colloidal nanocrystals

NASA Astrophysics Data System (ADS)

Wu, Mengfei; Jean, Joel; Bulović, Vladimir; Baldo, Marc A.

2017-05-01

Infrared-to-visible photon upconversion has potential applications in photovoltaics, sensing, and bioimaging. We demonstrate a solid-state thin-film device that utilizes sensitized triplet-triplet exciton annihilation, converting infrared photons absorbed by colloidal lead sulfide nanocrystals (NCs) into visible photons emitted from a luminescent dopant in rubrene at low incident light intensities. A typical bilayer device consisting of a monolayer of NCs and a doped film of rubrene is limited by low infrared absorption in the thin NC film. Here, we augment the bilayer with an optical spacer layer and a silver-film back reflector, resulting in interference effects that enhance the optical field and thus the absorption in the NC film. The interference-enhanced device shows an order-of-magnitude increase in the upconverted emission at the wavelength of λ = 610 nm when excited at λ = 980 nm. At incident light intensities above 1.1 W/cm2, the device attains maximum efficiency, converting (1.6 ± 0.2)% of absorbed infrared photons into higher-energy singlet excitons in rubrene.

Donor-Acceptor-Collector Ternary Crystalline Films for Efficient Solid-State Photon Upconversion.

PubMed

Ogawa, Taku; Hosoyamada, Masanori; Yurash, Brett; Nguyen, Thuc-Quyen; Yanai, Nobuhiro; Kimizuka, Nobuo

2018-06-25

It is pivotal to achieve efficient triplet-triplet annihilation based photon upconversion (TTA-UC) in the solid-state for enhancing potentials of renewable energy production devices. However, the UC efficiency of solid materials is largely limited by low fluorescence quantum yields that originate from the aggregation of TTA-UC chromophores, and also by severe back energy transfer from the acceptor singlet state to the singlet state of the triplet donor in the condensed state. In this work, to overcome these issues, we introduce a highly fluorescent singlet energy collector as the third component of donor-doped acceptor crystalline films, in which dual energy migration, i.e., triplet energy migration for TTA-UC and succeeding singlet energy migration for transferring energy to a collector, takes place. To demonstrate this scheme, a highly fluorescent singlet energy collector was added as the third component of donor-doped acceptor crystalline films. An anthracene-based acceptor containing alkyl chains and a carboxylic moiety is mixed with the triplet donor Pt(II) octaethylporphyrin (PtOEP) and the energy collector 2,5,8,11-tetra- tert-butylperylene (TTBP) in solution, and spin-coating of the mixed solution gives acceptor films of nanofibrous crystals homogeneously doped with PtOEP and TTBP. Interestingly, delocalized singlet excitons in acceptor crystals are found to diffuse effectively over the distance of ~37 nm. Thanks to this high diffusivity, only 0.5 mol% of doped TTBP can harvest most of the singlet excitons, which successfully doubles the solid-state fluorescent quantum yield of acceptor/TTBP blend films to 76%. Furthermore, since the donor PtOEP and the collector TTBP are separately isolated in the nanofibrous acceptor crystals, the singlet back energy transfer from the collector to the donor is effectively avoided. Such efficient singlet energy collection and inhibited back energy transfer processes result in a large increase of UC efficiency up to 9.0%, offering rational design principles towards ultimately efficient solid-state upconverters.

Photophysics of Zinc Porphyrin Aggregates in Dilute Water-Ethanol Solutions.

PubMed

Stevens, Amy L; Joshi, Neeraj K; Paige, Matthew F; Steer, Ronald P

2017-12-14

Dimeric and multimeric aggregates of a model metalloporphyrin, zinc tetraphenylporphyrin (ZnTPP), have been produced in a controlled manner by incrementally increasing the water content of dilute aqueous ethanol solutions. Steady state absorption, fluorescence emission, and fluorescence excitation spectra have been measured to identify the aggregates present as a function of solvent composition. The dynamics of the excited states of the aggregates produced initially by excitation in the Soret region have been measured by ultrafast fluorescence upconversion techniques. Only the monomer produces measurable emission from S 2 with a picosecond lifetime; all Soret-excited aggregates, including the dimer, decay radiationlessly on a femtosecond time scale. The S 1 state is the only significant product of the radiationless decay of the S 2 state of the excited monomer, and the aggregates also produce substantial quantum yields of S 1 fluorescence when initially excited in the Soret region. The resulting fluorescent aggregates all decay on a subnanosecond time scale, likely by a mechanism that involves dissociation of the excited monomer from the excitonic multimer. The ZnTPP dimers excited at their ground state geometries in the Soret region exhibit a dynamic behavior that is quite different from those produced following noncoherent triplet-triplet annihilation under the same conditions. The important implications of these observations in determining the aggregation conditions promoting efficient photon upconversion by excitonic annihilation in a variety of media are thoroughly discussed.

Generation and decay dynamics of triplet excitons in Alq3 thin films under high-density excitation conditions.

PubMed

Watanabe, Sadayuki; Furube, Akihiro; Katoh, Ryuzi

2006-08-31

We studied the generation and decay dynamics of triplet excitons in tris-(8-hydroxyquinoline) aluminum (Alq3) thin films by using transient absorption spectroscopy. Absorption spectra of both singlet and triplet excitons in the film were identified by comparison with transient absorption spectra of the ligand molecule (8-hydroxyquinoline) itself and the excited triplet state in solution previously reported. By measuring the excitation light intensity dependence of the absorption, we found that exciton annihilation dominated under high-density excitation conditions. Annihilation rate constants were estimated to be gammaSS = (6 +/- 3) x 10(-11) cm3 s(-1) for single excitons and gammaTT = (4 +/- 2) x 10(-13) cm3 s(-1) for triplet excitons. From detailed analysis of the light intensity dependence of the quantum yield of triplet excitons under high-density conditions, triplet excitons were mainly generated through fission from highly excited singlet states populated by singlet-singlet exciton annihilation. We estimated that 30% of the highly excited states underwent fission.

Triplet exciton diffusion in fac-tris(2-phenylpyridine) iridium(III)-cored electroluminescent dendrimers

NASA Astrophysics Data System (ADS)

Namdas, Ebinazar B.; Ruseckas, Arvydas; Samuel, Ifor D. W.; Lo, Shih-Chun; Burn, Paul L.

2005-02-01

We have studied triplet-triplet annihilation in neat films of electrophosphorescent fac-tris(2-phenylpyridine) iridium(III) [Ir(ppy)3]-cored dendrimers containing phenylene- and carbazole-based dendrons with 2-ethylhexyloxy surface groups using time-resolved photoluminescence. From measured annihilation rates, the limiting current densities above which annihilation would dominate in dendrimer light-emitting devices are found to be >1A/cm2. The triplet exciton diffusion length varies in the range of 2-10 nm depending on the dendron size. The distance dependence of the nearest-neighbor hopping rate shows that energy transfer is dominated by the exchange mechanism.

Exciplex-Sensitized Triplet-Triplet Annihilation in Heterojunction Organic Thin-Film.

PubMed

Lin, Bo-Yen; Easley, Connor J; Chen, Chia-Hsun; Tseng, Po-Chen; Lee, Ming-Zer; Sher, Pin-Hao; Wang, Juen-Kai; Chiu, Tien-Lung; Lin, Chi-Feng; Bardeen, Christopher J; Lee, Jiun-Haw

2017-03-29

A new concept for organic light-emitting diodes (OLEDs) is presented, which is called exciplex-sensitized triplet-triplet annihilation (ESTTA). The exciplex formed at the organic heterojunction interface of 4,4',4″-tris(N-3-methyphenyl-N-phenyl-amino) triphenylamine and 9,10-bis(2'-naphthyl) anthracene (ADN) is used to sensitize the triplet-triplet annihilation (TTA) process on the ADN molecules. This results in a turn-on voltage (2.2 V) of the blue emission from the OLED below the bandgap (2.9 eV). From the transient electroluminescence measurement, blue emission totally came from the TTA process without direct recombination on the ADN molecules. The blue singlet exciton from the TTA process can be quenched by energy transfer to the exciplex, as revealed by transient photoluminescence measurements. This can be prevented by blocking the energy transfer path and improving the radiative recombination rate of blue emission. With the insertion of the "triplet diffusion and singlet blocking (TDSB)" layer and the incorporation of the dopant material, an ESTTA-OLED with external quantum efficiency of 5.1% was achieved, which consists of yellow and blue emission coming from the exciplex and ESTTA process, respectively.

Solid-state infrared-to-visible upconversion sensitized by colloidal nanocrystals

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

Wu, Mengfei; Congreve, Daniel N.; Wilson, Mark W. B.

2015-11-23

Optical upconversion via sensitized triplet–triplet exciton annihilation converts incoherent low-energy photons to shorter wavelengths under modest excitation intensities1,2,3. Here, we report a solid-state thin film for infrared-to-visible upconversion that employs lead sulphide colloidal nanocrystals as a sensitizer. Upconversion is achieved from pump wavelengths beyond λ = 1 μm to emission at λ = 612 nm. When excited at λ = 808 nm, two excitons in the sensitizer are converted to one higher-energy state in the emitter at a yield of 1.2 ± 0.2%. Peak efficiency is attained at an absorbed intensity equivalent to less than one sun. We demonstrate thatmore » colloidal nanocrystals are an attractive alternative to existing molecular sensitizers, given their small exchange splitting, wide wavelength tunability, broadband infrared absorption, and our transient observations of efficient energy transfer. This solid-state architecture for upconversion may prove useful for enhancing the capabilities of solar cells and photodetectors.« less

Solid-state infrared-to-visible upconversion sensitized by colloidal nanocrystals

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

Wu, Mengfei; Congreve, Daniel N.; Wilson, Mark W. B.

2015-11-23

Optical upconversion via sensitized triplet–triplet exciton annihilation converts incoherent low-energy photons to shorter wavelengths under modest excitation intensities1, 2, 3. Here, we report a solid-state thin film for infrared-to-visible upconversion that employs lead sulphide colloidal nanocrystals as a sensitizer. Upconversion is achieved from pump wavelengths beyond λ = 1 μm to emission at λ = 612 nm. When excited at λ = 808 nm, two excitons in the sensitizer are converted to one higher-energy state in the emitter at a yield of 1.2 ± 0.2%. Peak efficiency is attained at an absorbed intensity equivalent to less than one sun. Wemore » demonstrate that colloidal nanocrystals are an attractive alternative to existing molecular sensitizers, given their small exchange splitting, wide wavelength tunability, broadband infrared absorption, and our transient observations of efficient energy transfer. This solid-state architecture for upconversion may prove useful for enhancing the capabilities of solar cells and photodetectors.« less

Analysis of the phosphorescent dye concentration dependence of triplet-triplet annihilation in organic host-guest systems

NASA Astrophysics Data System (ADS)

Zhang, L.; van Eersel, H.; Bobbert, P. A.; Coehoorn, R.

2016-10-01

Using a novel method for analyzing transient photoluminescence (PL) experiments, a microscopic description is obtained for the dye concentration dependence of triplet-triplet annihilation (TTA) in phosphorescent host-guest systems. It is demonstrated that the TTA-mechanism, which could be a single-step dominated process or a diffusion-mediated multi-step process, can be deduced for any given dye concentration from a recently proposed PL intensity analysis. A comparison with the results of kinetic Monte Carlo simulations provides the TTA-Förster radius and shows that the TTA enhancement due to triplet diffusion can be well described in a microscopic manner assuming Förster- or Dexter-type energy transfer.

Broadband sensitized photon up-conversion at subsolar irradiance (Conference Presentation)

NASA Astrophysics Data System (ADS)

Pedrini, Jacopo; Monguzzi, Angelo; Meinardi, Francesco

2016-09-01

A crucial limit of solar devices is their inability to harvest the full solar spectrum. Currently, sensitized up-conversion based on triplet-tripled annihilation (STTA-UC) in bi-component organic systems is the most promising technique to recover sub-bandgap photons, showing good efficiencies also at excitation intensities comparable to the solar irradiance. In STTA-UC, high-energy light is generated through annihilation of metastable triplet states of molecules acting as emitters, which are populated via resonant energy transfer from a light-harvesting sensitizer. However, suitable sensitizers show narrow absorption bands, limiting the fraction of recoverable photons, therefore preventing the application of STTA-UC to real-world devices. Here we demonstrate how to overcome the described limit by using multiple sensitizers that work cooperatively to broaden the overall system absorption band. This is obtained using an additional sensitizer that transfers the extra harvested energy to the main one (sensitization of the sensitizer), or a set of properly designed complementary absorbing sensitizers all able to excite simultaneously the same emitter (multi-sensitizers). In both cases STTA-UC performances result strongly enhanced compared to the corresponding mono-sensitizer system, increasing the up-converted light intensity generated at AM 1.5 up to two times. Remarkably, by coupling our light converters to a DSSC we prove its operation by exploiting exclusively sub-bandgap photons. A detailed modeling of the photophysical processes involved in these complex systems allows us to draw the guidelines for the design of the next generation STTA-UC materials, encouraging their application to photovoltaic technologies.

Electroluminescence of organic light-emitting diodes consisting of an undoped (pbi)2Ir(acac) phosphorescent layer

NASA Astrophysics Data System (ADS)

Lei, Xia; Yu, Junsheng; Zhao, Juan; Jiang, Yadong

2011-11-01

The electroluminescence (EL) characteristics of phosphorescent organic light-emitting diodes (OLEDs) with an undoped bis(1,2-dipheny1-1H-benzoimidazole) iridium (acetylacetonate) [(pbi)2Ir(acac)] emissive layer (EML) of various film thicknesses were studied. The results showed that the intensity of green light emission decreased rapidly with the increasing thickness of (pbi)2Ir(acac), which was relevant to the triplet excimer emission. It suggested that the concentration quenching of monomer emission in the undoped (pbi)2Ir(acac) film was mainly due to the formation of triplet excimer and partly due to the triplet-triplet annihilation (TTA) and triplet-polaron annihilation (TPA). A green OLED with a maximum luminance of 26,531 cd/m2, a current efficiency of 36.2 cd/A, and a power efficiency of 32.4 lm/W was obtained, when the triplet excimer emission was eliminated. Moreover, the white OLED with low efficiency roll-off was realized due to the broadened recombination zone and reduced quenching effects in the EML when no electron blocking layer was employed.

Up-conversion fluorescence: noncoherent excitation by sunlight.

PubMed

Baluschev, S; Miteva, T; Yakutkin, V; Nelles, G; Yasuda, A; Wegner, G

2006-10-06

We demonstrate up-conversion of noncoherent sunlight realized by ultralow excitation intensity. The bimolecular up-conversion process in our systems relies on the presence of a metastable triplet excited state, and thus has dramatically different photophysical characteristics relative to the other known methods for photon up-conversion (two-photon absorption, parametric processes, second harmonic generation, sequential multiphoton absorption, etc.).

Abnormal temperature dependent behaviors of intersystem crossing and triplet-triplet annihilation in organic planar heterojunction devices

NASA Astrophysics Data System (ADS)

Xiang, Jie; Chen, Yingbing; Yuan, De; Jia, Weiyao; Zhang, Qiaoming; Xiong, Zuhong

2016-09-01

Anomalous temperature dependent magneto-electroluminescence was observed at low and high magnetic field strength from organic planar heterojunction devices incorporated common phosphorescent host materials of N,N'-dicarbazolyl-3,5-benzene (mCP) or 4,4'-N,N'-dicarbazole-biphenyl (CBP) as an emissive layer. We found that intersystem crossing became stronger with decreasing temperature and that triplet-triplet annihilation (TTA) occurred at room temperature but ceased at low temperature. Analyses of the electroluminescence spectra of these devices and their temperature dependences indicated that the population of exciplex states increased at low temperature, which caused the abnormal behavior of intersystem crossing. Additionally, long lifetime of the excitons within mCP or CBP layer may allow TTA to occur at room temperature, while the reduced population of excitons at low temperature may account for the disappearance of TTA even though the excitons had increased lifetime.

Migration of CT triplet excitons in TCNB-biphenyl and TCNB-HMB crystals

NASA Astrophysics Data System (ADS)

Kozankiewicz, BolesAw

1994-01-01

Delayed fluorescence decay curves of charge transfer (CT) crystals of tetracyanobenzene with biphenyl (TCNB-B) and with hexamethylbenzene (TCNB-HMB) have been studied over a wide temperature range (5-200 K). The decay curves have been adequately described by decay expressions derived for different mechanisms of triplet-triplet annihilation. This analysis points to one-dimensional, thermally activated motion of CT triplet excitons. The estimated activation energies for the exciton hopping are 360±60 and 650±100 cm -1 (or 550±150 cm -1 depending on the applied model) for the TCNB-B and TCNB-HMB crystals, respectively. The results seem to confirm the self-trapping of triplet CT excitons.

Purely organic electroluminescent material realizing 100% conversion from electricity to light

PubMed Central

Kaji, Hironori; Suzuki, Hajime; Fukushima, Tatsuya; Shizu, Katsuyuki; Suzuki, Katsuaki; Kubo, Shosei; Komino, Takeshi; Oiwa, Hajime; Suzuki, Furitsu; Wakamiya, Atsushi; Murata, Yasujiro; Adachi, Chihaya

2015-01-01

Efficient organic light-emitting diodes have been developed using emitters containing rare metals, such as platinum and iridium complexes. However, there is an urgent need to develop emitters composed of more abundant materials. Here we show a thermally activated delayed fluorescence material for organic light-emitting diodes, which realizes both approximately 100% photoluminescence quantum yield and approximately 100% up-conversion of the triplet to singlet excited state. The material contains electron-donating diphenylaminocarbazole and electron-accepting triphenyltriazine moieties. The typical trade-off between effective emission and triplet-to-singlet up-conversion is overcome by fine-tuning the highest occupied molecular orbital and lowest unoccupied molecular orbital distributions. The nearly zero singlet–triplet energy gap, smaller than the thermal energy at room temperature, results in an organic light-emitting diode with external quantum efficiency of 29.6%. An external quantum efficiency of 41.5% is obtained when using an out-coupling sheet. The external quantum efficiency is 30.7% even at a high luminance of 3,000 cd m−2. PMID:26477390

Electron-Deficient Near-Infrared Pt(II) and Pd(II) Benzoporphyrins with Dual Phosphorescence and Unusually Efficient Thermally Activated Delayed Fluorescence: First Demonstration of Simultaneous Oxygen and Temperature Sensing with a Single Emitter.

PubMed

Zach, Peter W; Freunberger, Stefan A; Klimant, Ingo; Borisov, Sergey M

2017-11-01

We report a family of Pt and Pd benzoporphyrin dyes with versatile photophysical properties and easy access from cheap and abundant chemicals. Attaching 4 or 8 alkylsulfone groups onto a meso-tetraphenyltetrabenzoporphyrin (TPTBP) macrocylcle renders the dyes highly soluble in organic solvents, photostable, and electron-deficient with the redox potential raised up to 0.65 V versus the parent porphyrin. The new dyes intensively absorb in the blue (Soret band, 440-480 nm) and in the red (Q-band, 620-650 nm) parts of the electromagnetic spectrum and show bright phosphorescence at room-temperature in the NIR with quantum yields up to 30% in solution. The small singlet-triplet energy gap yields unusually efficient thermally activated delayed fluorescence (TADF) at elevated temperatures in solution and in polymeric matrices with quantum yields as high as 27% at 120 °C, which is remarkable for benzoporphyrins. Apart from oxygen sensing, these properties enable unprecedented simultaneous, self-referenced oxygen and temperature sensing with a single indicator dye: whereas oxygen can be determined either via the decay time of phosphorescence or TADF, the temperature is accessed via the ratio of the two emissions. Moreover, the dyes are efficient sensitizers for triplet-triplet annihilation (TTA)-based upconversion making possible longer sensitization wavelength than the conventional benzoporphyrin complexes. The Pt-octa-sulfone dye also features interesting semireversible transformation in basic media, which generates new NIR absorbing species.

Temperature dependence of the triplet diffusion and quenching rates in films of an Ir(ppy)3 -cored dendrimer

NASA Astrophysics Data System (ADS)

Ribierre, J. C.; Ruseckas, A.; Samuel, I. D. W.; Staton, S. V.; Burn, P. L.

2008-02-01

We study photoluminescence and triplet-triplet exciton annihilation in a neat film of a fac-tris(2-phenylpyridyl)iridium(III) [Ir(ppy)3] -cored dendrimer and in its blend with a 4,4' -bis( N -carbazolyl)biphenyl host for the temperature range of 77-300K . The nearest neighbor hopping rate of triplet excitons is found to increase by a factor of 2 with temperature between 150 and 300K and is temperature independent at lower temperature. The intermolecular quenching rate follows the Arrhenius law with an activation energy of 7meV , which can be explained by stronger dipole-dipole interactions with the donor molecule in the higher triplet substate. The results indicate that energy disorder has no significant effect on triplet transport and quenching in these materials.

The energies and kinetics of triplet carotenoids in the LH2 antenna complexes as determined by phosphorescence spectroscopy

NASA Astrophysics Data System (ADS)

Rondonuwu, Ferdy S.; Taguchi, Tokio; Fujii, Ritsuko; Yokoyama, Kyosuke; Koyama, Yasushi; Watanabe, Yasutaka

2004-01-01

The triplet (T 1) states of carotenoids (Cars) and bacteriochlorophyll a (BChl) in the LH2 antenna complexes from Rhodobacter sphaeroides G1C, Rba. sphaeroides 2.4.1 and Rhodospirillum molischianum, containing neurosporene, spheroidene and lycopene, respectively, were examined by stationary-state and time-resolved phosphorescence spectroscopy. The T 1 energies of Cars were determined, irrespective of the Car or BChl excitation, to be 7030 cm -1 (neurosporene), 6920 cm -1 (spheroidene) and 6870 cm -1 (lycopene), respectively, whereas that of BChl to be 7590 cm -1. In the Rba. sphaeroides G1C, the Car and BChl triplet states decayed in similar time constant as the BChl Q y state, a fact which indicates that the pair of triplet states decays through the triplet-triplet annihilation mechanism.

Triplet-triplet energy transfer from a UV-A absorber butylmethoxydibenzoylmethane to UV-B absorbers.

PubMed

Kikuchi, Azusa; Oguchi-Fujiyama, Nozomi; Miyazawa, Kazuyuki; Yagi, Mikio

2014-01-01

The phosphorescence decay of a UV-A absorber, 4-tert-butyl-4'-methoxydibenzolymethane (BMDBM) has been observed following a 355 nm laser excitation in the absence and presence of UV-B absorbers, 2-ethylhexyl 4-methoxycinnamate (octyl methoxycinnamate, OMC) and octocrylene (OCR) in ethanol at 77 K. The lifetime of the lowest excited triplet (T1) state of BMDBM is significantly reduced in the presence of OMC and OCR. The observed quenching of BMDBM triplet by OMC and OCR suggests that the intermolecular triplet-triplet energy transfer occurs from BMDBM to OMC and OCR. The T1 state of OCR is nonphosphorescent or very weakly phosphorescent. However, we have shown that the energy level of the T1 state of OCR is lower than that of the enol form of BMDBM. Our methodology of energy-donor phosphorescence decay measurements can be applied to the study of the triplet-triplet energy transfer between UV absorbers even if the energy acceptor is nonphosphorescent. In addition, the delayed fluorescence of BMDBM due to triplet-triplet annihilation was observed in the BMDBM-OMC and BMDBM-OCR mixtures in ethanol at 77 K. Delayed fluorescence is one of the deactivation processes of the excited states of BMDBM under our experimental conditions. © 2013 The American Society of Photobiology.

Triplet exciton confinement for enhanced fluorescent organic light-emitting diodes using a co-host system

NASA Astrophysics Data System (ADS)

Yoo, Han Kyu; Lee, Ho Won; Lee, Song Eun; Kim, Young Kwan; Kim, Se Hyun; Yoon, Seung Soo; Park, Jaehoon

2016-05-01

In this work, the co-host system within an emitting layer (EML) consists of the host and triplet managing (TM) host materials. A set of EML structures was fabricated with various concentrations of the TM host (0, 10, 30, 50, and 70%). The TM host triplet energy level is lower than the energy levels of the host and the guest, which leads to a reduction in the triplet exciton density and the singlet-triplet annihilation of the guest. Blue fluorescent organic light-emitting diodes exhibit a maximum luminous efficiency (LE) and an external quantum efficiency (EQE) of 9.74 cd/A and 4.92%, respectively. In addition, the efficiency roll-off ratios of the LE and the EQE are 14.25 and 13.16%, respectively.

The mechanisms of delayed fluorescence in charge-transfer crystal of tetracyanobenzene-hexamethylbenzene

NASA Astrophysics Data System (ADS)

Kozankiewicz, B.; Prochorow, J.

1989-08-01

Fluorescence, phosphorescence and delayed fluorescence emission characteristics of tetracyanobenzene-hexamethylbenzene (TCNB-HMB) charge-transfer crystal have been studied in the 1.7-340 K temperature range. Delayed fluorescence, originating from heterogeneous triplet-triplet annihilation indicates the presence of mobile charge-transfer triplet excitons at a temperature as low as 1.7 K. However, the behaviour of triplet excitons in TCNB-HMB crystal is strongly controlled by a very efficient trapping process in the whole temperature range investigated. It was found that thermally activated delayed fluorescence, which is a dominating emission of the crystal at elevated temperatures (>60 K), has a different origin (a different initial state) at different temperatures. These observations were analysed and interpreted in terms of a photokinetic model, which is considered to be typical for charge-transfer crystals with high charge-transfer character of triplet excitons.

Effect of Förster-mediated triplet-polaron quenching and triplet-triplet annihilation on the efficiency roll-off of organic light-emitting diodes

NASA Astrophysics Data System (ADS)

van Eersel, H.; Bobbert, P. A.; Janssen, R. A. J.; Coehoorn, R.

2016-04-01

We report the results of a systematic study of the interplay of triplet-polaron quenching (TPQ) and triplet-triplet annihilation (TTA) on the efficiency roll-off of organic light-emitting diodes (OLEDs) with increasing current density. First, we focus on OLEDs based on the green phosphorescent emitter tris[2-phenylpyridine]iridium(III) (Ir(ppy)3) and the red phosphorescent dye platinum octaethylporphyrin. It is found that the experimental data can be reproduced using kinetic Monte Carlo (kMC) simulations within which TPQ and TTA are due to a nearest-neighbor (NN) interaction, or due to a more long-range Förster-type process. Furthermore, we find a subtle interplay between TPQ and TTA: decreasing the contribution of one process can increase the contribution of the other process, so that the roll-off is not significantly reduced. Furthermore, we find that just analyzing the shape of the roll-off is insufficient for determining the relative role of TPQ and TTA. Subsequently, we investigate the wider validity of this picture using kMC simulations for idealized but realistic symmetric OLEDs, with an emissive layer containing a small concentration of phosphorescent dye molecules in a matrix material. Whereas for NN-interactions the roll-off can be reduced when the dye molecules act as shallow hole and electron traps, we find that such an approach becomes counterproductive for long-range TTA and TPQ. Developing well-founded OLED design rules will thus require that more quantitative information is available on the rate and detailed mechanism of the TPQ and TTA processes.

Exciton Correlations in Intramolecular Singlet Fission

DOE PAGES

Sanders, Samuel N.; Kumarasamy, Elango; Pun, Andrew B.; ...

2016-05-16

We have synthesized a series of asymmetric pentacene-tetracene heterodimers with a variable-length conjugated bridge that undergo fast and efficient intramolecular singlet fission (iSF). These compounds have distinct singlet and triplet energies, which allow us to study the spatial dynamics of excitons during the iSF process, including the significant role of exciton correlations in promoting triplet pair generation and recombination. We demonstrate that the primary photoexcitations in conjugated dimers are delocalized singlets that enable fast and efficient iSF. However, in these asymmetric dimers, the singlet becomes more localized on the lower energy unit as the length of the bridge is increased,more » slowing down iSF relative to analogous symmetric dimers. We resolve the recombination kinetics of the inequivalent triplets produced via iSF, and find that they primarily decay via concerted processes. By identifying different decay channels, including delayed fluorescence via triplet-triplet annihilation, we can separate transient species corresponding to both correlated triplet pairs and uncorrelated triplets. Recombination of the triplet pair proceeds rapidly despite our experimental and theoretical demonstration that individual triplets are highly localized and unable to be transported across the conjugated linker. In this class of compounds, the rate of formation and yield of uncorrelated triplets increases with bridge length. Overall, these constrained, asymmetric systems provide a unique platform to isolate and study transient species essential for singlet fission, which are otherwise difficult to observe in symmetric dimers or condensed phases.« less

Resonance Raman investigation of the photoreduction of methylviologen with Ru(bpy) 2+3 and proflavine as sensitizers

NASA Astrophysics Data System (ADS)

Forster, Martin; Hester, Ronald E.

1982-01-01

Reduced methylviologen (MV +) is detected by conventional resonance Raman spectroscopy in photoreactions of Ru(bpy) 2+3 or proflavine (PFH +) with MV 2+ Using apparatus for modulated excitation resonance Raman (MERR) spectroscopy, the irreversible MV + production with PFH + as sensitizer is traced back to triplet-triplet annihilation with simultaneous destruction of PFH +.

The Triplet State

NASA Astrophysics Data System (ADS)

Zahlan, A. B.

2010-01-01

Preface; List of participants; Part I. Spin-orbit Coupling and Intersystem Crossing: 1. Spin-orbit interactions in organic molecules; 2. Singlet-triplet transitions in organic molecules; 3. Triplet decay and intersystem crossing in aromatic hydrocarbons; 4. Statistical aspects of resonance energy transfer; Discussion; Part II. Magnetic Resonance and Magnetic Interactions: 5. Magnetic resonance spectra of organic molecules in triplet states in single crystals; 6. Magnetic interactions related to phosphorescence; 7. ESR investigations of naphthalene-d8:Naphthalene-h8 mixed crystals; 8. Biradicals and polyradicals in the nitroxide series; 9. Changes induced in the phosphorescent radiation of aromatic molecules by paramagnetic resonance in their metastable triplet states; 10. Paramagnetic resonance of the triplet state of tetramethylpyrazine; 11. On magnetic dipole contributions to the intrinsic S0 = T1 transition in simple aromatics; Discussion; Part III. Photochemistry: 12. The kinetics of energy transfer from the triplet state in rigid solutions; 13. Triplet states in gas-phase photochemistry; 14. Biphotonic photochemistry, involving the triplet state: polarisation of the effective T-T transition and solvent effects; 15. Direct and sensitised photo-oxidation of aromatic hydrocarbons in boric acid glass; Discussion; Part IV. Radiationless Transitions: 16. Radiationless transitions in gaseous benzene; 17. Low-lying excited triplet states and intersystem crossing in aromatic hydrocarbons; 18. De-excitation rates of triplet states in condensed media; 19. Lifetimes of the triplet state of aromatic hydrocarbons in the vapour phase; Discussion; Part V. Triplet Excitons: 20. Some comments on the properties of triplet excitons in molecular crystals; 21. Exact treatment of coherent and incoherent triplet exciton migration; 22. Magnetic susceptibility of a system of triplet excitons: Würster's Blue Perchlorate; 23. A study of triplet excitons in anthracene crystals under laser excitation; 24. The electronic states in crystaline anthracene; Discussion; Part VI. Delayed Fluorescent and Phosphorescence: 25. Delayed fluorescence of solutions; 26. The kinetics of the excited states of anthracene and phenanthrene vapor; 27. Optical investigations of the triplet states of naphthalene in different crystalline environments; 28. Excitation of the triplet states of organic molecules; 29. The delayed luminescence and triplet quantum yields of pyrene solutions; 30. Triplet state studies of some polyphenyls in rigid glasses; 31. Decay time of delayed fluorescence of anthracene as a function of temperature (2-30ºK); 32. Energy transfer between benzene and biacetyl and the lifetime of triplet benzene in the gas phase; 33. Charge transfer triplet state of molecular complexes. 34. Flash-photolytic detection of triplet acridine formed by energy transfer from biacetyl; 35. Extinction coefficients of triplet-triplet transitions between 3000 and 8800 A in anthracene; 36. Anthracene triplet-triplet annihilation rate constant; Discussion; Part VII. Triplet State Related to Biology: 37. ESR and optical studies of some triplet states of biological interest; 38. The triplet state of DNA; 39. Some characteristics of the triplet states of the nucleic bases; Discussion; Indexes.

Effect of Förster-mediated triplet-polaron quenching and triplet-triplet annihilation on the efficiency roll-off of organic light-emitting diodes

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

Eersel, H. van; Bobbert, P. A.; Janssen, R. A. J.

2016-04-28

We report the results of a systematic study of the interplay of triplet-polaron quenching (TPQ) and triplet-triplet annihilation (TTA) on the efficiency roll-off of organic light-emitting diodes (OLEDs) with increasing current density. First, we focus on OLEDs based on the green phosphorescent emitter tris[2-phenylpyridine]iridium(III) (Ir(ppy){sub 3}) and the red phosphorescent dye platinum octaethylporphyrin. It is found that the experimental data can be reproduced using kinetic Monte Carlo (kMC) simulations within which TPQ and TTA are due to a nearest-neighbor (NN) interaction, or due to a more long-range Förster-type process. Furthermore, we find a subtle interplay between TPQ and TTA: decreasingmore » the contribution of one process can increase the contribution of the other process, so that the roll-off is not significantly reduced. Furthermore, we find that just analyzing the shape of the roll-off is insufficient for determining the relative role of TPQ and TTA. Subsequently, we investigate the wider validity of this picture using kMC simulations for idealized but realistic symmetric OLEDs, with an emissive layer containing a small concentration of phosphorescent dye molecules in a matrix material. Whereas for NN-interactions the roll-off can be reduced when the dye molecules act as shallow hole and electron traps, we find that such an approach becomes counterproductive for long-range TTA and TPQ. Developing well-founded OLED design rules will thus require that more quantitative information is available on the rate and detailed mechanism of the TPQ and TTA processes.« less

Nonlinear optical properties, upconversion and lasing in metal-organic frameworks.

PubMed

Medishetty, Raghavender; Zaręba, Jan K; Mayer, David; Samoć, Marek; Fischer, Roland A

2017-08-14

The building block modular approach that lies behind coordination polymers (CPs) and metal-organic frameworks (MOFs) results not only in a plethora of materials that can be obtained but also in a vast array of material properties that could be aimed at. Optical properties appear to be particularly predetermined by the character of individual structural units and by the intricate interplay between them. Indeed, the "design principles" shaping the optical properties of these materials seem to be well explored for luminescence and second-harmonic generation (SHG) phenomena; these have been covered in numerous previous reviews. Herein, we shine light on CPs and MOFs as optical media for state-of-the-art photonic phenomena such as multi-photon absorption, triplet-triplet annihilation (TTA) and stimulated emission. In the first part of this review we focus on the nonlinear optical (NLO) properties of CPs and MOFs, with a closer look at the two-photon absorption property. We discuss the scope of applicability of most commonly used measurement techniques (Z-scan and two-photon excited fluorescence (TPEF)) that can be applied for proper determination of the NLO properties of these materials; in particular, we suggest recommendations for their use, along with a discussion of the best reporting practices of NLO parameters. We also outline design principles, employing both intramolecular and intermolecular strategies, that are necessary for maximizing the NLO response. A review of recent literature on two-, three- and multi-photon absorption in CPs and MOFs is further supplemented with application-oriented processes such as two-photon 3D patterning and data storage. Additionally, we provide an overview of the latest achievements in the field of frequency doubling (SHG) and tripling (third-harmonic generation, THG) in these materials. Apart from nonlinear processes, in the next sections we also target the photonic properties of MOFs that benefit from their porosity, and resulting from this their ability to serve as containers for optically-active molecules. Thus, we survey dye@MOF composites as novel media in which efficient upconversion via triplet energy migration (TEM) occurs as well as materials for stimulated emission and multi-photon pumped lasing. Prospects for producing lasing as an intrinsic property of MOFs has also been discussed. Overall, further development of the optical processes highlighted herein should allow for realization of various photonic, data storage, biomedical and optoelectronic applications.

Effect of broad recombination zone in multiple quantum well structures on lifetime and efficiency of blue organic light-emitting diodes

NASA Astrophysics Data System (ADS)

Lee, Seok Jae; Lee, Song Eun; Lee, Dong Hyung; Koo, Ja Ryong; Lee, Ho Won; Yoon, Seung Soo; Park, Jaehoon; Kim, Young Kwan

2014-10-01

Blue phosphorescent organic light-emitting diodes with multiple quantum well (MQW) structures (from one to four quantum wells) within an emitting layer (EML) are fabricated with charge control layers (CCLs) to control carrier movement. The distributed recombination zone and balanced charge carrier injection within EML are achieved through the MQW structure with CCLs. Remarkably, the half-decay lifetime of a blue device with three quantum wells, measured at an initial luminance of 500 cd/m2, is 3.5 times longer than that using a conventional structure. Additionally, the device’s efficiency improved. These results are explained with the effects of triplet exciton confinement and triplet-triplet annihilation within each EML.

Photophysics and Photochemistry of 2-Aminobenzoic Acid Anion in Aqueous Solution

NASA Astrophysics Data System (ADS)

Pozdnyakov, Ivan P.; Plyusnin, Victor F.; Grivin, Vjacheslav P.

2009-11-01

Nanosecond laser flash photolysis and absorption and fluorescence spectroscopy were used to study photochemical processes of 2-aminobenzoic acid anion (ABA-) in aqueous solutions. Excitation of this species gives rise to the ABA- triplet state to the ABA• radical and to the hydrated electron (eaq-). The last two species result from two-photon processes. In a neutral medium, the main decay channels of ABA- triplet state, the ABA• radical, and eaq- are T-T annihilation, recombination, and capture by the ABA- anion, respectively.

Endothermic singlet fission is hindered by excimer formation

NASA Astrophysics Data System (ADS)

Dover, Cameron B.; Gallaher, Joseph K.; Frazer, Laszlo; Tapping, Patrick C.; Petty, Anthony J.; Crossley, Maxwell J.; Anthony, John E.; Kee, Tak W.; Schmidt, Timothy W.

2018-03-01

Singlet fission is a process whereby two triplet excitons can be produced from one photon, potentially increasing the efficiency of photovoltaic devices. Endothermic singlet fission is desired for a maximum energy-conversion efficiency, and such systems have been considered to form an excimer-like state with multiexcitonic character prior to the appearance of triplets. However, the role of the excimer as an intermediate has, until now, been unclear. Here we show, using 5,12-bis((triisopropylsilyl)ethynyl)tetracene in solution as a prototypical example, that, rather than acting as an intermediate, the excimer serves to trap excited states to the detriment of singlet-fission yield. We clearly demonstrate that singlet fission and its conjugate process, triplet-triplet annihilation, occur at a longer intermolecular distance than an excimer intermediate would impute. These results establish that an endothermic singlet-fission material must be designed to avoid excimer formation, thus allowing singlet fission to reach its full potential in enhancing photovoltaic energy conversion.

Endothermic singlet fission is hindered by excimer formation.

PubMed

Dover, Cameron B; Gallaher, Joseph K; Frazer, Laszlo; Tapping, Patrick C; Petty, Anthony J; Crossley, Maxwell J; Anthony, John E; Kee, Tak W; Schmidt, Timothy W

2018-03-01

Singlet fission is a process whereby two triplet excitons can be produced from one photon, potentially increasing the efficiency of photovoltaic devices. Endothermic singlet fission is desired for a maximum energy-conversion efficiency, and such systems have been considered to form an excimer-like state with multiexcitonic character prior to the appearance of triplets. However, the role of the excimer as an intermediate has, until now, been unclear. Here we show, using 5,12-bis((triisopropylsilyl)ethynyl)tetracene in solution as a prototypical example, that, rather than acting as an intermediate, the excimer serves to trap excited states to the detriment of singlet-fission yield. We clearly demonstrate that singlet fission and its conjugate process, triplet-triplet annihilation, occur at a longer intermolecular distance than an excimer intermediate would impute. These results establish that an endothermic singlet-fission material must be designed to avoid excimer formation, thus allowing singlet fission to reach its full potential in enhancing photovoltaic energy conversion.

High efficiency and brightness fluorescent organic light emitting diode by triplet-triplet fusion

DOEpatents

Forrest, Stephen; Zhang, Yifan

2015-02-10

A first device is provided. The first device further comprises an organic light emitting device. The organic light emitting device further comprises an anode, a cathode, and an emissive layer disposed between the anode and the cathode. The emissive layer may include an organic host compound and at least one organic emitting compound capable of fluorescent emission at room temperature. Various configurations are described for providing a range of current densities in which T-T fusion dominates over S-T annihilation, leading to very high efficiency fluorescent OLEDs.

Photophysics and photochemistry of 2-aminobenzoic acid anion in aqueous solution.

PubMed

Pozdnyakov, Ivan P; Plyusnin, Victor F; Grivin, Vjacheslav P

2009-12-24

Nanosecond laser flash photolysis and absorption and fluorescence spectroscopy were used to study photochemical processes of 2-aminobenzoic acid anion (ABA(-)) in aqueous solutions. Excitation of this species gives rise to the ABA(-) triplet state to the ABA* radical and to the hydrated electron (e(aq)(-)). The last two species result from two-photon processes. In a neutral medium, the main decay channels of ABA(-) triplet state, the ABA* radical, and e(aq)(-) are T-T annihilation, recombination, and capture by the ABA(-) anion, respectively.

Control of Energy Flow Dynamics between Tetracene Ligands and PbS Quantum Dots by Size Tuning and Ligand Coverage

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

Kroupa, Daniel M.; Arias, Dylan H.; Blackburn, Jeffrey L.

We have prepared a series of samples with the ligand 6,13-bistri(iso-propyl)silylethynyl tetracene 2-carboxylic acid (TIPS-Tc-COOH) attached to PbS quantum dot (QD) samples of three different sizes in order to monitor and control the extent and time scales of energy flow after photoexcitation. Fast energy transfer (~1 ps) to the PbS QD occurs upon direct excitation of the ligand for all samples. The largest size QD maintains the microsecond exciton lifetime characteristic of the as-prepared oleate terminated PbS QDs. However, two smaller QD sizes with lowest exciton energies similar to or larger than the TIPS-Tc-COO- triplet energy undergo energy transfer betweenmore » QD core and ligand triplet on nanosecond to microsecond timescales. For the intermediate size QDs in particular, energy can be recycled many times between ligand and core, but the triplet remains the dominant excited species at long times, living for ~3 us for fully exchanged QDs and up to 30 us for partial ligand exchange, which is revealed as a method for controlling the triplet lifetime. A unique upconverted luminescence spectrum is observed that results from annihilation of triplets after exclusive excitation of the QD core.« less

Control of Energy Flow Dynamics between Tetracene Ligands and PbS Quantum Dots by Size Tuning and Ligand Coverage

DOE PAGES

Kroupa, Daniel M.; Arias, Dylan H.; Blackburn, Jeffrey L.; ...

2018-01-24

We have prepared a series of samples with the ligand 6,13-bistri(iso-propyl)silylethynyl tetracene 2-carboxylic acid (TIPS-Tc-COOH) attached to PbS quantum dot (QD) samples of three different sizes in order to monitor and control the extent and time scales of energy flow after photoexcitation. Fast energy transfer (~1 ps) to the PbS QD occurs upon direct excitation of the ligand for all samples. The largest size QD maintains the microsecond exciton lifetime characteristic of the as-prepared oleate terminated PbS QDs. However, two smaller QD sizes with lowest exciton energies similar to or larger than the TIPS-Tc-COO- triplet energy undergo energy transfer betweenmore » QD core and ligand triplet on nanosecond to microsecond timescales. For the intermediate size QDs in particular, energy can be recycled many times between ligand and core, but the triplet remains the dominant excited species at long times, living for ~3 us for fully exchanged QDs and up to 30 us for partial ligand exchange, which is revealed as a method for controlling the triplet lifetime. A unique upconverted luminescence spectrum is observed that results from annihilation of triplets after exclusive excitation of the QD core.« less

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

Zhang, Tingting; Holford, D. F.; Gu, Hang

The magnetic field effects on the electroluminescence of aluminium tris-(8-hydroxyqinoline) (Alq{sub 3}) based organic light emitting diodes have been investigated by varying the electron/hole ratio in the emissive layer. Experimental results reveal that a negative high field effect in the magneto-electroluminescence (MEL) can be found in devices with very low triplet exciton concentration at room temperature. This suggests triplet-triplet annihilation cannot be used to explain the negative high field MEL in the Alq{sub 3} system. Our results suggest that hole-exciton interaction may be the origin of the negative high field MEL and also, in parallel with this interaction, there ismore » also the more common positive high field process occurring which has been tentatively attributed to electron-exciton interactions. The competition between these different processes decides the final shape of the MEL at high fields.« less

Hole-exciton interaction induced high field decay of magneto-electroluminescence in Alq3-based organic light-emitting diodes at room temperature

NASA Astrophysics Data System (ADS)

Zhang, Tingting; Holford, D. F.; Gu, Hang; Kreouzis, T.; Zhang, Sijie; Gillin, W. P.

2016-01-01

The magnetic field effects on the electroluminescence of aluminium tris-(8-hydroxyqinoline) (Alq3) based organic light emitting diodes have been investigated by varying the electron/hole ratio in the emissive layer. Experimental results reveal that a negative high field effect in the magneto-electroluminescence (MEL) can be found in devices with very low triplet exciton concentration at room temperature. This suggests triplet-triplet annihilation cannot be used to explain the negative high field MEL in the Alq3 system. Our results suggest that hole-exciton interaction may be the origin of the negative high field MEL and also, in parallel with this interaction, there is also the more common positive high field process occurring which has been tentatively attributed to electron-exciton interactions. The competition between these different processes decides the final shape of the MEL at high fields.

Long-term luminescence of sensibilizers in tissues at the conditions of oxygen deficiency due to photodynamic effect

NASA Astrophysics Data System (ADS)

Ishemgulov, A. T.; Letuta, S. N.; Pashkevich, S. N.; Alidzhanov, E. K.; Lantukh, Yu. D.

2017-11-01

Long-term luminescence of organic dyes (xanthene dyes, halogen substituted fluoroscein) was used for an in vitro study of the photodynamic effect of exogenic probes in malignant tumors and healthy tissues of mice. It is shown that the photodynamic activity of oxygen and the dynamics of its concentration in tissues can be estimated from the delayed fluorescence of exogenic probes caused by singlet-triplet annihilation of singlet oxygen and excited triplet states of the molecules of photosensitizer dyes. It is found that quenching of long-term luminescence of photosensitizers significantly differs in tumors and normal tissues.

Up-Conversion Intersystem Crossing Rates in Organic Emitters for Thermally Activated Delayed Fluorescence: Impact of the Nature of Singlet vs Triplet Excited States.

PubMed

Samanta, Pralok K; Kim, Dongwook; Coropceanu, Veaceslav; Brédas, Jean-Luc

2017-03-22

The rates for up-conversion intersystem crossing (UISC) from the T 1 state to the S 1 state are calculated for a series of organic emitters with an emphasis on thermally activated delayed fluorescence (TADF) materials. Both the spin-orbit coupling and the energy difference between the S 1 and T 1 states (ΔE ST ) are evaluated, at the density functional theory (DFT) and time-dependent DFT levels. The calculated UISC rates and ΔE ST values are found to be in good agreement with available experimental data. Our results underline that small ΔE ST values and sizable spin-orbit coupling matrix elements have to be simultaneously realized in order to facilitate UISC and ultimately TADF. Importantly, the spatial separation of the highest occupied and lowest unoccupied molecular orbitals of the emitter, a widely accepted strategy for the design of TADF molecules, does not necessarily lead to a sufficient reduction in ΔE ST ; in fact, either a significant charge-transfer (CT) contribution to the T 1 state or a minimal energy difference between the local-excitation and charge-transfer triplet states is required to achieve a small ΔE ST . Also, having S 1 and T 1 states of a different nature is found to strongly enhance spin-orbit coupling, which is consistent with the El-Sayed rule for ISC rates. Overall, our results indicate that having either similar energies for the local-excitation and charge-transfer triplet states or the right balance between a substantial CT contribution to T 1 and somewhat different natures of the S 1 and T 1 states, paves the way toward UISC enhancement and thus TADF efficiency improvement.

Efficient triplet application in exciplex delayed-fluorescence OLEDs using a reverse intersystem crossing mechanism based on a ΔES-T of around zero.

PubMed

Zhang, Tianyou; Chu, Bei; Li, Wenlian; Su, Zisheng; Peng, Qi Ming; Zhao, Bo; Luo, Yongshi; Jin, Fangming; Yan, Xingwu; Gao, Yuan; Wu, Hairuo; Zhang, Feng; Fan, Di; Wang, Junbo

2014-08-13

We demonstrate highly efficient exciplex delayed-fluorescence organic light-emitting diodes (OLEDs) in which 4,4',4″-tris[3-methylphenyl(phenyl)aminotriphenylamine (m-MTDATA) and 4,7-diphenyl-1,10-phenanthroline (Bphen) were selected as donor and acceptor components, respectively. Our m-MTDATA:Bphen exciplex electroluminescence (EL) mechanism is based on reverse intersystem crossing (RISC) from the triplet to singlet excited states. As a result, an external quantum efficiency (EQE) of 7.79% at 10 mA/cm(2) was observed, which increases by 3.2 and 1.5 times over that reported in Nat. Photonics 2012, 6, 253 and Appl. Phys. Lett. 2012, 101, 023306, respectively. The high EQE would be attributed to a very easy RISC process because the energy difference between the singlet and triplet excited states is almost around zero. The verdict was proven by photoluminescence (PL) rate analysis at different temperatures and time-resolved spectral analysis. Besides, the study of the transient PL process indicates that the presence of an unbalanced charge in exciplex EL devices is responsible for the low EQE and high-efficiency roll-off. When the exciplex devices were placed in a 100 mT magnetic field, the permanently positive magnetoelectroluminescence and magnetoconductivity were observed. The magnetic properties confirm that the efficient exciplex EL only originates from delayed fluorescence via RISC processes but is not related to the triplet-triplet annihilation process.

Triplet exciton dissociation and electron extraction in graphene-templated pentacene observed with ultrafast spectroscopy.

PubMed

McDonough, Thomas J; Zhang, Lushuai; Roy, Susmit Singha; Kearns, Nicholas M; Arnold, Michael S; Zanni, Martin T; Andrew, Trisha L

2017-02-08

We compare the ultrafast dynamics of singlet fission and charge generation in pentacene films grown on glass and graphene. Pentacene grown on graphene is interesting because it forms large crystals with the long axis of the molecules "lying-down" (parallel to the surface). At low excitation fluence, spectra for pentacene on graphene contain triplet absorptions at 507 and 545 nm and no bleaching at 630 nm, which we show is due to the orientation of the pentacene molecules. We perform the first transient absorption anisotropy measurements on pentacene, observing negative anisotropy of the 507 and 545 nm peaks, consistent with triplet absorption. A broad feature at 853 nm, observed on both glass and graphene, is isotropic, suggesting hole absorption. At high fluence, there are additional features, whose kinetics and anisotropies are not explained by heating, that we assign to charge generation; we propose a polaron pair absorption at 614 nm. The lifetimes are shorter at high fluence for both pentacene on glass and graphene, indicative of triplet-triplet annihilation that likely enhances charge generation. The anisotropy decays more slowly for pentacene on graphene than on glass, in keeping with the smaller domain size observed via atomic force microscopy. Coherent acoustic phonons are observed for pentacene on graphene, which is a consequence of more homogeneous domains. Measuring the ultrafast dynamics of pentacene as a function of molecular orientation, fluence, and polarization provides new insight to previous spectral assignments.

Decreasing luminescence lifetime of evaporating phosphorescent droplets

NASA Astrophysics Data System (ADS)

van der Voort, D. D.; Dam, N. J.; Sweep, A. M.; Kunnen, R. P. J.; van Heijst, G. J. F.; Clercx, H. J. H.; van de Water, W.

2016-12-01

Laser-induced phosphorescence has been used extensively to study spray dynamics. It is important to understand the influence of droplet evaporation in the interpretation of such measurements, as it increases luminescence quenching. By suspending a single evaporating n-heptane droplet in an acoustic levitator, the properties of lanthanide-complex europium-thenoyltrifluoroacetone-trioctylphosphine oxide (Eu-TTA-TOPO) phosphorescence are determined through high-speed imaging. A decrease was found in the measured phosphorescence decay coefficient (780 → 200 μs) with decreasing droplet volumes (10-9 → 10-11 m3) corresponding to increasing concentrations (10-4 → 10-2 M). This decrease continues up to the point of shell-formation at supersaturated concentrations. The diminished luminescence is shown not to be attributable to triplet-triplet annihilation, quenching between excited triplet-state molecules. Instead, the pure exponential decays found in the measurements show that a non-phosphorescent quencher, such as free TTA/TOPO, can be attributable to this decay. The concentration dependence of the phosphorescence lifetime can therefore be used as a diagnostic of evaporation in sprays.

Heavy dark matter annihilation from effective field theory.

PubMed

Ovanesyan, Grigory; Slatyer, Tracy R; Stewart, Iain W

2015-05-29

We formulate an effective field theory description for SU(2)_{L} triplet fermionic dark matter by combining nonrelativistic dark matter with gauge bosons in the soft-collinear effective theory. For a given dark matter mass, the annihilation cross section to line photons is obtained with 5% precision by simultaneously including Sommerfeld enhancement and the resummation of electroweak Sudakov logarithms at next-to-leading logarithmic order. Using these results, we present more accurate and precise predictions for the gamma-ray line signal from annihilation, updating both existing constraints and the reach of future experiments.

Spatial exciton allocation strategy with reduced energy loss for high-efficiency fluorescent/phosphorescent hybrid white organic light-emitting diodes

DOE PAGES

Zhao, Fangchao; Wei, Ying; Xu, Hui; ...

2017-05-17

Due to the poor operational lifetime of blue phosphorescent dopants and blue thermally activated delayed fluorescent (TADF) materials, hybrid white organic light-emitting diodes (WOLEDs) with conventional blue fluorescent emitters are still preferred for commercial applications in general lighting. However, the improvement in the overall efficiency of hybrid WOLEDs has been limited due to energy losses during the energy transfer process and exciton quenching after the spatial separation of the singlet and triplet excitons. Here we demonstrate the development of a Spatial Exciton Allocation Strategy (SEAS) to achieve close to 100% internal quantum efficiency (IQE) in blue-yellow complementary color hybrid WOLEDs.more » The employed blue fluorophore not only has a resonant triplet level with the yellow phosphor to reduce energy loss during energy transfer processes and triplet–triplet annihilation (TTA), but also has a resonant singlet level with the electron transport layer to extend singlet exciton distribution and enhance both singlet and triplet exciton utilization. Thus, the resulting hybrid WOLEDs exhibited 104 lm W -1 efficacy at 100 cd m -2 and 74 lm W -1 at 1000 cd m -2 with CIE coordinates of (0.42, 0.44) which is warm white and suitable for indoor lighting.« less

Spatial exciton allocation strategy with reduced energy loss for high-efficiency fluorescent/phosphorescent hybrid white organic light-emitting diodes

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

Zhao, Fangchao; Wei, Ying; Xu, Hui

Due to the poor operational lifetime of blue phosphorescent dopants and blue thermally activated delayed fluorescent (TADF) materials, hybrid white organic light-emitting diodes (WOLEDs) with conventional blue fluorescent emitters are still preferred for commercial applications in general lighting. However, the improvement in the overall efficiency of hybrid WOLEDs has been limited due to energy losses during the energy transfer process and exciton quenching after the spatial separation of the singlet and triplet excitons. Here we demonstrate the development of a Spatial Exciton Allocation Strategy (SEAS) to achieve close to 100% internal quantum efficiency (IQE) in blue-yellow complementary color hybrid WOLEDs.more » The employed blue fluorophore not only has a resonant triplet level with the yellow phosphor to reduce energy loss during energy transfer processes and triplet–triplet annihilation (TTA), but also has a resonant singlet level with the electron transport layer to extend singlet exciton distribution and enhance both singlet and triplet exciton utilization. Thus, the resulting hybrid WOLEDs exhibited 104 lm W -1 efficacy at 100 cd m -2 and 74 lm W -1 at 1000 cd m -2 with CIE coordinates of (0.42, 0.44) which is warm white and suitable for indoor lighting.« less

Donor-σ-Acceptor Motifs: Thermally Activated Delayed Fluorescence Emitters with Dual Upconversion.

PubMed

Geng, Yan; D'Aleo, Anthony; Inada, Ko; Cui, Lin-Song; Kim, Jong Uk; Nakanotani, Hajime; Adachi, Chihaya

2017-12-22

A family of organic emitters with a donor-σ-acceptor (D-σ-A) motif is presented. Owing to the weakly coupled D-σ-A intramolecular charge-transfer state, a transition from the localized excited triplet state ( 3 LE) and charge-transfer triplet state ( 3 CT) to the charge-transfer singlet state ( 1 CT) occurred with a small activation energy and high photoluminescence quantum efficiency. Two thermally activated delayed fluorescence (TADF) components were identified, one of which has a very short lifetime of 200-400 ns and the other a longer TADF lifetime of the order of microseconds. In particular, the two D-σ-A materials presented strong blue emission with TADF properties in toluene. These results will shed light on the molecular design of new TADF emitters with short delayed lifetimes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sensitized phosphorescence of benzil-doped ladder-type methyl-poly(para-phenylene)

NASA Astrophysics Data System (ADS)

Bagnich, S. A.; Bässler, H.; Neher, D.

2004-11-01

The delayed luminescence and phosphorescence of ladder-type methyl-poly(para-phenylene) (MeLPPP) doped with benzil at a concentration of 20% by weight has been measured. The introduction of benzil leads to a dramatic reduction of the polymer singlet emission. At the same time, a new band with maximum at 611 nm appears, corresponding to the phosphorescence of MeLPPP. The phosphorescence decay on the short time scale is close to an exponential law with a time decay of 15 ms. This indicates that benzil can efficiently sensitize the phosphorescence of the polymer. In addition, a broad and featureless emission is observed in the delayed luminescence spectra of benzil-doped MeLPPP, which is attributed to an exciplex formed between the polymer host and the dopant. We further observe that the delayed fluorescence is enhanced by the addition of benzil. It is concluded that the delayed fluorescence of benzil-doped MeLPPP is mainly due to the annihilation of triplet excitons on the polymer. Finally, efficient triplet-triplet energy transfer from the benzil-doped polymer to the red-emitting phosphorescent dye Pt(II)octaethylporphyrin is established.

Low amplified spontaneous emission threshold and suppression of electroluminescence efficiency roll-off in layers doped with ter(9,9'-spirobifluorene)

NASA Astrophysics Data System (ADS)

Inoue, Munetomo; Matsushima, Toshinori; Adachi, Chihaya

2016-03-01

We demonstrate that ter(9,9'-spirobifluorene) (TSBF) doped in a host matrix layer of 4,4'-bis(carbazol-9-yl)biphenyl (CBP) shows a low amplified spontaneous emission (ASE) threshold (Eth = 1.0 μJ cm-2) and suppressed electroluminescence efficiency roll-off at high current densities (no roll-off up to 100 mA cm-2). One origin of the low ASE threshold is that the TSBF-doped CBP layer possesses a very large radiative decay constant (kr = 1.1 × 109 s-1). Singlet-triplet annihilation is almost suppressed in the TSBF-doped CBP layer, which can be ascribed to the small overlap between the emission and triplet absorption of TSBF. Also, the small energy level difference between TSBF and CBP minimizes carrier trapping in TSBF, leading to the suppression of singlet-polaron annihilation. TSBF showed one of the lowest Eth and the most suppressed efficiency roll-off among organic laser dyes investigated in this study and, therefore, is believed to be a promising candidate to realize electrically pumped organic semiconductor laser diodes in the future.

Theory of Transient Excited State Absorptions in Pentacene and Derivatives: Triplet-Triplet Biexciton versus Free Triplets.

PubMed

Khan, Souratosh; Mazumdar, Sumit

2017-12-07

Recent experiments in several singlet-fission materials have found that the triplet-triplet biexciton either is the primary product of photoexcitation or has a much longer lifetime than believed until now. It thus becomes essential to determine the difference in the spectroscopic signatures of the bound triplet-triplet and free triplets to distinguish between them optically. We report calculations of excited state absorptions (ESAs) from the singlet and triplet excitons and from the triplet-triplet biexciton for a pentacene crystal with the herringbone structure and for nanocrystals of bis(triisopropylsilylethynyl) (TIPS)-pentacene. The triplet-triplet biexciton absorbs in both the visible and the near-infrared (NIR), while the monomer free triplet absorbs only in the visible. The intensity of the NIR absorption depends on the extent of intermolecular coupling, in agreement with observations in TIPS-pentacene nanocrystals. We predict additional weak ESA from the triplet-triplet but not from the triplet, at still lower energy.

Photon Upconversion Using Baird-Type (Anti)Aromatic Quinoidal Naphthalene Derivative as a Sensitizer

DOE PAGES

Shokri, Siamak; Wiederrecht, Gary P.; Gosztola, David J.; ...

2017-10-02

In this study, a naphtho-p-quinodimethane (QDM) exhibiting Baird’s 4n - π antiaromaticity was used as green photonsharvesting chromophore to sensitize perylene (Per) leading to upconverted blue photoluminescence. The solution phase QDM → Per triplet energy transfer (TET) could not be unraveled via the Stern-Volmer method, but transient absorption measurements revealed that the kinetics of T 1 → T n for QDM (τ = 1.4 μs) was 1 order of magnitude reduced (τ= 0.17 μs) as a result of 3(Per)* formation. Lastly, we demonstrated that incident light with power densities in the microwatt regime is sufficient to perform photon upconversion usingmore » the present set of molecular systems.« less

Triplet-triplet annihilation in highly efficient fluorescent organic light-emitting diodes: current state and future outlook.

PubMed

Kondakov, Denis Y

2015-06-28

Studies of delayed electroluminescence in highly efficient fluorescent organic light-emitting diodes (OLEDs) of many dissimilar architectures indicate that the triplet-triplet annihilation (TTA) significantly increases yield of excited singlet states-emitting molecules in this type of device thereby contributes substantially to their efficiency. Towards the end of the 2000s, the essential role of TTA in realizing highly efficient fluorescent devices was widely recognized. Analysis of a diverse set of fluorescent OLEDs shows that high efficiencies are often cor-related to TTA extents. It is therefore likely that it is the long-term empirical optimization of OLED efficiencies that has resulted in fortuitous emergence of TTA as a large and ubiquitous contributor to efficiency. TTA contributions as high as 20-30% are common in the state-of-the-art OLEDs, and even become dominant in special cases, where TTA is shown to substantially exceed the spin-statistical limit. The fundamental features of OLED efficiency enhancement via TTA-molecular structure-dependent contributions, current density-dependent intensities in practical devices and frequently observed antagonistic relationships between TTA extent and OLED lifetime-came to be understood over the course of the next few years. More recently, however, there was much less reported progress with respect to all-important quantitative details of the TTA mechanism. It should be emphasized that, to this day and despite the decades of work on improving blue phosphorescent OLEDs as well as the recent advent of thermally activated delayed fluorescence OLEDs, the majority of practical blue OLEDs still rely on TTA. Considering such practical importance of fluorescent blue OLEDs, the design of blue OLED-compatible materials capable of substantially exceeding the spin-statistical limit in TTA, elimination of the antagonistic relationship between TTA-related efficiency gains and lifetime losses, and designing devices with an extended range of current densities producing near-maximum TTA electroluminescence are the areas where future improvements would be most beneficial. © 2015 The Author(s) Published by the Royal Society. All rights reserved.

On the possibility of singlet fission in crystalline quaterrylene

NASA Astrophysics Data System (ADS)

Wang, Xiaopeng; Liu, Xingyu; Cook, Cameron; Schatschneider, Bohdan; Marom, Noa

2018-05-01

Singlet fission (SF), the spontaneous down-conversion of a singlet exciton into two triplet excitons residing on neighboring molecules, is a promising route to improve organic photovoltaic (OPV) device efficiencies by harvesting two charge carriers from one photon. However, only a few materials have been discovered that exhibit intermolecular SF in the solid state, most of which are acene derivatives. Recently, there has been a growing interest in rylenes as potential SF materials. We use many-body perturbation theory in the GW approximation and the Bethe-Salpeter equation to investigate the possibility of intermolecular SF in crystalline perylene and quaterrylene. A new method is presented for determining the percent charge transfer (%CT) character of an exciton wave-function from double-Bader analysis. This enables relating exciton probability distributions to crystal packing. Based on comparison to known and predicted SF materials with respect to the energy conservation criterion (ES-2ET) and %CT, crystalline quaterrylene is a promising candidate for intermolecular SF. Furthermore, quaterrylene is attractive for OPV applications, thanks to its high stability and narrow optical gap. Perylene is not expected to exhibit SF; however, it is a promising candidate for harvesting sub-gap photons by triplet-triplet annihilation.

Kinetic Monte Carlo modeling of the efficiency roll-off in a multilayer white organic light-emitting device

NASA Astrophysics Data System (ADS)

Mesta, M.; van Eersel, H.; Coehoorn, R.; Bobbert, P. A.

2016-03-01

Triplet-triplet annihilation (TTA) and triplet-polaron quenching (TPQ) in organic light-emitting devices (OLEDs) lead to a roll-off of the internal quantum efficiency (IQE) with increasing current density J. We employ a kinetic Monte Carlo modeling study to analyze the measured IQE and color balance as a function of J in a multilayer hybrid white OLED that combines fluorescent blue with phosphorescent green and red emission. We investigate two models for TTA and TPQ involving the phosphorescent green and red emitters: short-range nearest-neighbor quenching and long-range Förster-type quenching. Short-range quenching predicts roll-off to occur at much higher J than measured. Taking long-range quenching with Förster radii for TTA and TPQ equal to twice the Förster radii for exciton transfer leads to a fair description of the measured IQE-J curve, with the major contribution to the roll-off coming from TPQ. The measured decrease of the ratio of phosphorescent to fluorescent component of the emitted light with increasing J is correctly predicted. A proper description of the J-dependence of the ratio of red and green phosphorescent emission needs further model refinements.

On the possibility of singlet fission in crystalline quaterrylene.

PubMed

Wang, Xiaopeng; Liu, Xingyu; Cook, Cameron; Schatschneider, Bohdan; Marom, Noa

2018-05-14

Singlet fission (SF), the spontaneous down-conversion of a singlet exciton into two triplet excitons residing on neighboring molecules, is a promising route to improve organic photovoltaic (OPV) device efficiencies by harvesting two charge carriers from one photon. However, only a few materials have been discovered that exhibit intermolecular SF in the solid state, most of which are acene derivatives. Recently, there has been a growing interest in rylenes as potential SF materials. We use many-body perturbation theory in the GW approximation and the Bethe-Salpeter equation to investigate the possibility of intermolecular SF in crystalline perylene and quaterrylene. A new method is presented for determining the percent charge transfer (%CT) character of an exciton wave-function from double-Bader analysis. This enables relating exciton probability distributions to crystal packing. Based on comparison to known and predicted SF materials with respect to the energy conservation criterion (E S -2E T ) and %CT, crystalline quaterrylene is a promising candidate for intermolecular SF. Furthermore, quaterrylene is attractive for OPV applications, thanks to its high stability and narrow optical gap. Perylene is not expected to exhibit SF; however, it is a promising candidate for harvesting sub-gap photons by triplet-triplet annihilation.

Sensitized phosphorescence of benzil-doped ladder-type methyl-poly(para-phenylene).

PubMed

Bagnich, S A; Bässler, H; Neher, D

2004-11-08

The delayed luminescence and phosphorescence of ladder-type methyl-poly(para-phenylene) (MeLPPP) doped with benzil at a concentration of 20% by weight has been measured. The introduction of benzil leads to a dramatic reduction of the polymer singlet emission. At the same time, a new band with maximum at 611 nm appears, corresponding to the phosphorescence of MeLPPP. The phosphorescence decay on the short time scale is close to an exponential law with a time decay of 15 ms. This indicates that benzil can efficiently sensitize the phosphorescence of the polymer. In addition, a broad and featureless emission is observed in the delayed luminescence spectra of benzil-doped MeLPPP, which is attributed to an exciplex formed between the polymer host and the dopant. We further observe that the delayed fluorescence is enhanced by the addition of benzil. It is concluded that the delayed fluorescence of benzil-doped MeLPPP is mainly due to the annihilation of triplet excitons on the polymer. Finally, efficient triplet-triplet energy transfer from the benzil-doped polymer to the red-emitting phosphorescent dye Pt(II)octaethylporphyrin is established. Copyright 2004 American Institute of Physics.

Perinatal death of triplet pregnancies by chorionicity.

PubMed

Kawaguchi, Haruna; Ishii, Keisuke; Yamamoto, Ryo; Hayashi, Shusaku; Mitsuda, Nobuaki

2013-07-01

The purpose of this study was to evaluate the perinatal risk of death by chorionicity at >22 weeks of gestation of triplet pregnancies. In a retrospective cohort study, the perinatal data were collected from triplet pregnancies in Japanese perinatal care centers between 1999 and 2009. We included maternal characteristics and examined the following factors: prenatal interventions, pregnancy outcome, and neonatal outcome. The association between fetal or neonatal death of triplets and chorionicity was evaluated by logistic regression analysis. After the exclusion of 253 cases, the study group comprised 701 cases: 507 trichorionic triamniotic (TT) triplet pregnancies, 144 diamniotic triamniotic (DT) triplet pregnancies, and 50 monochorionic triamniotic (MT) triplet pregnancies. The mortality rate (fetal death at >22 weeks of gestation; neonatal death) in triplets was 2.6% and included 2.1% of TT triplet pregnancies, 3.2% of DT triplet pregnancies, and 5.3% of MT triplet pregnancies. No significant risk of death was identified in DT triplet pregnancies; however, MT triplet pregnancies had a 2.6-fold greater risk (adjusted odds ratio, 2.60; 95% confidence interval, 1.17-5.76; P = .019) compared with TT triplet pregnancies. Prophylactic cervical cerclage did not reduce the perinatal mortality rate at >22 weeks of gestation in triplets. The risk of death for MT triplet pregnancies is significantly higher than that of TT triplet pregnancies; however, the risk of death for DT triplet pregnancies is not. Copyright © 2013 Mosby, Inc. All rights reserved.

Kinetic Monte Carlo simulation of the efficiency roll-off, emission color, and degradation of organic light-emitting diodes (Presentation Recording)

NASA Astrophysics Data System (ADS)

Coehoorn, Reinder; van Eersel, Harm; Bobbert, Peter A.; Janssen, Rene A. J.

2015-10-01

The performance of Organic Light Emitting Diodes (OLEDs) is determined by a complex interplay of the charge transport and excitonic processes in the active layer stack. We have developed a three-dimensional kinetic Monte Carlo (kMC) OLED simulation method which includes all these processes in an integral manner. The method employs a physically transparent mechanistic approach, and is based on measurable parameters. All processes can be followed with molecular-scale spatial resolution and with sub-nanosecond time resolution, for any layer structure and any mixture of materials. In the talk, applications to the efficiency roll-off, emission color and lifetime of white and monochrome phosphorescent OLEDs [1,2] are demonstrated, and a comparison with experimental results is given. The simulations show to which extent the triplet-polaron quenching (TPQ) and triplet-triplet-annihilation (TTA) contribute to the roll-off, and how the microscopic parameters describing these processes can be deduced properly from dedicated experiments. Degradation is treated as a result of the (accelerated) conversion of emitter molecules to non-emissive sites upon a triplet-polaron quenching (TPQ) process. The degradation rate, and hence the device lifetime, is shown to depend on the emitter concentration and on the precise type of TPQ process. Results for both single-doped and co-doped OLEDs are presented, revealing that the kMC simulations enable efficient simulation-assisted layer stack development. [1] H. van Eersel et al., Appl. Phys. Lett. 105, 143303 (2014). [2] R. Coehoorn et al., Adv. Funct. Mater. (2015), publ. online (DOI: 10.1002/adfm.201402532)

Improved color stability of white organic light-emitting diodes without interlayer between red, orange and blue emission layers

NASA Astrophysics Data System (ADS)

Xue, Kaiwen; Chen, Ping; Duan, Yu; Sheng, Ren; Han, Guangguang; Zhao, Yi

2016-03-01

We demonstrated color stability improved white phosphorescent organic light-emitting diodes (WOLEDs) based on red, orange and blue emission layers. Iridium(III) Bis(3,5-diflouro)-2-(2-pyridyl)phenyl-(2-carboxypyridyl) was doped into red emission layer (R-EML) and orange emission layer (O-EML) to lower the electrons injection barrier and facilitate the ambipolar charge carriers balance. Consequently, the recombination region was extended to the R-EML and O-EML, leading to the excellently stable spectra and the reduction of triplet-triplet annihilation. Then the resulting device with a negligible Commission International de L'Eclairage coordinates shift of (0.003, 0.007) within a wide luminance range as well as a high color rendering index of 90 was gained, which was comparable to the profit caused by the conventional method of introducing the interlayer. And the emission mechanism of the WOLEDs was also discussed.

Kinetic Monte Carlo modeling of the efficiency roll-off in a multilayer white organic light-emitting device

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

Mesta, M.; Coehoorn, R.; Bobbert, P. A.

2016-03-28

Triplet-triplet annihilation (TTA) and triplet-polaron quenching (TPQ) in organic light-emitting devices (OLEDs) lead to a roll-off of the internal quantum efficiency (IQE) with increasing current density J. We employ a kinetic Monte Carlo modeling study to analyze the measured IQE and color balance as a function of J in a multilayer hybrid white OLED that combines fluorescent blue with phosphorescent green and red emission. We investigate two models for TTA and TPQ involving the phosphorescent green and red emitters: short-range nearest-neighbor quenching and long-range Förster-type quenching. Short-range quenching predicts roll-off to occur at much higher J than measured. Taking long-rangemore » quenching with Förster radii for TTA and TPQ equal to twice the Förster radii for exciton transfer leads to a fair description of the measured IQE-J curve, with the major contribution to the roll-off coming from TPQ. The measured decrease of the ratio of phosphorescent to fluorescent component of the emitted light with increasing J is correctly predicted. A proper description of the J-dependence of the ratio of red and green phosphorescent emission needs further model refinements.« less

Current-induced spin polarization on a Pt surface: A new approach using spin-polarized positron annihilation spectroscopy

NASA Astrophysics Data System (ADS)

Kawasuso, A.; Fukaya, Y.; Maekawa, M.; Zhang, H.; Seki, T.; Yoshino, T.; Saitoh, E.; Takanashi, K.

2013-09-01

Transversely spin-polarized positrons were injected near Pt and Au surfaces under an applied electric current. The three-photon annihilation of spin-triplet positronium, which was emitted from the surfaces into vacuum, was observed. When the positron spin polarization was perpendicular to the current direction, the maximum asymmetry of the three-photon annihilation intensity was observed upon current reversal for the Pt surfaces, whereas it was significantly reduced for the Au surface. The experimental results suggest that electrons near the Pt surfaces were in-plane and transversely spin-polarized with respect to the direction of the electric current. The maximum electron spin polarization was estimated to be more than 0.01 (1%).

Organic photochemical storage of solar energy. Progress report, February 1, 1979-January 31, 1980

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

Jones, G. II

1980-02-01

Study of valence isomerization of organic compounds has focused on two mechanisms of photosensitization involving either electron donor-acceptor interaction or energy transfer. The quenching of fluorescent sensitizers by isomerizable substrates results in the formation of excited complexes. These sensitizer-substrate pairs are highly polarized, leading to changes in bond order for the substrates. For several substrates such as quadricyclene, hexamethyldewarbenzene, and a nonbornadiene derivative, this perturbation results in efficient valence isomerization. Isomerization observed on irradiation of charge transfer complexes of isomerizable substrates is consistent with a similar exciplex - template mechanism. The energy transfer mechanism of photosensitization has been studied bymore » measuring the temperature dependence of quantum yield for isomerization of dimethyl norbornadiene-2,3-dicarboxylate sensitized by benzanthrone. From temperature and quencher concentration profiles quenching constants have been obtained which are consistent with an endoergic triplet energy transfer mechanism. The thermal upconversion of the low energy triplet of benzanthrone results in a threefold increase in isomerization quantum yield over a 90/sup 0/ temperature range.« less

Low amplified spontaneous emission threshold and suppression of electroluminescence efficiency roll-off in layers doped with ter(9,9′-spirobifluorene)

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

Inoue, Munetomo; Center for Organic Photonics and Electronics Research, Kyushu University, 744 Motooka, Nishi, Fukuoka 819-0395; Matsushima, Toshinori

2016-03-28

We demonstrate that ter(9,9′-spirobifluorene) (TSBF) doped in a host matrix layer of 4,4′-bis(carbazol-9-yl)biphenyl (CBP) shows a low amplified spontaneous emission (ASE) threshold (E{sub th} = 1.0 μJ cm{sup −2}) and suppressed electroluminescence efficiency roll-off at high current densities (no roll-off up to 100 mA cm{sup −2}). One origin of the low ASE threshold is that the TSBF-doped CBP layer possesses a very large radiative decay constant (k{sub r} = 1.1 × 10{sup 9 }s{sup −1}). Singlet–triplet annihilation is almost suppressed in the TSBF-doped CBP layer, which can be ascribed to the small overlap between the emission and triplet absorption of TSBF. Also, the small energy level difference between TSBF and CBPmore » minimizes carrier trapping in TSBF, leading to the suppression of singlet–polaron annihilation. TSBF showed one of the lowest E{sub th} and the most suppressed efficiency roll-off among organic laser dyes investigated in this study and, therefore, is believed to be a promising candidate to realize electrically pumped organic semiconductor laser diodes in the future.« less

The entangled triplet pair state in acene and heteroacene materials

PubMed Central

Yong, Chaw Keong; Musser, Andrew J.; Bayliss, Sam L.; Lukman, Steven; Tamura, Hiroyuki; Bubnova, Olga; Hallani, Rawad K.; Meneau, Aurélie; Resel, Roland; Maruyama, Munetaka; Hotta, Shu; Herz, Laura M.; Beljonne, David; Anthony, John E.; Clark, Jenny; Sirringhaus, Henning

2017-01-01

Entanglement of states is one of the most surprising and counter-intuitive consequences of quantum mechanics, with potent applications in cryptography and computing. In organic materials, one particularly significant manifestation is the spin-entangled triplet-pair state, which mediates the spin-conserving fission of one spin-0 singlet exciton into two spin-1 triplet excitons. Despite long theoretical and experimental exploration, the nature of the triplet-pair state and inter-triplet interactions have proved elusive. Here we use a range of organic semiconductors that undergo singlet exciton fission to reveal the photophysical properties of entangled triplet-pair states. We find that the triplet pair is bound with respect to free triplets with an energy that is largely material independent (∼30 meV). During its lifetime, the component triplets behave cooperatively as a singlet and emit light through a Herzberg–Teller-type mechanism, resulting in vibronically structured photoluminescence. In photovoltaic blends, charge transfer can occur from the bound triplet pairs with >100% photon-to-charge conversion efficiency. PMID:28699637

The entangled triplet pair state in acene and heteroacene materials

NASA Astrophysics Data System (ADS)

Yong, Chaw Keong; Musser, Andrew J.; Bayliss, Sam L.; Lukman, Steven; Tamura, Hiroyuki; Bubnova, Olga; Hallani, Rawad K.; Meneau, Aurélie; Resel, Roland; Maruyama, Munetaka; Hotta, Shu; Herz, Laura M.; Beljonne, David; Anthony, John E.; Clark, Jenny; Sirringhaus, Henning

2017-07-01

Entanglement of states is one of the most surprising and counter-intuitive consequences of quantum mechanics, with potent applications in cryptography and computing. In organic materials, one particularly significant manifestation is the spin-entangled triplet-pair state, which mediates the spin-conserving fission of one spin-0 singlet exciton into two spin-1 triplet excitons. Despite long theoretical and experimental exploration, the nature of the triplet-pair state and inter-triplet interactions have proved elusive. Here we use a range of organic semiconductors that undergo singlet exciton fission to reveal the photophysical properties of entangled triplet-pair states. We find that the triplet pair is bound with respect to free triplets with an energy that is largely material independent (~30 meV). During its lifetime, the component triplets behave cooperatively as a singlet and emit light through a Herzberg-Teller-type mechanism, resulting in vibronically structured photoluminescence. In photovoltaic blends, charge transfer can occur from the bound triplet pairs with >100% photon-to-charge conversion efficiency.

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

Makarov, Nikolay S.; Lin, Qianglu; Pietryga, Jeffrey M.

One source of efficiency losses in photovoltaic cells is their transparency toward solar photons with energies below the band gap of the absorbing layer. This loss can be reduced using a process of up-conversion whereby two or more sub-band-gap photons generate a single above-gap exciton. Traditional approaches to up-conversion, such as nonlinear two-photon absorption (2PA) or triplet fusion, suffer from low efficiency at solar light intensities, a narrow absorption bandwidth, nonoptimal absorption energies, and difficulties for implementing in practical devices. We show that these deficiencies can be alleviated using the effect of Auger up-conversion in thick-shell PbSe/CdSe quantum dots. Thismore » process relies on Auger recombination whereby two low-energy, core-based excitons are converted into a single higher-energy, shell-based exciton. When compared to their monocomponent counterparts, the tailored PbSe/CdSe heterostructures feature enhanced absorption cross-sections, a higher efficiency of the “productive” Auger pathway involving re-excitation of a hole, and longer lifetimes of both core- and shell-localized excitons. These features lead to effective up-conversion cross-sections that are more than 6 orders of magnitude higher than for standard nonlinear 2PA, which allows for efficient up-conversion of continuous wave infrared light at intensities as low as a few watts per square centimeter.« less

Molecular-Barrier-Enhanced Aromatic Fluorophores in Cocrystals with Unity Quantum Efficiency.

PubMed

Ye, Huanqing; Liu, Guangfeng; Liu, Sheng; Casanova, David; Ye, Xin; Tao, Xutang; Zhang, Qichun; Xiong, Qihua

2018-02-12

Singlet-triplet conversion in organic light-emitting materials introduces non-emissive (dark) and long-lived triplet states, which represents a significant challenge in constraining the optical properties. There have been considerable attempts at separating singlets and triplets in long-chain polymers, scavenging triplets, and quenching triplets with heavy metals; nonetheless, such triplet-induced loss cannot be fully eliminated. Herein, a new strategy of crafting a periodic molecular barrier into the π-conjugated matrices of organic aromatic fluorophores is reported. The molecular barriers effectively block the singlet-to-triplet pathway, resulting in near-unity photoluminescence quantum efficiency (PLQE) of the organic fluorophores. The transient optical spectroscopy measurements confirm the absence of the triplet absorption. These studies provide a general approach to preventing the formation of dark triplet states in organic semiconductors and bring new opportunities for the development of advanced organic optics and photonics. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Auger Up-Conversion of Low-Intensity Infrared Light in Engineered Quantum Dots

DOE PAGES

Makarov, Nikolay S.; Lin, Qianglu; Pietryga, Jeffrey M.; ...

2016-11-29

One source of efficiency losses in photovoltaic cells is their transparency toward solar photons with energies below the band gap of the absorbing layer. This loss can be reduced using a process of up-conversion whereby two or more sub-band-gap photons generate a single above-gap exciton. Traditional approaches to up-conversion, such as nonlinear two-photon absorption (2PA) or triplet fusion, suffer from low efficiency at solar light intensities, a narrow absorption bandwidth, nonoptimal absorption energies, and difficulties for implementing in practical devices. We show that these deficiencies can be alleviated using the effect of Auger up-conversion in thick-shell PbSe/CdSe quantum dots. Thismore » process relies on Auger recombination whereby two low-energy, core-based excitons are converted into a single higher-energy, shell-based exciton. When compared to their monocomponent counterparts, the tailored PbSe/CdSe heterostructures feature enhanced absorption cross-sections, a higher efficiency of the “productive” Auger pathway involving re-excitation of a hole, and longer lifetimes of both core- and shell-localized excitons. These features lead to effective up-conversion cross-sections that are more than 6 orders of magnitude higher than for standard nonlinear 2PA, which allows for efficient up-conversion of continuous wave infrared light at intensities as low as a few watts per square centimeter.« less

Magnetic Field Effect in Conjugated Molecules-Based Devices

DTIC Science & Technology

2017-10-23

triplet annihilation process (TTA) process in charge- balanced polymer light emitting diode (PLED) containing a super yellow poly-(phenylene vinylene...current density. Our results demonstrate a clear correlation between TTA process and current density as well as temperature in charge- balanced SY-PPV...dimethyl sulfoxide (DMSO) (7:3, v/v) at 60 °C for 12 h inside the nitrogen -filled glove box. The perovskite films were spin-cast by a consecutive two-step

Mimicking the photosynthetic triplet energy-transfer relay

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

Gust, D.; Moore, T.A.; Moore, A.L.

1993-06-30

In the reaction centers of photosynthetic organisms, chlorophyll triplet states are sometimes formed by recombination of charge-separated intermediates. These triplets are excellent sensitizers for singlet oxygen formation. Carotenoid polyenes can provide photoprotection from singlet oxygen generation by rapidly quenching chlorophyll triplet states via triplet-triplet energy transfer. Because in bacteria the reaction center carotenoid is not located adjacent to the bacteriochlorophyll special pair, which is the origin of the charge separation, it has been postulated that quenching may occur via a triplet relay involving an intermediate chlorophyll monomer. We now report the synthesis and spectroscopic study of a covalently linked carotenoidmore » (C)-porphyrin (P)-pyropheophorbide (Ppd) triad molecule which mimics this triplet relay. The pyropheophorbide singlet-state C-P-[sup 1]Ppd (generated by direct excitation or energy transfer from the attached porphyrin) undergoes intersystem crossing to the triplet C-P-[sup 3]Ppd. In oxygen-free solutions, this triplet decays to [sup 3]C-p-Ppd through a triplet-transfer relay involving an intermediate C-[sup 3]P-Ppd species. In aerated solutions, quenching of C-P-[sup 3]Ppd by the attached carotenoid competes with singlet oxygen sensitization and thus provides a degree of photoprotection. In a similar traid containing a zinc porphyrin moiety, triplet transfer is slow due to the higher energy of the C-[sup 3]P[sub Zn]-Ppd intermediate, and photoprotection via the relay is nonexistent. The triplet relay ceases to function at low temperatures in both the natural and biomimetic cases due to the endergonicity of the first step. 37 refs., 6 figs., 1 tab.« less

Sensitized and heavy atom induced production of acenaphthylene triplet: A laser flash photolysis study

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

Samanta, A.; Fessenden, R.W.

1989-07-27

The triplet state of acenaphthylene has been examined by nanosecond laser flash photolysis using sensitization and heavy atom perturbation techniques. Although acenaphthylene does not form any observable triplet upon direct flash excitation, a transient with microsecond lifetime ({lambda}{sub max} = 315 nm) is observable when a solution of the sample is excited by sensitizers (benzophenone, thioxanthone, benzil). This transient is ascribed to the triplet of acenaphthylene on the basis of its quenching behavior toward oxygen, ferrocene, azulene, and {beta}-carotene. Quantitative data concerning the triplet-triplet absorption and quenching constants are presented. The triplet energy is estimated to lie between 46 andmore » 47 kcal/mol. The triplet can also be produced by direct excitation in solvents containing heavy atoms (ethyl bromide, ethyl iodide). The triplet yield is found to increase with an increase of the amount of the heavy atom containing solvent. No saturation limit is obtained. These facts together with the effect of heavy atoms on the T{sub 1} {yields} S{sub 0} process allow the differing behavior of ethyl bromide and ethyl iodide on the photodimerization process of acenaphthylene to be explained. Triplet-state parameters (extinction coefficient and triplet yield) have been estimated in these solvents by the energy-transfer technique and actinometry.« less

Definition and determination of the triplet-triplet energy transfer reaction coordinate.

PubMed

Zapata, Felipe; Marazzi, Marco; Castaño, Obis; Acuña, A Ulises; Frutos, Luis Manuel

2014-01-21

A definition of the triplet-triplet energy transfer reaction coordinate within the very weak electronic coupling limit is proposed, and a novel theoretical formalism is developed for its quantitative determination in terms of internal coordinates The present formalism permits (i) the separation of donor and acceptor contributions to the reaction coordinate, (ii) the identification of the intrinsic role of donor and acceptor in the triplet energy transfer process, and (iii) the quantification of the effect of every internal coordinate on the transfer process. This formalism is general and can be applied to classical as well as to nonvertical triplet energy transfer processes. The utility of the novel formalism is demonstrated here by its application to the paradigm of nonvertical triplet-triplet energy transfer involving cis-stilbene as acceptor molecule. In this way the effect of each internal molecular coordinate in promoting the transfer rate, from triplet donors in the low and high-energy limit, could be analyzed in detail.

Definition and determination of the triplet-triplet energy transfer reaction coordinate

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

Zapata, Felipe; Marazzi, Marco; Castaño, Obis

2014-01-21

A definition of the triplet-triplet energy transfer reaction coordinate within the very weak electronic coupling limit is proposed, and a novel theoretical formalism is developed for its quantitative determination in terms of internal coordinates The present formalism permits (i) the separation of donor and acceptor contributions to the reaction coordinate, (ii) the identification of the intrinsic role of donor and acceptor in the triplet energy transfer process, and (iii) the quantification of the effect of every internal coordinate on the transfer process. This formalism is general and can be applied to classical as well as to nonvertical triplet energy transfermore » processes. The utility of the novel formalism is demonstrated here by its application to the paradigm of nonvertical triplet-triplet energy transfer involving cis-stilbene as acceptor molecule. In this way the effect of each internal molecular coordinate in promoting the transfer rate, from triplet donors in the low and high-energy limit, could be analyzed in detail.« less

Dual emission behavior of phenyleneethynylene gold(I) complexes dictated by intersystem crossing: a theoretical perspective.

PubMed

Wang, Li; Li, Yuanyuan; Zhang, Yanxin; He, Hongqing; Zhang, Jinglai

2015-02-25

In commonly studied gold(I) complexes with oligo (o-, p-, or m-phenyleneethynylene) (PE) ligands, an intriguing photophysical behavior is dual emission composed of fluorescence from S1 and phosphorescence from T1 which is dictated by effective intersystem crossing (ISC) process. In order to explore the salient photodynamics of such oligo-PE gold(I) complexes effectively, we have deliberately chosen three model complexes, namely, Ph-C≡C-Au(PMe3) (1a') and Ph-C≡C-(1,m)C6H4-C≡C-Au(PMe3) (m=4, 2a'; m=3, 3a') in place of the real system. Firstly, electronic structure methods based on DFT and TD-DFT are utilized to perform optimization calculations for the ground- and lowest-lying excited states, respectively. Next, basic photophysical properties including absorption and emission spectra are investigated by TD-DFT under the optimized geometries. Besides, on the basis of the electronic spectra herein, we succeed in searching for surface intersections as the minima on the seam of singlet-triplet surface crossings (SCs) at the CASSCF level of theory. By integration of the results available, the process of delayed fluorescence of triplet-triplet annihilation (TTA) and phosphorescence was displayed in detail with SCs playing the lead in monitoring the ISC. Copyright © 2014 Elsevier B.V. All rights reserved.

Electroluminescence Properties of IrQ(ppy)2 Dual-Emitter Organometallic Compound in Organic Light-Emitting Devices

NASA Astrophysics Data System (ADS)

Ciobotaru, Constantin Claudiu; Polosan, Silviu; Ciobotaru, Iulia Corina

2018-02-01

This paper reports the influence of the charge carrier mobility on the electroluminescent properties of a dual-emitter organometallic compound dispersed in two conjugated organic small-molecule host materials and embedded in organic light-emitting devices (OLEDs). The electroluminescent processes in OLEDs are strongly influenced by the host-guest interaction. The charge carrier mobility in the host material plays an important role in the electroluminescent processes but also depends on the triplet-triplet interaction with the organometallic compound. The low charge carrier mobility in 4,4'-bis( N-carbazolyl)-1,1'-biphenyl (CBP) host material reduces the electroluminescent processes, but they are slightly enhanced by the triplet-triplet exothermic charge transfer. The higher charge carrier mobility in the case of N, N'-bis(3-methylphenyl)- N, N'-diphenylbenzidine (TPD) host material influences the electroluminescent processes by the endothermic energy transfer at room temperature, which facilitates the triplet-triplet harvesting in the host-guest system. The excitation is transferred to the guest molecules by triplet-triplet interaction as a Dexter transfer, which occurs by endothermic transfer from the triplet exciton in the host to the triplet exciton in the guest.

Selectively Modulating Triplet Exciton Formation in Host Materials for Highly Efficient Blue Electrophosphorescence.

PubMed

Li, Huanhuan; Bi, Ran; Chen, Ting; Yuan, Kai; Chen, Runfeng; Tao, Ye; Zhang, Hongmei; Zheng, Chao; Huang, Wei

2016-03-23

The concept of limiting the triplet exciton formation to fundamentally alleviate triplet-involved quenching effects is introduced to construct host materials for highly efficient and stable blue phosphorescent organic light-emitting diodes (PhOLEDs). The low triplet exciton formation is realized by small triplet exciton formation fraction and rate with high binding energy and high reorganization energy of triplet exciton. Demonstrated in two analogue molecules in conventional donor-acceptor molecule structure for bipolar charge injection and transport with nearly the same frontier orbital energy levels and triplet excited energies, the new concept host material shows significantly suppressed triplet exciton formation in the host to avoid quenching effects, leading to much improved device efficiencies and stabilities. The low-voltage-driving blue PhOLED devices exhibit maximum efficiencies of 43.7 cd A(-1) for current efficiency, 32.7 lm W(-1) for power efficiency, and 20.7% for external quantum efficiency with low roll-off and remarkable relative quenching effect reduction ratio up to 41%. Our fundamental solution for preventing quenching effects of long-lived triplet excitons provides exciting opportunities for fabricating high-performance devices using the advanced host materials with intrinsically small triplet exciton formation cross section.

Triplet correlation in sheared suspensions of Brownian particles

NASA Astrophysics Data System (ADS)

Yurkovetsky, Yevgeny; Morris, Jeffrey F.

2006-05-01

Triplet microstructure of sheared concentrated suspensions of Brownian monodisperse spherical particles is studied by sampling realizations of a three-dimensional unit cell subject to periodic boundary conditions obtained in accelerated Stokesian dynamics simulations. Triplets are regarded as a bridge between particle pairs and many-particle clusters thought responsible for shear thickening. Triplet-correlation data for weakly sheared near-equilibrium systems display an excluded volume effect of accumulated correlation for equilateral contacting triplets. As the Péclet number increases, there is a change in the preferred contacting isosceles triplet configuration, away from the "closed" triplet where the particles lie at the vertices of an equilateral triangle and toward the fully extended rod-like linear arrangement termed the "open" triplet. This transition is most pronounced for triplets lying in the plane of shear, where the open triplets' angular orientation with respect to the flow is very similar to that of a contacting pair. The correlation of suspension rheology to observed structure signals onset of larger clusters. An investigation of the predictive ability of Kirkwood's superposition approximation (KSA) provides valuable insights into the relationship between the pair and triplet probability distributions and helps achieve a better and more detailed understanding of the interplay of the pair and triplet dynamics. The KSA is seen more successfully to predict the shape of isosceles contacting triplet nonequilibrium distributions in the plane of shear than for similar configurations in equilibrium hard-sphere systems; in the sheared case, the discrepancies in magnitudes of distribution peaks are attributable to two interaction effects when pair average trajectories and locations of particles change in response to real, or "hard," and probabilistically favored ("soft") neighboring excluded volumes and, in the case of open triplets, due to changes in the correlation of the farthest separated pair caused by the fixed presence of the particle in the middle.

Singlet-to-triplet intermediates and triplet exciton dynamics in pentacene thinfilms

NASA Astrophysics Data System (ADS)

Thorsmolle, Verner; Korber, Michael; Obergfell, Emanuel; Kuhlman, Thomas; Campbell, Ian; Crone, Brian; Taylor, Antoinette; Averitt, Richard; Demsar, Jure

Singlet-to-triplet fission in organic semiconductors is a spin-conserving multiexciton process in which one spin-zero singlet excitation is converted into two spin-one triplet excitations on an ultrafast timescale. Current scientific interest into this carrier multiplication process is largely driven by prospects of enhancing the efficiency in photovoltaic applications by generating two long-lived triplet excitons by one photon. The fission process is known to involve intermediate states, known as correlated triplet pairs, with an overall singlet character, before being interchanged into uncorrelated triplets. Here we use broadband femtosecond real-time spectroscopy to study the excited state dynamics in pentacene thin films, elucidating the fission process and the role of intermediate triplet states. VKT and AJT acknowledge support by the LDRD program at Los Alamos National Laboratory and the Department of Energy, Grant No. DE-FG02-04ER118. MK, MO and JD acknowledge support by the Alexander von Humboldt Foundation.

Spin-Triplet Pairing Induced by Spin-Singlet Interactions in Noncentrosymmetric Superconductors

NASA Astrophysics Data System (ADS)

Matsuzaki, Tomoaki; Shimahara, Hiroshi

2017-02-01

In noncentrosymmetric superconductors, we examine the effect of the difference between the intraband and interband interactions, which becomes more important when the band splitting increases. We define the difference ΔVμ between their coupling constants, i.e., that between the intraband and interband hopping energies of intraband Cooper pairs. Here, the subscript μ of ΔVμ indicates that the interactions scatter the spin-singlet and spin-triplet pairs when μ = 0 and μ = 1,2,3, respectively. It is shown that the strong antisymmetric spin-orbit interaction reverses the target spin parity of the interaction: it converts the spin-singlet and spin-triplet interactions represented by ΔV0 and ΔVμ>0 into effective spin-triplet and spin-singlet pairing interactions, respectively. Hence, for example, triplet pairing can be induced solely by the singlet interaction ΔV0. We name the pairing symmetry of the system after that of the intraband Cooper pair wave function, but with an odd-parity phase factor excluded. The pairing symmetry must then be even, even for the triplet component, and the following results are obtained. When ΔVμ is small, the spin-triplet p-wave interactions induce spin-triplet s-wave and spin-triplet d-wave pairings in the regions where the repulsive singlet s-wave interaction is weak and strong, respectively. When ΔV0 is large, a repulsive interband spin-singlet interaction can stabilize spin-triplet pairing. When the Rashba interaction is adopted for the spin-orbit interaction, the spin-triplet pairing interactions mediated by transverse magnetic fluctuations do not contribute to triplet pairing.

Inert Higgs Doublet Dark Matter in Type-II Seesaw

NASA Astrophysics Data System (ADS)

Chen, Chuan-Hung; Nomura, Takaaki

2016-04-01

Weakly interacting massive particle (WIMP) as a dark matter (DM) candidate is further inspired by recent AMS-02 data, which confirm the excess of positron fraction observed earlier by PAMELA and Fermi-LAT experiments. Additionally, the excess of positron+electron flux is still significant in the measurement of Fermi-LAT. For solving the problem of massive neutrinos and observed excess of cosmic-ray by DM annihilation, we study the model with an inert Higgs doublet (IHD) in the framework of type-II seesaw mechanism by imposing a Z2 symmetry on the IHD, where the lightest particle of IHD is the DM candidate while the neutrino masses origin from the Higgs triplet in type-II seesaw model. We calculate the cosmic-ray production in our model and find that if leptonic triplet decays are dominant, the observed excess of positron/electron flux could be explained well in normal ordered neutrino mass spectrum, when the constraints of DM relic density and comic-ray antiproton spectrum are taken into account.

Galaxy triplets in Sloan Digital Sky Survey Data Release 7 - II. A connection with compact groups?

NASA Astrophysics Data System (ADS)

Duplancic, Fernanda; O'Mill, Ana Laura; Lambas, Diego G.; Sodré, Laerte; Alonso, Sol

2013-08-01

We analyse a sample of 71 triplets of luminous galaxies derived from the work of O'Mill et al. We compare the properties of triplets and their members with those of control samples of compact groups, the 10 brightest members of rich clusters and galaxies in pairs. The triplets are restricted to have members with spectroscopic redshifts in the range 0.01 ≤ z ≤ 0.14 and absolute r-band luminosities brighter than Mr = -20.5. For these member galaxies, we analyse the stellar mass content, the star formation rates, the Dn(4000) parameter and (Mg - Mr) colour index. Since galaxies in triplets may finally merge in a single system, we analyse different global properties of these systems. We calculate the probability that the properties of galaxies in triplets are strongly correlated. We also study total star formation activity and global colours, and define the triplet compactness as a measure of the percentage of the system total area that is filled by the light of member galaxies. We concentrate in the comparison of our results with those of compact groups to assess how the triplets are a natural extension of these compact systems. Our analysis suggests that triplet galaxy members behave similarly to compact group members and galaxies in rich clusters. We also find that systems comprising three blue, star-forming, young stellar population galaxies (blue triplets) are most probably real systems and not a chance configuration of interloping galaxies. The same holds for triplets composed of three red, non-star-forming galaxies, showing the correlation of galaxy properties in these systems. From the analysis of the triplet as a whole, we conclude that, at a given total stellar mass content, triplets show a total star formation activity and global colours similar to compact groups. However, blue triplets show a high total star formation activity with a lower stellar mass content. From an analysis of the compactness parameter of the systems we find that light is even more concentrated in triplets than in compact groups. We propose that triplets composed of three luminous galaxies, should not be considered as an analogous of galaxy pairs with a third extra member, but rather they are a natural extension of compact groups.

Identification of a triplet pair intermediate in singlet exciton fission in solution

PubMed Central

Stern, Hannah L.; Musser, Andrew J.; Gelinas, Simon; Parkinson, Patrick; Herz, Laura M.; Bruzek, Matthew J.; Anthony, John; Friend, Richard H.; Walker, Brian J.

2015-01-01

Singlet exciton fission is the spin-conserving transformation of one spin-singlet exciton into two spin-triplet excitons. This exciton multiplication mechanism offers an attractive route to solar cells that circumvent the single-junction Shockley–Queisser limit. Most theoretical descriptions of singlet fission invoke an intermediate state of a pair of spin-triplet excitons coupled into an overall spin-singlet configuration, but such a state has never been optically observed. In solution, we show that the dynamics of fission are diffusion limited and enable the isolation of an intermediate species. In concentrated solutions of bis(triisopropylsilylethynyl)[TIPS]—tetracene we find rapid (<100 ps) formation of excimers and a slower (∼10 ns) break up of the excimer to two triplet exciton-bearing free molecules. These excimers are spectroscopically distinct from singlet and triplet excitons, yet possess both singlet and triplet characteristics, enabling identification as a triplet pair state. We find that this triplet pair state is significantly stabilized relative to free triplet excitons, and that it plays a critical role in the efficient endothermic singlet fission process. PMID:26060309

Tetrahymena Poc1 ensures proper intertriplet microtubule linkages to maintain basal body integrity

PubMed Central

Meehl, Janet B.; Bayless, Brian A.; Giddings, Thomas H.; Pearson, Chad G.; Winey, Mark

2016-01-01

Basal bodies comprise nine symmetric triplet microtubules that anchor forces produced by the asymmetric beat pattern of motile cilia. The ciliopathy protein Poc1 stabilizes basal bodies through an unknown mechanism. In poc1∆ cells, electron tomography reveals subtle defects in the organization of intertriplet linkers (A-C linkers) that connect adjacent triplet microtubules. Complete triplet microtubules are lost preferentially near the posterior face of the basal body. Basal bodies that are missing triplets likely remain competent to assemble new basal bodies with nine triplet microtubules, suggesting that the mother basal body microtubule structure does not template the daughter. Our data indicate that Poc1 stabilizes basal body triplet microtubules through linkers between neighboring triplets. Without this stabilization, specific triplet microtubules within the basal body are more susceptible to loss, probably due to force distribution within the basal body during ciliary beating. This work provides insights into how the ciliopathy protein Poc1 maintains basal body integrity. PMID:27251062

Parent-infant synchrony and the social-emotional development of triplets.

PubMed

Feldman, Ruth; Eidelman, Arthur I

2004-11-01

To study the social-emotional development of triplets, 23 sets of triplets, 23 sets of twins, and 23 singleton infants (N=138) were followed from birth to 2 years. Maternal depression and social support were assessed in the postpartum period, mother-infant and father-infant interaction and the home environment were observed at 3 months, a separation-reunion episode and a maternal interview were conducted at 12 months, and infant behavior problems were evaluated at 24 months. Lower parent-infant synchrony was observed for triplets. Triplets showed less distress during maternal separation and less approach at reunion. Mothers reported lower adjustment and differentiation among siblings for triplets than for twins. Higher internalizing problems were reported for triplets, and the triplet with intrauterine growth retardation showed the poorest outcomes. Behavior problems were predicted by medical risk, maternal depression, parent-infant synchrony, infant approach, and mother adjustment. Discussion focuses on developmental risk when the exclusivity of the parent-infant relationship is compromised. (c) 2004 APA, all rights reserved

[An analysis of cephalometric polygons in 21 sets of triplets].

PubMed

Kosovcević, Z; Marković, M

1991-01-01

Lateral cephalometric radiographs of 21 sets of triplets (4 monozygotic, 12 dizygotic and 5 three zygotic) were used for this study. The following two polygons were analysed: SNA and NSAr Go Me. Superimposition of the cephalometric tracings was made on the S-N line with S as the registration point. Intra- and inter-set comparisons between monozygotic (MZ), dizygotic (DZ) and three zygotic (TZ) triplets were made. Members of MZ triplets demonstrated the greatest similarity in size and form of the polygons. The second greatest similarity was found between MZ members of the DZ triplets, while the third DZ member of all such triplets showed much higher difference compared with the MZ members. Finally, triplets of TZ sets demonstrated the greatest difference between each other. The results obtained from this study indicated that genetic factors played a dominant role in growth and development of the craniofacial complex. However, difference found between members of MZ triplets suggested an importance of environmental factors in these processes as well.

Triplet Transport to and Trapping by Acceptor End Groups on Conjugated Polyfluorene Chains

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

Sreearunothai, P.; Miller, J.; Estrada, A.

2011-08-31

Triplet excited states created in polyfluorene (pF) molecules having average lengths up to 170 repeat units were transported to and captured by trap groups at the ends in less {approx}40 ns. Almost all of the triplets attached to the chains reached the trap groups, ruling out the presence of substantial numbers of defects that prevent transport. The transport yields a diffusion coefficient D of at least 3 x 10{sup -4} cm{sup 2} s{sup -1}, which is 30 times typical molecular diffusion and close to a value for triplet transport reported by Keller (J. Am. Chem. Soc.2011, 133, 11289-11298). The tripletmore » states were created in solution by pulse radiolysis; time resolution was limited by the rate of attachment of triplets to the pF chains. Naphthylimide (NI) or anthraquinone (AQ) groups attached to the ends of the chains acted as traps for the triplets, although AQ would not have been expected to serve as a trap on the basis of triplet energies of the separate molecules. The depths of the NI and AQ triplet traps were determined by intermolecular triplet transfer equilibria and temperature dependence. The trap depths are shallow, just a few times thermal energy for both, so a small fraction of the triplets reside in the pF chains in equilibrium with the end-trapped triplets. Trapping by AQ appears to arise from charge transfer interactions between the pF chains and the electron-accepting AQ groups. Absorption bands of the end-trapped triplet states are similar in peak wavelength (760 nm) and shape to the 760 nm bands of triplets in the pF chains but have reduced intensities. When an electron donor, N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD), is added to the solution, it reacts with the end-trapped triplets to remove the 760 nm bands and to make the trapping irreversible. New bands created upon reaction with TMPD may be due to charge transfer states.« less

Dielectric controlled excited state relaxation pathways of a representative push-pull stilbene: a mechanistic study using femtosecond fluorescence up-conversion technique.

PubMed

Rafiq, Shahnawaz; Sen, Pratik

2013-02-28

Femtosecond fluorescence up-conversion technique was employed to reinvestigate the intriguing dependence of fluorescence quantum yield of trans-4-dimethylamino-4(')-nitrostilbene (DNS) on dielectric properties of the media. In polar solvents, such as methanol and acetonitrile, the two time components of the fluorescence transients were assigned to intramolecular charge transfer (ICT) dynamics and to the depletion of the ICT state to the ground state via internal conversion along the torsional coordinate of nitro moiety. The viscosity independence of the first time component indicates the absence of any torsional coordinate in the charge transfer process. In slightly polar solvent (carbon tetrachloride) the fluorescence transients show a triple exponential behavior. The first time component was assigned to the formation of the ICT state on a 2 ps time scale. Second time component was assigned to the relaxation of the ICT state via two torsion controlled channels. First channel involves the torsional motion about the central double bond leading to the trans-cis isomerization via a conical intersection or avoided crossing. The other channel contributing to the depopulation of ICT state involves the torsional coordinates of dimethylanilino and∕or nitrophenyl moieties and leads to the formation of a conformationally relaxed state, which subsequently relaxes back to the ground state radiatively, and is responsible for the high fluorescence quantum yield of DNS in slightly polar solvents such as carbon tetrachloride, toluene, etc. The excited singlet state which is having a dominant π-π∗ character may also decay via intersystem crossing to the n-π∗ triplet manifold and thus accounts for the observed triplet yield of the molecule in slightly polar solvents.

Dielectric controlled excited state relaxation pathways of a representative push-pull stilbene: A mechanistic study using femtosecond fluorescence up-conversion technique

NASA Astrophysics Data System (ADS)

Rafiq, Shahnawaz; Sen, Pratik

2013-02-01

Femtosecond fluorescence up-conversion technique was employed to reinvestigate the intriguing dependence of fluorescence quantum yield of trans-4-dimethylamino-4'-nitrostilbene (DNS) on dielectric properties of the media. In polar solvents, such as methanol and acetonitrile, the two time components of the fluorescence transients were assigned to intramolecular charge transfer (ICT) dynamics and to the depletion of the ICT state to the ground state via internal conversion along the torsional coordinate of nitro moiety. The viscosity independence of the first time component indicates the absence of any torsional coordinate in the charge transfer process. In slightly polar solvent (carbon tetrachloride) the fluorescence transients show a triple exponential behavior. The first time component was assigned to the formation of the ICT state on a 2 ps time scale. Second time component was assigned to the relaxation of the ICT state via two torsion controlled channels. First channel involves the torsional motion about the central double bond leading to the trans-cis isomerization via a conical intersection or avoided crossing. The other channel contributing to the depopulation of ICT state involves the torsional coordinates of dimethylanilino and/or nitrophenyl moieties and leads to the formation of a conformationally relaxed state, which subsequently relaxes back to the ground state radiatively, and is responsible for the high fluorescence quantum yield of DNS in slightly polar solvents such as carbon tetrachloride, toluene, etc. The excited singlet state which is having a dominant π-π* character may also decay via intersystem crossing to the n-π* triplet manifold and thus accounts for the observed triplet yield of the molecule in slightly polar solvents.

Effect of horizontal molecular orientation on triplet-exciton diffusion in amorphous organic films

NASA Astrophysics Data System (ADS)

Sawabe, T.; Takasu, I.; Yonehara, T.; Ono, T.; Yoshida, J.; Enomoto, S.; Amemiya, I.; Adachi, C.

2012-09-01

Triplet harvesting is a candidate technology for highly efficient and long-life white OLEDs, where green or red phosphorescent emitters are activated by the triplet-excitons diffused from blue fluorescent emitters. We examined two oxadiazole-based electron transport materials with different horizontal molecular orientation as a triplet-exciton diffusion layer (TDL) in triplet-harvesting OLEDs. The device characteristics and the transient electroluminescent analyses of the red phosphorescent emitter showed that the triplet-exciton diffusion was more effective in the highly oriented TDL. The results are ascribed to the strong orbital overlap between the oriented molecules, which provides rapid electron exchange (Dexter energy transfer) in the TDL.

Photoinduced triplet-triplet energy transfer via the 2-ureido-4[1H]-pyrimidinone self-complementary quadruple hydrogen-bonded module.

PubMed

Wang, Su-Min; Yu, Mao-Lin; Ding, Jie; Tung, Chen-Ho; Wu, Li-Zhu

2008-05-01

Phosphorescence quenching and flash photolysis experiments demonstrate that photoinduced intra-assembly triplet-triplet energy transfer can take place via a 2-ureido-4[1H]-pyrimidinone-bridged benzophenone-naphthalene assembly I with a rate constant of 3.0 x 106 s-1 and an efficiency of 95% in CH2Cl2. This new finding suggests that with high binding strength and directionality, the 2-ureido-4[1H]-pyrimidinone hydrogen-bonded module may serve as a new model to illustrate the fundamental principles governing the triplet-triplet energy-transfer process through hydrogen bonds.

Toward Triplet Ground State NaLi Molecules

NASA Astrophysics Data System (ADS)

Ebadi, Sepehr; Jamison, Alan; Rvachov, Timur; Jing, Li; Son, Hyungmok; Jiang, Yijun; Zwierlein, Martin; Ketterle, Wolfgang

2016-05-01

The NaLi molecule is expected to have a long lifetime in the triplet ground-state due to its fermionic nature, large rotational constant, and weak spin-orbit coupling. The triplet state has both electric and magnetic dipole moments, affording unique opportunities in quantum simulation and ultracold chemistry. We have mapped the excited state NaLi triplet potential by means of photoassociation spectroscopy. We report on this and our further progress toward the creation of the triplet ground-state molecules using STIRAP. NSF, ARO-MURI, Samsung, NSERC.

Experimental Study of the Triplet Synchronization of Coupled Nonidentical Mechanical Metronomes

PubMed Central

Jia, Ji; Song, Zhiwen; Liu, Weiqing; Kurths, Jürgen; Xiao, Jinghua

2015-01-01

Triplet synchrony is an interesting state when the phases and the frequencies of three coupled oscillators fulfill the conditions of a triplet locking, whereas every pair of systems remains asynchronous. Experimental observation of triplet synchrony is firstly realized in three coupled nonidentical mechanical metronomes. A more direct method based on the phase diagram is proposed to observe and determine triplet synchronization. Our results show that the stable triplet synchrony is observed in several intervals of the parameter space. Moreover, the experimental results are verified according to the theoretical model of the coupled metronomes. The outcomes are useful to understand the inner regimes of collective dynamics in coupled oscillators. PMID:26598175

One-way Z→E isomerization around the double bond of N-methoxy- 1- (2-anthryl) ethanimine in the excited triplet state. Direct observation of one-way isomerization from Z triplet to E triplet of the C dbnd N bond

NASA Astrophysics Data System (ADS)

Arai, Tatsuo; Furuya, Yasunori; Furuuchi, Hideo; Tokumaru, Katsumi

1993-09-01

On direct as well as benzil-sensitized irradiation in degassed benzene N-methoxy-1-(2-anthryl) ethanimine ( I), ArC (CH 3) dbnd N sbnd OCH 3 (Ar: 2-anthryl), underwent one-way Z→E isomerization through a quantum chain process. The barrier to Z→E isomerization of I in the excited triplet state was determined by directly observing the change of T—T absorption spectra from the Z triplet to the E triplet. Based on these results the potential energy surface of photoisomerization of I is discussed.

Direct observation of triplet energy transfer from semiconductor nanocrystals.

PubMed

Mongin, Cédric; Garakyaraghi, Sofia; Razgoniaeva, Natalia; Zamkov, Mikhail; Castellano, Felix N

2016-01-22

Triplet excitons are pervasive in both organic and inorganic semiconductors but generally remain confined to the material in which they originate. We demonstrated by transient absorption spectroscopy that cadmium selenide semiconductor nanoparticles, selectively excited by green light, engage in interfacial Dexter-like triplet-triplet energy transfer with surface-anchored polyaromatic carboxylic acid acceptors, extending the excited-state lifetime by six orders of magnitude. Net triplet energy transfer also occurs from surface acceptors to freely diffusing molecular solutes, further extending the lifetime while sensitizing singlet oxygen in an aerated solution. The successful translation of triplet excitons from semiconductor nanoparticles to the bulk solution implies that such materials are generally effective surrogates for molecular triplets. The nanoparticles could thereby potentially sensitize a range of chemical transformations that are relevant for fields as diverse as optoelectronics, solar energy conversion, and photobiology. Copyright © 2016, American Association for the Advancement of Science.

Higher triplet state of fullerene C{sub 70} revealed by electron spin relaxation

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

Uvarov, Mikhail N., E-mail: uvarov@kinetics.nsc.ru; Behrends, Jan; Kulik, Leonid V.

2015-12-28

Spin-lattice relaxation times T{sub 1} of photoexcited triplets {sup 3}C{sub 70} in glassy decalin were obtained from electron spin echo inversion recovery dependences. In the range 30–100 K, the temperature dependence of T{sub 1} was fitted by the Arrhenius law with an activation energy of 172 cm{sup −1}. This indicates that the dominant relaxation process of {sup 3}C{sub 70} is described by an Orbach-Aminov mechanism involving the higher triplet state t{sub 2} which lies 172 cm{sup −1} above the lowest triplet state t{sub 1}. Chemical modification of C{sub 70} fullerene not only decreases the intrinsic triplet lifetime by about tenmore » times but also increases T{sub 1} by several orders of magnitude. The reason for this is the presence of a low-lying excited triplet state in {sup 3}C{sub 70} and its absence in triplet C{sub 70} derivatives. The presence of the higher triplet state in C{sub 70} is in good agreement with the previous results from phosphorescence spectroscopy.« less

The Lowest Triplet of Tetracyanoquinodimethane via UV-vis Absorption Spectroscopy with Br-Containing Solvents.

PubMed

Khvostenko, Olga G; Kinzyabulatov, Renat R; Khatymova, Laysan Z; Tseplin, Evgeniy E

2017-10-05

This study was undertaken to find the previously unknown lowest triplet of the isolated molecule of tetracyanoquinodimethane (TCNQ), which is a widely used organic semiconductor. The problem is topical because the triplet excitation of this compound is involved in some processes which occur in electronic devices incorporating TCNQ and its derivatives, and information on the TCNQ triplet is needed for better understanding of these processes. The lowest triplet of TCNQ was obtained at 1.96 eV using UV-vis absorption spectroscopy with Br-containing solvents. Production of the triplet band with sufficient intensity in the spectra was provided by the capacity of the Br atom to augment the triplet excitation and through using a 100 mm cuvette. The assignment of the corresponding spectral band to the triplet transition was made by observation that this band appeared only in the spectra recorded in Br-containing solvents but not in spectra recorded in other solvents. Additional support for the triplet assignment came from the overall UV-vis absorption spectra of TCNQ recorded in various solvents, using a 10 mm cuvette, in the 1.38-6.5 eV energy range. Singlet transitions of the neutral TCNQ o molecule and doublet transitions of the TCNQ ¯ negative ion were identified in these overall spectra and were assigned with TD B3LYP/6-31G calculations. Determination of the lowest triplet of TCNQ attained in this work may be useful for theoretical studies and practical applications of this important compound.

Different AIS triplets: Different mortality predictions in identical ISS and NISS.

PubMed

Aharonson-Daniel, Limor; Giveon, Adi; Stein, Michael; Peleg, Kobi

2006-09-01

Previous studies demonstrated different mortality predictions for identical Injury Severity Scores (ISS) from different Abbreviated Injury Scale (AIS) triplets. This study elaborates in both scope and volume producing results of a larger magnitude, applicable to specific injury subgroups of blunt or penetrating, traumatic brain injury, various age groups, and replicated on NISS. All patients hospitalized after trauma at 10 hospitals, with ISS/NISS (new ISS) generated by two AIS triplets, excluding patients with isolated minor or moderate injuries to a single body region were studied. Patients were separated into two groups based on the different triplets. Inpatient-mortality rates were calculated for each triplet group. Odds ratios were calculated to estimate the risk of dying in one triplet group as compared with the other. The chi test determined whether the difference in mortality rate between the two groups was significantly different. Differences were further explored for various subgroups. There were 35,827 patients who had ISS/NISS scores generated by two different AIS triplets. Significant differences in death rates were noted between triplet groups forming identical ISS/NISS. Odds ratio for being in the second group (always containing the higher AIS score) ranged from 2.3 to 7.4. ISS and NISS that are formed by different AIS triplets have significantly different inpatient-mortality rates. The triplet with the higher AIS score has higher inpatient-mortality rates, overall and in several sub-populations of varying vulnerability. The comparison of populations and the interpretation of ISS/NISS based outcome data should take this important information into account and the components of AIS triplets creating each ISS and NISS should be reported.

Theoretical descriptions of novel triplet germylenes M1-Ge-M2-M3 (M1 = H, Li, Na, K; M2 = Be, Mg, Ca; M3 = H, F, Cl, Br).

PubMed

Kassaee, Mohamad Zaman; Ashenagar, Samaneh

2018-02-06

In a quest to identify new ground-state triplet germylenes, the stabilities (singlet-triplet energy differences, ΔE S-T ) of 96 singlet (s) and triplet (t) M 1 -Ge-M 2 -M 3 species were compared and contrasted at the B3LYP/6-311++G**, QCISD(T)/6-311++G**, and CCSD(T)/6-311++G** levels of theory (M 1  = H, Li, Na, K; M 2  = Be, Mg, Ca; M 3  = H, F, Cl, Br). Interestingly, F-substituent triplet germylenes (M 3  = F) appear to be more stable and linear than the corresponding Cl- or Br-substituent triplet germylenes (M 3  = Cl or Br). Triplets with M 1  = K (i.e., the K-Ge-M 2 -M 3 series) seem to be more stable than the corresponding triplets with M 1  = H, Li, or Na. This can be attributed to the higher electropositivity of potassium. Triplet species with M 3  = Cl behave similarly to those with M 3  = Br. Conversely, triplets with M 3  = H show similar stabilities and linearities to those with M 3  = F. Singlet species of formulae K-Ge-Ca-Cl and K-Ge-Ca-Br form unexpected cyclic structures. Finally, the triplet germylenes M 1 -Ge-M 2 -M 3 become more stable as the electropositivities of the α-substituents (M 1 and M 2 ) and the electronegativity of the β-substituent (M 3 ) increase.

Aqueous reactions of triplet excited states with allylic compounds

NASA Astrophysics Data System (ADS)

Kaur, R.; Anastasio, C.; Hudson, B. M.; Tantillo, D. J.

2016-12-01

Triplet excited states of dissolved organic matter react with several classes of aromatic organics such as phenols, anilines, sulfonamide antibiotics and phenylurea herbicides. Aqueous triplets appear to be among the most important oxidants for atmospheric phenols in regions with biomass burning, with phenol lifetimes on the order of a few hours to a day. However, little is known of the reactions of triplets with other classes of organic compounds. Recent work from our group shows that triplets react rapidly with several biogenic volatile organic compounds (BVOCs), such as methyl jasmonate, cis-3-hexenyl acetate, and cis-3-hexen-1-ol. However, there are only a few rate constants for aqueous reactions between alkenes such as these and triplet excited states. For our work, we refer to these and similar alkenes which have hydrogen(s) attached to a carbon adjacent to the double bond, as allylic compounds. To better assess the importance of triplets as aqueous oxidants, we measured second-order rate constants (kAC+3BP*) for a number of allylic compounds (ACs) with the triplet state of benzophenone; then established a quantitative structure-activity relationship (QSAR) between kAC+3BP* and computed oxidation potential of the ACs (R2 =0.65). Using the QSAR, we estimated the rate constants for triplets with some allylic isoprene and limonene oxidation products that have high Henry's law constants (KH>103 M atm-1). Hydroxylated limonene products and the delta-isomers of isoprene hydroxyhydroperoxides (δ4ISOPOOH) and hydroxynitrates (δ4ISONO2) were faster with predicted kAC+3BP* values ranging between (0.5-3.5) x 109 M-1-s-1 whereas the beta-isomers of ISOPOOH and ISONO2 were slower (kAC+3BP* < 0.5 x 109 M-1s-1). We scaled the predicted kAC+3BP* to represent less reactive atmospheric triplets that have been measured in fog drops, and compared to gas and aqueous hydroxyl radical and ozone, triplets in fog could account for up to 20 % of the measured loss of these compounds in the atmosphere. We are currently evaluating the importance of triplets in particulate matter (PM) which can have much higher concentrations of triplet precursors than fog. Our results show that as oxidants of unsaturated organic compounds, triplet excited states are of modest significance in fog/cloud drops but could be very significant in PM.

Collective aspects of singlet fission in molecular crystals

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

Teichen, Paul E.; Eaves, Joel D., E-mail: joel.eaves@colorado.edu

2015-07-28

We present a model to describe collective features of singlet fission in molecular crystals and analyze it using many-body theory. The model we develop allows excitonic states to delocalize over several chromophores which is consistent with the character of the excited states in many molecular crystals, such as the acenes, where singlet fission occurs. As singlet states become more delocalized and triplet states more localized, the rate of singlet fission increases. We also determine the conditions under which the two triplets resulting from fission are correlated. Using the Bethe Ansatz and an entanglement measure for indistinguishable bipartite systems, we calculatemore » the triplet-triplet entanglement as a function of the biexciton interaction strength. The biexciton interaction can produce bound biexciton states and provides a source of entanglement between the two triplets even when the triplets are spatially well separated. Significant entanglement between the triplet pair occurs well below the threshold for bound pair formation. Our results paint a dynamical picture that helps to explain why fission has been observed to be more efficient in molecular crystals than in their covalent dimer analogues and have consequences for photovoltaic efficiency models that assume that the two triplets can be extracted independently.« less

Weak-triplet, color-octet scalars and the CDF dijet excess

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

Dobrescu, Bogdan A.; Krnjaic, Gordan Z.

2012-04-24

We extend the standard model to include a weak-triplet and color-octet scalar. This 'octo-triplet' field consists of three particles, two charged and one neutral, whose masses and renormalizable interactions depend only on two new parameters. The charged octo-triplet decay into a W boson and a gluon is suppressed by a loop factor and an accidental cancellation. Thus, the main decays of the charged octo-triplet may occur through higher-dimensional operators, mediated by a heavy vectorlike fermion, into quark pairs. For an octo-triplet mass below the tb¯ threshold, the decay into Wb b¯ through an off-shell top quark has a width comparablemore » to that into cs¯ or cb¯. Pair production with one octo-triplet decaying to two jets and the other decaying to a W and two soft b jets may explain the dijet-plus-W excess reported by the CDF Collaboration. The same higher-dimensional operators lead to CP violation in B s-B¯ s mixing.« less

Thermally activated delayed photoluminescence from pyrenyl-functionalized CdSe quantum dots

NASA Astrophysics Data System (ADS)

Mongin, Cédric; Moroz, Pavel; Zamkov, Mikhail; Castellano, Felix N.

2018-02-01

The generation and transfer of triplet excitons across semiconductor nanomaterial-molecular interfaces will play an important role in emerging photonic and optoelectronic technologies, and understanding the rules that govern such phenomena is essential. The ability to cooperatively merge the photophysical properties of semiconductor quantum dots with those of well-understood and inexpensive molecular chromophores is therefore paramount. Here we show that 1-pyrenecarboxylic acid-functionalized CdSe quantum dots undergo thermally activated delayed photoluminescence. This phenomenon results from a near quantitative triplet-triplet energy transfer from the nanocrystals to 1-pyrenecarboxylic acid, producing a molecular triplet-state 'reservoir' that thermally repopulates the photoluminescent state of CdSe through endothermic reverse triplet-triplet energy transfer. The photoluminescence properties are systematically and predictably tuned through variation of the quantum dot-molecule energy gap, temperature and the triplet-excited-state lifetime of the molecular adsorbate. The concepts developed are likely to be applicable to semiconductor nanocrystals interfaced with molecular chromophores, enabling potential applications of their combined excited states.

Phenomenology of left-right symmetric dark matter

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

Garcia-Cely, Camilo; Heeck, Julian, E-mail: Camilo.Alfredo.Garcia.Cely@ulb.ac.be, E-mail: Julian.Heeck@ulb.ac.be

We present a detailed study of dark matter phenomenology in low-scale left-right symmetric models. Stability of new fermion or scalar multiplets is ensured by an accidental matter parity that survives the spontaneous symmetry breaking of the gauge group by scalar triplets. The relic abundance of these particles is set by gauge interactions and gives rise to dark matter candidates with masses above the electroweak scale. Dark matter annihilations are thus modified by the Sommerfeld effect, not only in the early Universe, but also today, for instance, in the Center of the Galaxy. Majorana candidates—triplet, quintuplet, bi-doublet, and bi-triplet—bring only onemore » new parameter to the model, their mass, and are hence highly testable at colliders and through astrophysical observations. Scalar candidates—doublet and 7-plet, the latter being only stable at the renormalizable level—have additional scalar-scalar interactions that give rise to rich phenomenology. The particles under discussion share many features with the well-known candidates wino, Higgsino, inert doublet scalar, sneutrino, and Minimal Dark Matter. In particular, they all predict a large gamma-ray flux from dark matter annihilations, which can be searched for with Cherenkov telescopes. We furthermore discuss models with unequal left-right gauge couplings, g{sub R} ≠ g{sub L}, taking the recent experimental hints for a charged gauge boson with 2 TeV mass as a benchmark point. In this case, the dark matter mass is determined by the observed relic density.« less

Photocyclization Reactions of Diarylethenes via the Excited Triplet State.

PubMed

Murata, Ryutaro; Yago, Tomoaki; Wakasa, Masanobu

2015-11-12

Cyclization reactions of three diarylethene derivatives, 1,2-bis(2-methyl-3-benzothienyl)perfluorocyclopentene (BT), 1,2-bis(2-hexyl-3-benzothienyl)perfluorocyclopentene (BTHex), and 1,2-bis(2-isopropyl-3-benzothienyl)perfluorocyclopentene (BTiPr), via their excited triplet states were studied by means of steady-state and nanosecond transient absorption spectroscopy. The excited triplet states of BT, BTHex, and BTiPr were generated by energy transfer from the photoexcited triplet states of sensitizers such as xanthone, phenanthrene, and pyrene. The single-step quantum yields of the cyclization reactions from the excited triplet states of BT, BTHex, and BTiPr were determined to be 0.34, 0.53, and 0.65, respectively. The triplet energies of these three BTs were estimated to be 190-200 kJ mol(-1).

Strongly exchange-coupled triplet pairs in an organic semiconductor

NASA Astrophysics Data System (ADS)

Weiss, Leah R.; Bayliss, Sam L.; Kraffert, Felix; Thorley, Karl J.; Anthony, John E.; Bittl, Robert; Friend, Richard H.; Rao, Akshay; Greenham, Neil C.; Behrends, Jan

2017-02-01

From biological complexes to devices based on organic semiconductors, spin interactions play a key role in the function of molecular systems. For instance, triplet-pair reactions impact operation of organic light-emitting diodes as well as photovoltaic devices. Conventional models for triplet pairs assume they interact only weakly. Here, using electron spin resonance, we observe long-lived, strongly interacting triplet pairs in an organic semiconductor, generated via singlet fission. Using coherent spin manipulation of these two-triplet states, we identify exchange-coupled (spin-2) quintet complexes coexisting with weakly coupled (spin-1) triplets. We measure strongly coupled pairs with a lifetime approaching 3 μs and a spin coherence time approaching 1 μs, at 10 K. Our results pave the way for the utilization of high-spin systems in organic semiconductors.

Nearly Perfect Triplet-Triplet Energy Transfer from Wannier Excitons to Naphthalene in Organic-Inorganic Hybrid Quantum-Well Materials

NASA Astrophysics Data System (ADS)

Ema, K.; Inomata, M.; Kato, Y.; Kunugita, H.; Era, M.

2008-06-01

We report the observation of extremely efficient energy transfer (greater than 99%) in an organic-inorganic hybrid quantum-well structure consisting of perovskite-type lead bromide well layers and naphthalene-linked ammonium barrier layers. Time-resolved photoluminescence measurements confirm that the transfer is triplet-triplet Dexter-type energy transfer from Wannier excitons in the inorganic well to the triplet state of naphthalene molecules in the organic barrier. Using measurements in the 10 300 K temperature range, we also investigated the temperature dependence of the energy transfer.

Exciplex emission and decay of co-deposited 4,4',4″-tris[3-methylphenyl(phenyl)amino]triphenylamine:tris-[3-(3-pyridyl)mesityl]borane organic light-emitting devices with different electron transporting layer thicknesses

NASA Astrophysics Data System (ADS)

Huang, Qingyu; Zhao, Suling; Xu, Zheng; Fan, Xing; Shen, Chongyu; Yang, Qianqian

2014-04-01

Highly efficient fluorescence organic light-emitting diodes (OLEDs) based on the mixed 4,4',4″-tris[3-methylphenyl(phenyl)amino]triphenylamine:tris-[3-(3-pyridyl)mesityl]borane (1:1) system are reported. The electroluminescence due to the exciplex emission is red shifted when the thickness of the electron-transporting layer increases. The prepared OLEDs achieve a low turn-on voltage of 2.1 V, a high current efficiency of 36.79 cd/A, and a very high luminescence of 17 100 cd/m2, as well as a low efficiency roll-off. The current efficiency of the optimized OLED is maintained at more than 28.33 cd/A up to 10 000 cd m-2. The detailed recombination mechanism of the prepared OLEDs is investigated by the transient electroluminescence method. It is concluded that there are no contributions from trapped charges and annihilations of triplet-triplet excitons to the detected electroluminescence.

Mechanism of phosphorescence quenching in photomagnetic molecules determined by positron annihilation spectroscopy

NASA Technical Reports Server (NTRS)

Singh, Jag J.; Eftekhari, A.; Naidu, S. V. N.

1994-01-01

Platinum Octaethyl Porphyrin (Pt.OEP) is an efficient phosphor under ultraviolet excitation. The phosphorescent triplet state (T(sub 1)) is readily quenched by the oxygen (O2) molecules. This phenomenon is being utilized as the basis for global air pressure measurements in aerodynamic facilities at various laboratories. The exact mechanism by which O2 molecules quench the (T(sub 1)-S(sub 0)) transitions is still unknown. The diamagnetic S(sub n) singlet states, which feed T(sub 1) states via intersystem crossings, would presumably not be affected by O2. It must be the magnetic T(sub 1) states, which can interact with the paramagnetic O2 molecules, that are affected. However, our positron lifetime and Doppler broadening studies suggest the formation of (S(sub n).02) complexes which can also eventually reduce the population of the T(sub 1) states (i.e. quench phosphorescence). This is possible since higher triplet states in (Pt-OEP) are admixed with the S(sub n) states via spin orbit interactions. The experimental procedures and the results of various measurements are discussed in this paper.

Mechanism of phosphorescence quenching in photomagnetic molecules determined by positron annihilation spectroscopy

NASA Technical Reports Server (NTRS)

Singh, Jag J.; Eftekhari, A.; Naidu, S. V. N.

1994-01-01

Platinum Octaethyl Porphyrin (Pt.OEP) is an efficient phosphor under ultraviolet excitation. The phosphorescent triplet state (T(sub 1)) is readily quenched by the oxygen (O2) molecules. This phenomenon is being utilized as the basis for global air pressure measurements in aerodynamic facilities at various laboratories. The exact mechanism by which O2 molecules quench the (T(sub 1) - S(sub 0)) transitions is still unknown. The diamagnetic S(sub n) singlet states, which feed T(sub 1) states via intersystem crossings, would presumably not be affected by O2. It must be the magnetic T(sub 1) states, which can interact with the paramagnetic O2 molecules, that are affected. However, our positron lifetime and Doppler broadening studies suggest the formation of (S(sub n) central dot O2) complexes which can also eventually reduce the population of the T(sub 1) states (i.e. quench phosphorescence). This is possible since higher triplet states in (Pt.OEP) are admixed with the S(sub n) states via spin orbit interactions. The experimental procedures and the results of various measurements are discussed in this paper.

Three-Triplet Model with Double SU(3) Symmetry

DOE R&D Accomplishments Database

Han, M. Y.; Nambu, Y.

1965-01-01

With a view to avoiding some of the kinematical and dynamical difficulties involved in the single triplet quark model, a model for the low lying baryons and mesons based on three triplets with integral charges is proposed, somewhat similar to the two-triplet model introduced earlier by one of us (Y. N.). It is shown that in a U(3) scheme of triplets with integral charges, one is naturally led to three triplets located symmetrically about the origin of I{sub 3} - Y diagram under the constraint that Nishijima-Gell-Mann relation remains intact. A double SU(3) symmetry scheme is proposed in which the large mass splittings between different representations are ascribed to one of the SU(3), while the other SU(3) is the usual one for the mass splittings within a representation of the first SU(3).

Parenting Stress, Infant Emotion Regulation, Maternal Sensitivity, and the Cognitive Development of Triplets: A Model for Parent and Child Influences in a Unique Ecology

ERIC Educational Resources Information Center

Feldman, Ruth; Eidelman, Arthur I.; Rotenberg, Noa

2004-01-01

To examine the development of triplets, 23 sets of triplets were matched with 23 sets of twins and 23 singletons (N138). Maternal sensitivity was observed at newborn, 3, 6, and 12 months, and infants' cognitive and symbolic skills at 1 year. Triplets received lower maternal sensitivity across infancy and exhibited poorer cognitive competencies…

OXYGEN ABUNDANCES IN CEPHEIDS

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

Luck, R. E.; Andrievsky, S. M.; Korotin, S. N.

2013-07-01

Oxygen abundances in later-type stars, and intermediate-mass stars in particular, are usually determined from the [O I] line at 630.0 nm, and to a lesser extent, from the O I triplet at 615.7 nm. The near-IR triplets at 777.4 nm and 844.6 nm are strong in these stars and generally do not suffer from severe blending with other species. However, these latter two triplets suffer from strong non-local thermodynamic equilibrium (NLTE) effects and thus see limited use in abundance analyses. In this paper, we derive oxygen abundances in a large sample of Cepheids using the near-IR triplets from an NLTEmore » analysis, and compare those abundances to values derived from a local thermodynamic equilibrium (LTE) analysis of the [O I] 630.0 nm line and the O I 615.7 nm triplet as well as LTE abundances for the 777.4 nm triplet. All of these lines suffer from line strength problems making them sensitive to either measurement complications (weak lines) or to line saturation difficulties (strong lines). Upon this realization, the LTE results for the [O I] lines and the O I 615.7 nm triplet are in adequate agreement with the abundance from the NLTE analysis of the near-IR triplets.« less

Triplet-triplet energy transfer between luminescent probes bound to albumins

NASA Astrophysics Data System (ADS)

Mel'Nikov, A. G.; Saletskii, A. M.; Kochubey, V. I.; Pravdin, A. B.; Kurchatov, I. S.; Mel'Nikov, G. V.

2010-08-01

The interaction of polar and nonpolar luminescent probes with human blood serum albumins is studied by absorption and luminescence spectroscopy. It is found that the probes (polar eosin and nonpolar anthracene) can efficiently bind to proteins. The radii of the quenching spheres of energy-donor (eosin) triplet states in the presence of an acceptor (anthracene) in the process of the triplet-triplet energy transfer in proteins are determined for homogeneous and inhomogeneous distributions of acceptor molecules over the solution volume. It is shown that a decrease in the radius of the quenching sphere observed upon the addition of sodium dodecylsulfate surfactant is caused by structural changes in the protein.

Numerical investigation on the viewing angle of a lenticular three-dimensional display with a triplet lens array.

PubMed

Kim, Hwi; Hahn, Joonku; Choi, Hee-Jin

2011-04-10

We investigate the viewing angle enhancement of a lenticular three-dimensional (3D) display with a triplet lens array. The theoretical limitations of the viewing angle and view number of the lenticular 3D display with the triplet lens array are analyzed numerically. For this, the genetic-algorithm-based design method of the triplet lens is developed. We show that a lenticular 3D display with viewing angle of 120° and 144 views without interview cross talk can be realized with the use of an optimally designed triplet lens array. © 2011 Optical Society of America

Time-resolved infrared spectroscopy of the lowest triplet state of thymine and thymidine

PubMed Central

Hare, Patrick M.; Middleton, Chris T.; Mertel, Kristin I.

2008-01-01

Vibrational spectra of the lowest energy triplet states of thymine and its 2’-deoxyribonucleoside, thymidine, are reported for the first time. Time-resolved infrared (TRIR) difference spectra were recorded over seven decades of time from 300 fs – 3 µs using femtosecond and nanosecond pump-probe techniques. The carbonyl stretch bands in the triplet state are seen at 1603 and ~1700 cm−1 in room-temperature acetonitrile-d3 solution. These bands and additional ones observed between 1300 and 1450 cm−1 are quenched by dissolved oxygen on a nanosecond time scale. Density-functional calculations accurately predict the difference spectrum between triplet and singlet IR absorption cross sections, confirming the peak assignments and elucidating the nature of the vibrational modes. In the triplet state, the C4=O carbonyl exhibits substantial single-bond character, explaining the large (~70 cm−1) red shift in this vibration, relative to the singlet ground state. Femtosecond TRIR measurements unambiguously demonstrate that the triplet state is fully formed within the first 10 ps after excitation, ruling out a relaxed 1nπ* state as the triplet precursor. PMID:19936322

Production and installation of the LHC low-beta triplets

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

Feher, S.; Bossert, R.; DiMarco, J.

2005-09-01

The LHC performance depends critically on the low-{beta}, triplets, located on either side of the four interaction points. Each triplet consists of four superconducting quadrupole magnets, which must operate reliably at up to 215 T/m, sustain extremely high heat loads and have an excellent field quality. A collaboration of CERN, Fermilab and KEK was formed in 1996 to design and build the triplet systems, and after nine years of joint effort the production has been completed in 2005. We retrace the main events of the project and present the design features and performance of the low-{beta} quadrupoles, built by KEKmore » and Fermilab, as well as of other vital elements of the triplet. The tunnel installation of the first triplet and plans for commissioning in the LHC are also presented. Apart from the excellent technical results, the construction of the LHC low-{beta} triplets has been a highly enriching experience combining harmoniously the different competences and approaches to engineering in a style reminiscent of high energy physics experiment collaborations, and rarely before achieved in construction of an accelerator.« less

On static triplet structures in fluids with quantum behavior.

PubMed

Sesé, Luis M

2018-03-14

The problem of the equilibrium triplet structures in fluids with quantum behavior is discussed. Theoretical questions of interest to the real space structures are addressed by studying the three types of structures that can be determined via path integrals (instantaneous, centroid, and total thermalized-continuous linear response). The cases of liquid para-H 2 and liquid neon on their crystallization lines are examined with path-integral Monte Carlo simulations, the focus being on the instantaneous and the centroid triplet functions (equilateral and isosceles configurations). To analyze the results further, two standard closures, Kirkwood superposition and Jackson-Feenberg convolution, are utilized. In addition, some pilot calculations with path integrals and closures of the instantaneous triplet structure factor of liquid para-H 2 are also carried out for the equilateral components. Triplet structural regularities connected to the pair radial structures are identified, a remarkable usefulness of the closures employed is observed (e.g., triplet spatial functions for medium-long distances, triplet structure factors for medium k wave numbers), and physical insight into the role of pair correlations near quantum crystallization is gained.

On static triplet structures in fluids with quantum behavior

NASA Astrophysics Data System (ADS)

Sesé, Luis M.

2018-03-01

The problem of the equilibrium triplet structures in fluids with quantum behavior is discussed. Theoretical questions of interest to the real space structures are addressed by studying the three types of structures that can be determined via path integrals (instantaneous, centroid, and total thermalized-continuous linear response). The cases of liquid para-H2 and liquid neon on their crystallization lines are examined with path-integral Monte Carlo simulations, the focus being on the instantaneous and the centroid triplet functions (equilateral and isosceles configurations). To analyze the results further, two standard closures, Kirkwood superposition and Jackson-Feenberg convolution, are utilized. In addition, some pilot calculations with path integrals and closures of the instantaneous triplet structure factor of liquid para-H2 are also carried out for the equilateral components. Triplet structural regularities connected to the pair radial structures are identified, a remarkable usefulness of the closures employed is observed (e.g., triplet spatial functions for medium-long distances, triplet structure factors for medium k wave numbers), and physical insight into the role of pair correlations near quantum crystallization is gained.

Benchmarking singlet and triplet excitation energies of molecular semiconductors for singlet fission: Tuning the amount of HF exchange and adjusting local correlation to obtain accurate functionals for singlet-triplet gaps

NASA Astrophysics Data System (ADS)

Brückner, Charlotte; Engels, Bernd

2017-01-01

Vertical and adiabatic singlet and triplet excitation energies of molecular p-type semiconductors calculated with various DFT functionals and wave-function based approaches are benchmarked against MS-CASPT2/cc-pVTZ reference values. A special focus lies on the singlet-triplet gaps that are very important in the process of singlet fission. Singlet fission has the potential to boost device efficiencies of organic solar cells, but the scope of existing singlet-fission compounds is still limited. A computational prescreening of candidate molecules could enlarge it; yet it requires efficient methods accurately predicting singlet and triplet excitation energies. Different DFT formulations (Tamm-Dancoff approximation, linear response time-dependent DFT, Δ-SCF) and spin scaling schemes along with several ab initio methods (CC2, ADC(2)/MP2, CIS(D), CIS) are evaluated. While wave-function based methods yield rather reliable singlet-triplet gaps, many DFT functionals are shown to systematically underestimate triplet excitation energies. To gain insight, the impact of exact exchange and correlation is in detail addressed.

Centriole triplet microtubules are required for stable centriole formation and inheritance in human cells

PubMed Central

Wang, Jennifer T; Kong, Dong; Hoerner, Christian R; Loncarek, Jadranka

2017-01-01

Centrioles are composed of long-lived microtubules arranged in nine triplets. However, the contribution of triplet microtubules to mammalian centriole formation and stability is unknown. Little is known of the mechanism of triplet microtubule formation, but experiments in unicellular eukaryotes indicate that delta-tubulin and epsilon-tubulin, two less-studied tubulin family members, are required. Here, we report that centrioles in delta-tubulin and epsilon-tubulin null mutant human cells lack triplet microtubules and fail to undergo centriole maturation. These aberrant centrioles are formed de novo each cell cycle, but are unstable and do not persist to the next cell cycle, leading to a futile cycle of centriole formation and disintegration. Disintegration can be suppressed by paclitaxel treatment. Delta-tubulin and epsilon-tubulin physically interact, indicating that these tubulins act together to maintain triplet microtubules and that these are necessary for inheritance of centrioles from one cell cycle to the next. PMID:28906251

Singlet and triplet trions in WS2 monolayer encapsulated in hexagonal boron nitride.

PubMed

Vaclavkova, D; Wyzula, J; Nogajewski, K; Bartos, M; Slobodeniuk, A O; Faugeras, C; Potemski, M; Molas, M R

2018-08-10

Embedding a WS 2 monolayer in flakes of hexagonal boron nitride allowed us to resolve and study the photoluminescence response due to both singlet and triplet states of negatively charged excitons (trions) in this atomically thin semiconductor. The energy separation between the singlet and triplet states has been found to be relatively small reflecting rather weak effects of the electron-electron exchange interaction for the trion triplet in a WS 2 monolayer, which involves two electrons with the same spin but from different valleys. Polarization-resolved experiments demonstrate that the helicity of the excitation light is better preserved in the emission spectrum of the triplet trion than in that of the singlet trion. Finally, the singlet (intravalley) trions are found to be observable even at ambient conditions whereas the emission due to the triplet (intervalley) trions is only efficient at low temperatures.

Diphotons from electroweak triplet-singlet mixing

DOE PAGES

Howe, Kiel; Knapen, Simon; Robinson, Dean J.

2016-08-23

The neutral component of a real pseudoscalar electroweak (EW) triplet can produce a diphoton excess at 750 GeV, if it is somewhat mixed with an EW singlet pseudoscalar. This triplet-singlet mixing allows for greater freedom in the diboson branching ratios than the singlet-only case, but it is still possible to probe the parameter space extensively with 300 fb -1. The charged component of the triplet is pair produced at the LHC, which results in a striking signal in the form of a pair of Wγ resonances with an irreducible rate of 0.27 fb. Other signatures include multiboson final states from cascade decaysmore » of the triplet-singlet neutral states. In conclusion, a large class of composite models feature both EW singlet and triplet pseudo-Nambu-Goldstone bosons in their spectrum, with the diboson couplings generated by axial anomalies.« less

Experimental Investigation of Triplet Correlation Approximations for Fluid Water.

PubMed

Pallewela, Gayani N; Ploetz, Elizabeth A; Smith, Paul E

2018-08-25

Triplet correlations play a central role in our understanding of fluids and their properties. Of particular interest is the relationship between the pair and triplet correlations. Here we use a combination of Fluctuation Solution Theory and experimental pair radial distribution functions to investigate the accuracy of the Kirkwood Superposition Approximation (KSA), as given by integrals over the relevant pair and triplet correlation functions, at a series of state points for pure water using only experimental quantities. The KSA performs poorly, in agreement with a variety of other studies. Several additional approximate relationships between the pair and triplet correlations in fluids are also investigated and generally provide good agreement for the fluid thermodynamics for regions of the phase diagram where the compressibility is small. A simple power law relationship between the pair and triplet fluctuations is particularly successful for state points displaying low to moderately high compressibilities.

Centriole triplet microtubules are required for stable centriole formation and inheritance in human cells.

PubMed

Wang, Jennifer T; Kong, Dong; Hoerner, Christian R; Loncarek, Jadranka; Stearns, Tim

2017-09-14

Centrioles are composed of long-lived microtubules arranged in nine triplets. However, the contribution of triplet microtubules to mammalian centriole formation and stability is unknown. Little is known of the mechanism of triplet microtubule formation, but experiments in unicellular eukaryotes indicate that delta-tubulin and epsilon-tubulin, two less-studied tubulin family members, are required. Here, we report that centrioles in delta-tubulin and epsilon-tubulin null mutant human cells lack triplet microtubules and fail to undergo centriole maturation. These aberrant centrioles are formed de novo each cell cycle, but are unstable and do not persist to the next cell cycle, leading to a futile cycle of centriole formation and disintegration. Disintegration can be suppressed by paclitaxel treatment. Delta-tubulin and epsilon-tubulin physically interact, indicating that these tubulins act together to maintain triplet microtubules and that these are necessary for inheritance of centrioles from one cell cycle to the next.

Delocalisation of photoexcited triplet states probed by transient EPR and hyperfine spectroscopy

NASA Astrophysics Data System (ADS)

Richert, Sabine; Tait, Claudia E.; Timmel, Christiane R.

2017-07-01

Photoexcited triplet states play a crucial role in photochemical mechanisms: long known to be of paramount importance in the study of photosynthetic reaction centres, they have more recently also been shown to play a major role in a number of applications in the field of molecular electronics. Their characterisation is crucial for an improved understanding of these processes with a particular focus on the determination of the spatial distribution of the triplet state wavefunction providing information on charge and energy transfer efficiencies. Currently, active research in this field is mostly focussed on the investigation of materials for organic photovoltaics (OPVs) and organic light emitting diodes (OLEDs). As the properties of triplet states and their spatial extent are known to have a major impact on device performance, a detailed understanding of the factors governing triplet state delocalisation is at the basis of the further development and improvement of these devices. Electron Paramagnetic Resonance (EPR) has proven a valuable tool in the study of triplet state properties and both experimental methods as well as data analysis and interpretation techniques have continuously improved over the last few decades. In this review, we discuss the theoretical and practical aspects of the investigation of triplet states and triplet state delocalisation by transient continuous wave and pulse EPR and highlight the advantages and limitations of the presently available techniques and the current trends in the field. Application of EPR in the study of triplet state delocalisation is illustrated on the example of linear multi-porphyrin chains designed as molecular wires.

Triplet energy transfer and triplet exciton recycling in singlet fission sensitized organic heterojunctions

NASA Astrophysics Data System (ADS)

Hamid, Tasnuva; Yambem, Soniya D.; Crawford, Ross; Roberts, Jonathan; Pandey, Ajay K.

2017-08-01

Singlet exciton fission is a process where an excited singlet state splits into two triplets, thus leading to generation of multiple excitons per absorbed photon in organic semiconductors. Herein, we report a detailed exciton management approach for multiexciton harvesting over a broadband region of the solar spectrum in singlet fission sensitized organic photodiodes. Through systematic studies on the model cascade of pentacene/rubrene/C60, we found that efficient photocurrent generation from pentacene can still occur despite the presence of a >10nm thick interlayer of rubrene in between the pentacene/C60 heterojunction. Our results show that thin rubrene interlayers of thickness < 5 nm are effective in maintaining the delicate balance between two free charge generation channels that progress independently via the electron and hole transfer routes. The contribution to photocurrent from pentacene despite having a reasonably thick rubrene interlayer, that too with higher triplet energy (T1=1.12 eV) than pentacene (T1= 0.86 eV), makes its operation a rather interesting result. We discuss the role of rubrene interlayer film discontinuity, triplet exciton reflection from rubrene interlayer and triplet energy transfer from rubrene to pentacene layer followed by diffusion of triplet excitons through rubrene as plausible mechanisms that would enable triplet excitons from pentacene to generate significant photocurrent in a multilayer organic heterojunction.

Transport of triplet excitons along continuous 100 nm polyfluorene chains

DOE PAGES

Xi, Liang; Bird, Matthew; Mauro, Gina; ...

2014-12-03

Triplet excitons created in poly-2,7-(9,9-dihexyl)fluorene (pF) chains with end trap groups in solution are efficiently transported to and captured by the end groups. The triplets explore the entire lengths of the chains, even for ~100 nm long chains enabling determination of the completeness of end capping. The results show that the chains continuous: they may contain transient barriers or traps, such as those from fluctuations of dihedral angles, but are free of major defects that stop motion of the triplets. Quantitative determinations are aided by the addition of a strong electron donor, TMPD, which removes absorption bands of the end-trappedmore » triplets. For chains having at least one end trap, triplet capture is quantitative on the 1 µs timescale imposed by the use of the donor. Fractions of chains having no end traps were 0.15 for pF samples with anthraquinone (AQ) end traps and 0.063 with naphthylimide (NI) end traps. These determinations agreed with measurements by NMR for short (<40 polymer repeat units (PRU)) chains, where NMR determinations are accurate. The results find no evidence for traps or barriers to transport of triplets, and places limits on the possible presence of defects as impenetrable barriers to less than one per 300 PRU. The present results present a paradigm different from the current consensus, derived from observations of singlet excitons, that conjugated chains are divided into “segments,” perhaps by some kind of defects. For the present pF chains, the segmentation either does not apply to triplet excitons or is transient so that the defects are healed or surmounted in times much shorter than 1 µs. Triplets on chains without end trap groups transfer to chains with end traps on a slower time scale. Rate constants for these bimolecular triplet transfer reactions were found to increase with the length of the accepting chain, as did rate constants for triplet transfer to the chains from small molecules like biphenyl. As a result, a second set of polyfluorenes with 2-butyloctyl side chains was found to have a much lower completeness of end capping.« less

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.

On the Effect of Triplet or Doublet Chemotherapy in Advanced Gastric Cancer: Results From a National Cancer Registry.

PubMed

Carmona-Bayonas, Alberto; Jiménez-Fonseca, Paula; Lorenzo, Maria Luisa Sánchez; Ramchandani, Avinash; Martínez, Elena Asensio; Custodio, Ana; Garrido, Marcelo; Echavarría, Isabel; Cano, Juana María; Barreto, Jose Enrique Lorenzo; García, Teresa García; Manceñido, Felipe Álvarez; Lacalle, Alejandra; Cardona, Marta Ferrer; Mangas, Monserrat; Visa, Laura; Buxó, Elvira; Azkarate, Aitor; Díaz-Serrano, Asunción; Montes, Ana Fernández; Rivera, Fernando

2016-11-01

There is currently no consensus regarding first-line chemotherapy for patients with advanced gastric cancer (AGC) who are ineligible to receive trastuzumab. The objective of this study was to evaluate the efficacy and tolerance of triplets versus doublets by analyzing a national gastric cancer registry. Patients with AGC treated with polychemotherapy without associating trastuzumab were included from 2008 through 2016. The effect of triplets versus doublets was compared using 3 methods: Cox proportional hazards regression, propensity score matching (PSM), and coarsened exact matching (CEM). A total of 970 patients were recruited (doublets: n=569; triplets: n=401). In the multivariate Cox model, the use of triplets was associated with better overall survival (OS), with a hazard ratio (HR) of 0.84 (95% CI, 0.72-0.98; P=.035). After PSM, the sample contained 340 pairs. A significant increase in OS, 11.14 months (95% CI, 9.60-12.68) versus 9.60 months (95% CI, 8.44-10.75), was seen in favor of triplets (HR, 0.77; 95% CI, 0.65-0.92; stratified log-rank test, P=.004). The effect appeared to be comparable for anthracycline-based (HR, 0.78; 95% CI, 0.64-0.94) or docetaxel-based triplets (HR, 0.78; 95% CI, 0.60-1.009). The trend was similar after applying the CEM algorithm, with an HR of 0.78 (95% CI, 0.63-0.97; P=.03). Triplet therapy was viable and relative dose intensities exceeded 85%, except for cisplatin in DCX (docetaxel, cisplatin, capecitabine). Triplets had more severe toxicity overall, especially hematologic, hepatic, and mucosal adverse events. With the limitations of a retrospective study that examines a heterogeneous set of chemotherapy regimens, we found that triplets are feasible in daily practice and are associated with a discreet benefit in efficacy at the expense of a moderate increase in toxicity. Copyright © 2016 by the National Comprehensive Cancer Network.

Time-resolved infrared spectroscopy of the lowest triplet state of thymine and thymidine

NASA Astrophysics Data System (ADS)

Hare, Patrick M.; Middleton, Chris T.; Mertel, Kristin I.; Herbert, John M.; Kohler, Bern

2008-05-01

Vibrational spectra of the lowest energy triplet states of thymine and its 2'-deoxyribonucleoside, thymidine, are reported for the first time. Time-resolved infrared (TRIR) difference spectra were recorded over seven decades of time from 300 fs to 3 μs using femtosecond and nanosecond pump-probe techniques. The carbonyl stretch bands in the triplet state are seen at 1603 and ˜1700 cm -1 in room-temperature acetonitrile- d3 solution. These bands and additional ones observed between 1300 and 1450 cm -1 are quenched by dissolved oxygen on a nanosecond time scale. Density-functional calculations accurately predict the difference spectrum between triplet and singlet IR absorption cross sections, confirming the peak assignments and elucidating the nature of the vibrational modes. In the triplet state, the C4 dbnd O carbonyl exhibits substantial single-bond character, explaining the large (˜70 cm -1) red shift in this vibration, relative to the singlet ground state. Femtosecond TRIR measurements unambiguously demonstrate that the triplet state is fully formed within the first 10 ps after excitation, ruling out a relaxed 1nπ ∗ state as the triplet precursor.

Non-thermal leptogenesis with distinct CP violation and minimal dark matter

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

Zhou, Hang; Gu, Pei-Hong, E-mail: einsteinzh@sjtu.edu.cn, E-mail: peihong.gu@sjtu.edu.cn

We demonstrate a unified scenario for neutrino mass, baryon asymmetry, dark matter and inflation. In addition to a fermion triplet for the so-called minimal dark matter, we extend the standard model by three heavy fields including a scalar singlet, a fermion triplet and a fermion singlet/Higgs triplet. The heavy scalar singlet, which is expected to drive an inflation, and the dark matter fermion triplet are odd under an unbroken Z {sub 2} discrete symmetry, while the other fields are all even. The heavy fermion triplet offers a tree-level type-III seesaw and then mediates a three-body decay of the inflaton intomore » the standard model lepton and Higgs doublets with the dark matter fermion triplet. The heavy fermion singlet/Higgs triplet not only results in a type-I/II seesaw at tree level but also contributes to the inflaton decay at one-loop level. In this scenario, the type-I/II seesaw contains all of the physical CP phases in the lepton sector and hence the CP violation for the non-thermal leptogenesis by the inflaton decay exactly comes from the imaginary part of the neutrino mass matrix.« less

Resolution of Port/Starboard Ambiguity Using a Linear Array of Triplets and a Twin-Line Planar Array

DTIC Science & Technology

2016-06-01

STARBOARD AMBIGUITY USING A LINEAR ARRAY OF TRIPLETS AND A TWIN- LINE PLANAR ARRAY by Stilson Veras Cardoso June 2016 Thesis Advisor...OF TRIPLETS AND A TWIN-LINE PLANAR ARRAY 5. FUNDING NUMBERS 6. AUTHOR(S) Stilson Veras Cardoso 7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES...A LINEAR ARRAY OF TRIPLETS AND A TWIN-LINE PLANAR ARRAY Stilson Veras Cardoso Civilian, Brazilian Navy B.S., University of Brasília, 1993

Development of the triplet singularity for the analysis of wings and bodies in supersonic flow

NASA Technical Reports Server (NTRS)

Woodward, F. A.

1981-01-01

A supersonic triplet singularity was developed which eliminates internal waves generated by panels having supersonic edges. The triplet is a linear combination of source and vortex distributions which gives directional properties to the perturbation flow field surrounding the panel. The theoretical development of the triplet singularity is described together with its application to the calculation of surface pressures on wings and bodies. Examples are presented comparing the results of the new method with other supersonic methods and with experimental data.

[Percentile Values for the Anthropometric Dimensions of Triplet Neonates - Analysis of German Perinatal Survey Data of 2007-2011 from all States of Germany].

PubMed

Voigt, M; Olbertz, D; Hentschel, R; Kunze, M; Hagenah, H-P; Scholz, R; Wittwer-Backofen, U; Hesse, V; Straube, S

2016-04-01

We aimed to develop national reference values for birth weight, length, head circumference, and weight for length for newborn triplets based on data from the German perinatal survey of 2007-2011. Perinatal survey data of 3,690 newborn triplets from all the states of Germany were kindly provided to us by the AQUA Institute in Göttingen, Germany. Data of 3,567 newborn triplets were included in the analyses. Sex-specific percentile values were calculated using cumulative frequencies. Percentile values at birth were computed for the 3rd, 10th, 25th, 50th, 75th, 90th, and 97th percentiles for 21-36 completed weeks of gestation. We present the first German reference values (tables and curves) for the anthropometric dimensions of triplet neonates and compare selected birth weight and length percentiles of triplets (after 32 and 34 completed weeks of gestation) to those of singletons and twins. The differences in the 50th birth weight percentiles between singletons and triplets after 32 completed weeks of gestation were 180 g for girls and 210 g for boys; after 34 weeks of gestation the differences were 320 and 325 g, respectively. The differences between twins and triplets after 32 weeks of gestation were 100 g for girls and 120 g for boys; after 34 weeks of gestation they were 130 and 135 g, respectively. The data presented here enable the classification of newborn triplets according to somatic parameters making reference to German perinatal data. © Georg Thieme Verlag KG Stuttgart · New York.

Singlet-triplet fission of carotenoid excitation in light-harvesting LH2 complexes of purple phototrophic bacteria.

PubMed

Klenina, I B; Makhneva, Z K; Moskalenko, A A; Gudkov, N D; Bolshakov, M A; Pavlova, E A; Proskuryakov, I I

2014-03-01

The current generally accepted structure of light-harvesting LH2 complexes from purple phototrophic bacteria conflicts with the observation of singlet-triplet carotenoid excitation fission in these complexes. In LH2 complexes from the purple bacterium Allochromatium minutissimum, a drop in the efficiency of carotenoid triplet generation is demonstrated, which correlates with the extent of selective photooxidation of bacteriochlorophylls absorbing at ~850 nm. We conclude that singlet-triplet fission of carotenoid excitation proceeds with participation of these excitonically coupled bacteriochlorophylls. In the framework of the proposed mechanism, the contradiction between LH2 structure and photophysical properties of carotenoids is eliminated. The possibility of singlet-triplet excitation fission involving a third mediator molecule was not considered earlier.

Perturbation Theory of Spin-Triplet Superconductivity for Sr 2RuO 4

NASA Astrophysics Data System (ADS)

Nomura, Takuji; Yamada, Kosaku

2000-11-01

We discuss the possibility of spin-triplet superconductivity within the third order perturbation theory with respect to on-site Coulomb repulsion U. Critical temperature T c for spin-triplet pairing state is calculated in a single-band two-dimensional Hubbard modeland relatively high T c is obtained for moderately large U. The present situation considered here is particularly intended for the main branch γ in Sr2RuO4. According to the calculation, third order vertex correction terms, which are not direct contribution from spin fluctuation, are important, while the bare susceptibility χ0(q) need not always have a prominent peak at q=0 for the spin-triplet pairing state. The picture that strong ferromagnetic spin fluctuations mainly induce the spin-triplet superconductivity in Sr2RuO4 may not be appropriate, and such momentum dependence of renormalized effective interaction between quasi-particles as is not sufficiently taken into accountin spin fluctuation mediated interaction is essential for realizing the spin-triplet pairing.

Cooperative Singlet and Triplet Exciton Transport in Tetracene Crystals Visualized by Ultrafast Microscopys

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

Wan, Yan; Guo, Zhi; Zhu, Tong

2015-09-14

Singlet fission presents an attractive solution to overcome the Shockley–Queisser limit by generating two triplet excitons from one singlet exciton. Although triplet excitons are long-lived, their transport occurs through a Dexter transfer, making them slower than singlet excitons, which travel by means of a Förster mechanism. A thorough understanding of the interplay between singlet fission and exciton transport is therefore necessary to assess the potential and challenges of singlet-fission utilization. We report a direct visualization of exciton transport in single tetracene crystals using transient absorption microscopy with 200 fs time resolution and 50 nm spatial precision. Moreover, these measurements revealmore » a new singlet-mediated transport mechanism for triplets, which leads to an enhancement in effective triplet exciton diffusion of more than one order of magnitude on picosecond to nanosecond timescales. These results establish that there are optimal energetics of singlet and triplet excitons that benefit both singlet fission and exciton diffusion.« less

Formation of (DNA)2-LNA triplet with recombinant base recognition: A quantum mechanical study

NASA Astrophysics Data System (ADS)

Mall, Vijaya Shri; Tiwari, Rakesh Kumar

2018-05-01

The formation of DNA triple helix offers the verity of new possibilities in molecular biology. However its applications are limited to purine and pyrimidine rich sequences recognized by forming Hoogsteen/Reverse Hoogsteen triplets in major groove sites of DNA duplex. To overcome this drawback modification in bases backbone and glucose of nucleotide unit of DNA have been proposed so that the third strand base recognized by both the bases of DNA duplex by forming Recombinant type(R-type) of bonding in mixed sequences. Here we performed Quanrum Mechanical (Hartree-Fock and DFT) methodology on natural DNA and Locked Nucleic Acids(LNA) triplets using 6-31G and some other new advance basis sets. Study suggests energetically stable conformation has been observed for recombinant triplets in order of G-C*G > A-T*A > G-C*C > T-A*T for both type of triplets. Interestingly LNA leads to more stable conformation in all set of triplets, clearly suggests an important biological tool to overcome above mentioned drawbacks.

Cooperative singlet and triplet exciton transport in tetracene crystals visualized by ultrafast microscopy

NASA Astrophysics Data System (ADS)

Wan, Yan; Guo, Zhi; Zhu, Tong; Yan, Suxia; Johnson, Justin; Huang, Libai

2015-10-01

Singlet fission presents an attractive solution to overcome the Shockley-Queisser limit by generating two triplet excitons from one singlet exciton. However, although triplet excitons are long-lived, their transport occurs through a Dexter transfer, making them slower than singlet excitons, which travel by means of a Förster mechanism. A thorough understanding of the interplay between singlet fission and exciton transport is therefore necessary to assess the potential and challenges of singlet-fission utilization. Here, we report a direct visualization of exciton transport in single tetracene crystals using transient absorption microscopy with 200 fs time resolution and 50 nm spatial precision. These measurements reveal a new singlet-mediated transport mechanism for triplets, which leads to an enhancement in effective triplet exciton diffusion of more than one order of magnitude on picosecond to nanosecond timescales. These results establish that there are optimal energetics of singlet and triplet excitons that benefit both singlet fission and exciton diffusion.

Energy harvesting of non-emissive triplet excitons in tetracene by emissive PbS nanocrystals

NASA Astrophysics Data System (ADS)

Thompson, Nicholas J.; Wilson, Mark W. B.; Congreve, Daniel N.; Brown, Patrick R.; Scherer, Jennifer M.; Bischof, Thomas S.; Wu, Mengfei; Geva, Nadav; Welborn, Matthew; Voorhis, Troy Van; Bulović, Vladimir; Bawendi, Moungi G.; Baldo, Marc A.

2014-11-01

Triplet excitons are ubiquitous in organic optoelectronics, but they are often an undesirable energy sink because they are spin-forbidden from emitting light and their high binding energy hinders the generation of free electron-hole pairs. Harvesting their energy is consequently an important technological challenge. Here, we demonstrate direct excitonic energy transfer from ‘dark’ triplets in the organic semiconductor tetracene to colloidal PbS nanocrystals, thereby successfully harnessing molecular triplet excitons in the near infrared. Steady-state excitation spectra, supported by transient photoluminescence studies, demonstrate that the transfer efficiency is at least (90 ± 13)%. The mechanism is a Dexter hopping process consisting of the simultaneous exchange of two electrons. Triplet exciton transfer to nanocrystals is expected to be broadly applicable in solar and near-infrared light-emitting applications, where effective molecular phosphors are lacking at present. In particular, this route to ‘brighten’ low-energy molecular triplet excitons may permit singlet exciton fission sensitization of conventional silicon solar cells.

Long-Lived Correlated Triplet Pairs in a π-Stacked Crystalline Pentacene Derivative.

PubMed

Folie, Brendan D; Haber, Jonah B; Refaely-Abramson, Sivan; Neaton, Jeffrey B; Ginsberg, Naomi S

2018-02-14

Singlet fission is the spin-conserving process by which a singlet exciton splits into two triplet excitons. Singlet fission occurs via a correlated triplet pair intermediate, but direct evidence of this state has been scant, and in films of TIPS-pentacene, a small molecule organic semiconductor, even the rate of fission has been unclear. We use polarization-resolved transient absorption microscopy on individual crystalline domains of TIPS-pentacene to establish the fission rate and demonstrate that the initially created triplets remain bound for a surprisingly long time, hundreds of picoseconds, before separating. Furthermore, using a broadband probe, we show that it is possible to determine absorbance spectra of individual excited species in a crystalline solid. We find that triplet interactions perturb the absorbance, and provide evidence that triplet interaction and binding could be caused by the π-stacked geometry. Elucidating the relationship between the lattice structure and the electronic structure and dynamics has important implications for the creation of photovoltaic devices that aim to boost efficiency via singlet fission.

Abnormal maternal echocardiographic findings in triplet pregnancies presenting with dyspnoea.

PubMed

Elhenicky, Marie; Distelmaier, Klaus; Mailath-Pokorny, Mariella; Worda, Christof; Langer, Martin; Worda, Katharina

2016-03-01

The objective of our study was to evaluate the prevalence of abnormal maternal echocardiographic findings in triplet pregnancies presenting with dyspnoea. Between 2003 and 2013, patients' records of 96 triplet pregnancies at our department were analysed including maternal and fetal outcome, echocardiographic parameters and N-terminal pro-B-type natriuretic peptide (NT-proBNP) levels. After exclusion of triplet pregnancies with fetal demise before 23 + 0 weeks, selective feticide or missing outcome data, the study population consisted of 60 triplet pregnancies. All women with dyspnoea underwent echocardiography and measurement of NT-proBNP. Dyspnoea towards the end of pregnancy was observed in 13.3% (8/60) of all women with triplet pregnancies, and all of these women underwent echocardiography. The prevalence of abnormal echocardiographic findings in women with dyspnoea was 37.5% (3/8) with peripartum cardiomyopathy in one woman. Median serum NT-proBNP was significantly higher in women with abnormal echocardiographic findings compared with those without (1779 ng/ml, range 1045-6076 ng/ml vs 172 ng/ml, range 50-311 ng/ml; p < 0.001 by Mann-Whitney-U Test). We conclude that triplet pregnancies presenting with dyspnoea show a high prevalence of abnormal echocardiographic findings. Since dyspnoea is a common sign in triplet pregnancies and is associated with a high rate of cardiac involvement, echocardiography and evaluation of maternal NT-proBNP could be considered to improve early diagnosis and perinatal management.

3-base periodicity in coding DNA is affected by intercodon dinucleotides

PubMed Central

Sánchez, Joaquín

2011-01-01

All coding DNAs exhibit 3-base periodicity (TBP), which may be defined as the tendency of nucleotides and higher order n-tuples, e.g. trinucleotides (triplets), to be preferentially spaced by 3, 6, 9 etc, bases, and we have proposed an association between TBP and clustering of same-phase triplets. We here investigated if TBP was affected by intercodon dinucleotide tendencies and whether clustering of same-phase triplets was involved. Under constant protein sequence intercodon dinucleotide frequencies depend on the distribution of synonymous codons. So, possible effects were revealed by randomly exchanging synonymous codons without altering protein sequences to subsequently document changes in TBP via frequency distribution of distances (FDD) of DNA triplets. A tripartite positive correlation was found between intercodon dinucleotide frequencies, clustering of same-phase triplets and TBP. So, intercodon C|A (where “|” indicates the boundary between codons) was more frequent in native human DNA than in the codon-shuffled sequences; higher C|A frequency occurred along with more frequent clustering of C|AN triplets (where N jointly represents A, C, G and T) and with intense CAN TBP. The opposite was found for C|G, which was less frequent in native than in shuffled sequences; lower C|G frequency occurred together with reduced clustering of C|GN triplets and with less intense CGN TBP. We hence propose that intercodon dinucleotides affect TBP via same-phase triplet clustering. A possible biological relevance of our findings is briefly discussed. PMID:21814388

Dynamics of exciton transfer in coupled polymer chains.

PubMed

Zhang, Y L; Liu, X J; Sun, Z; An, Z

2013-05-07

The dynamics of singlet and triplet exciton transfer in coupled polymer chains are investigated within the Su-Schrieffer-Heeger+Pariser-Parr-Pople model including both electron-phonon (e-p) coupling and electron-electron (e-e) interactions, using a multi-configurational time-dependent Hartree-Fock dynamic method. In order to explain the processes involved, the effects of on-site and long-range e-e interactions on the locality of the singlet and triplet excitons are first investigated on an isolated chain. It is found that the locality of the singlet exciton decreases, while the locality of the triplet exciton increases with an increase in the on-site e-e interactions. On the other hand, an increase in the long-range e-e interaction results in a more localized singlet exciton and triplet exciton. In coupled polymer chains, we then quantitatively show the yields of singlet and triplet exciton transfer products under the same interchain coupling. It is found that the yield of singlet interchain excitons is much higher than that of triplet interchain excitons, that is to say, singlet exciton transfer is significantly easier than that for triplet excitons. This results from the fact that the singlet exciton is more delocalized than the triplet exciton. In addition, hopping of electrons with opposite spins between the coupled chains can facilitate the transfer of singlet excitons. The results are of great significance for understanding the photoelectric conversion process and developing high-power organic optoelectronic applications.

Two Birds with One Stone: Tailoring Singlet Fission for Both Triplet Yield and Exciton Diffusion Length

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

Zhu, Tong; Wan, Yan; Guo, Zhi

2016-06-27

By direct imaging of singlet and triplet populations with ultrafast microscopy, it is shown that the triplet diffusion length and singlet fission yield can be simultaneously optimized for tetracene and its derivatives, making them ideal structures for application in bilayer solar cells.

The supersonic triplet - A new aerodynamic panel singularity with directional properties. [internal wave elimination

NASA Technical Reports Server (NTRS)

Woodward, F. A.; Landrum, E. J.

1979-01-01

A new supersonic triplet singularity has been developed which eliminates internal waves generated by panels having supersonic edges. The triplet is a linear combination of source and vortex distributions which provides the desired directional properties in the flow field surrounding the panel. The theoretical development of the triplet is described, together with its application to the calculation of surface pressure on arbitrary body shapes. Examples are presented comparing the results of the new method with other supersonic panel methods and with experimental data.

Optimization of hybrid blue organic light-emitting diodes based on singlet and triplet exciton diffusion length

NASA Astrophysics Data System (ADS)

Lee, Song Eun; Lee, Ho Won; Lee, Jae Woo; Hwang, Kyo Min; Park, Soo Na; Yoon, Seung Soo; Kim, Young Kwan

2015-06-01

The hybrid blue organic light-emitting diodes (HB OLEDs) with triplet harvesting (TH) structures within an emitting layer (EML) are fabricated with fluorescent and phosphorescent EMLs. The TH is to transfer triplet excitons from fluorescence to phosphorescence, where they can decay radiatively. Remarkably, the half-decay lifetime of a hybrid blue device with fluorescent and phosphorescent EML thickness of 5 and 25 nm, measured at an initial luminance of 500 cd/m2, has improved twice than that of using a conventional structure. Additionally, the blue device’s efficiency improved. We attribute this improvement to the efficient triplet excitons energy transfer and the optimized distribution of the EML which depends on singlet and triplet excitons diffusion length that occurs within each the EML.

The Scattering of X-ray and the induction phenomenon

NASA Astrophysics Data System (ADS)

Fahd, Ziad A.; Mohanty, R. C., , Dr.

2004-11-01

This paper discusses the well-established Faraday's Law of Induction and the associated Lenz's law and compares these laws with a similar law which appears to exist in the triplet production process achieved by bombardment of emulsion with 0-9- Mev X-ray. This comparison shows that an induction-like process occurs during triplet production, leading to the supposition that a force which may be called the ``Matteromotive force'' exists for triplet production. An associated Lenz's-law-like law also appears to exist in this process. For this study, 1935 triplets were observed in 54433 fields of view of the microscopes; out of these, 1872 triplets were measured in the energy interval of 2-90 Mev. In addition, the angular distribution of recoil electrons was observed, and is presented in the paper.

The scattering of X-rays and the induction phenomenon

NASA Astrophysics Data System (ADS)

Mohanty, Rama

2005-03-01

This paper discusses the well-established Faraday’s Law of Induction and the associated Lenz’s law and compares these laws with a similar law which appears to exist in the triplet production process achieved by bombardment of emulsion with 0-9- Mev X-ray. This comparison shows that an induction-like process occurs during triplet production, leading to the supposition that a force which may be called the ``Matteromotive force'' exists for triplet production. An associated Lenz’s-law-like law also appears to exist in this process. For this study, 1935 triplets were observed in 54433 fields of view of the microscopes; out of these, 1872 triplets were measured in the energy interval of 2-90 Mev. In addition, the angular distribution of recoil electrons was observed, and is presented here.

Near Infrared Emission of Highly Electronically Excited CO: A Sensitive Probe to Study the Interstellar Medium??

NASA Technical Reports Server (NTRS)

Gudipati, Murthy S.

2002-01-01

Among the various spectroscopic features of the second most abundant molecule in the space, CO, "the triplet - triplet transitions involving the lowest triplet state a(sup 3)II and the higher-lying a(sup 1)3 SIGMA (sup +), d(sup 3) (DELTA), e (sup 3) SIGMA (sup -) states spanning near-UV to mid-IR spectral range" have so far not been explored in astrophysical observations. The energies of these transitions are highly sensitive to the surroundings in which CO exists, i.e. gas-phase, polar or non-polar condensed phase. It is proposed here that these triplet-triplet emission/absorption bands can be used as a sensitive probe to investigate the local environments of CO, whether in the planetary atmosphere, stellar atmosphere or interstellar medium.

Photoinduced triplet-triplet energy transfer in a 2-ureido-4(1H)-pyrimidinone-bridged, quadruply hydrogen-bonded ferrocene-fullerene assembly.

PubMed

Feng, Ke; Yu, Mao-Lin; Wang, Su-Min; Wang, Ge-Xia; Tung, Chen-Ho; Wu, Li-Zhu

2013-01-14

2-Ureido-4(1H)-pyrimidinone-bridged ferrocene-fullerene assembly I is designed and synthesized for elaborating the photoinduced electron-transfer processes in self-complementary quadruply hydrogen-bonded modules. Unexpectedly, steady-state and time-resolved spectroscopy reveal an inefficient electron-transfer process from the ferrocene to the singlet or triplet excited state of the fullerene, although the electron-transfer reactions are thermodynamically feasible. Instead, an effective intra-assembly triplet-triplet energy-transfer process is found to be operative in assembly I with a rate constant of 9.2×10(5) s(-1) and an efficiency of 73% in CH(2)Cl(2) at room temperature. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Marvel Analysis of the Measured High-resolution Rovibronic Spectra of TiO

NASA Astrophysics Data System (ADS)

McKemmish, Laura K.; Masseron, Thomas; Sheppard, Samuel; Sandeman, Elizabeth; Schofield, Zak; Furtenbacher, Tibor; Császár, Attila G.; Tennyson, Jonathan; Sousa-Silva, Clara

2017-02-01

Accurate, experimental rovibronic energy levels, with associated labels and uncertainties, are reported for 11 low-lying electronic states of the diatomic {}48{{Ti}}16{{O}} molecule, determined using the Marvel (Measured Active Rotational-Vibrational Energy Levels) algorithm. All levels are based on lines corresponding to critically reviewed and validated high-resolution experimental spectra taken from 24 literature sources. The transition data are in the 2-22,160 cm-1 region. Out of the 49,679 measured transitions, 43,885 are triplet-triplet, 5710 are singlet-singlet, and 84 are triplet-singlet transitions. A careful analysis of the resulting experimental spectroscopic network (SN) allows 48,590 transitions to be validated. The transitions determine 93 vibrational band origins of {}48{{Ti}}16{{O}}, including 71 triplet and 22 singlet ones. There are 276 (73) triplet-triplet (singlet-singlet) band-heads derived from Marvel experimental energies, 123(38) of which have never been assigned in low- or high-resolution experiments. The highest J value, where J stands for the total angular momentum, for which an energy level is validated is 163. The number of experimentally derived triplet and singlet {}48{{Ti}}16{{O}} rovibrational energy levels is 8682 and 1882, respectively. The lists of validated lines and levels for {}48{{Ti}}16{{O}} are deposited in the supporting information to this paper.

The excited spin-triplet state of a charged exciton in quantum dots.

PubMed

Molas, M R; Nicolet, A A L; Piętka, B; Babiński, A; Potemski, M

2016-09-14

We report on spectroscopic studies of resonances related to ladder of states of a charged exciton in single GaAlAs/AlAs quantum dot structures. Polarization-resolved photoluminescence, photoluminescence excitation and photon-correlation measurements were performed at low (T  =  4.2 K) temperature also in magnetic field applied in Faraday configuration. The investigated resonances are assigned to three different configurations of a positively charged exciton. Together with a singlet ground state and a conventional triplet state (involving an electron from the ground state electronic s-shell), an excited triplet state, which involved an electron from the excited electronic p-shell was identified in single dots. The appearance of an emission line related to the latter complex is due to a partially suppressed electron relaxation in the investigated dots. An analysis of this emission line allows us to scrupulously determine properties of the excited triplet state and compare them with those of the conventional triplet state. Both triplets exhibit similar patterns of anisotropic fine structure and Zeeman splitting, however their amplitudes significantly differ for those two states. Presented results emphasize the role of the symmetry of the electronic state on the properties of the triplet states of two holes  +  electron excitonic complex.

Three-Photon-Annihilation Contributions to Positronium Energies at Order m α7

NASA Astrophysics Data System (ADS)

Adkins, Gregory S.; Kim, Minji; Parsons, Christian; Fell, Richard N.

2015-12-01

Positronium spectroscopy (n =1 hyperfine splitting, n =2 fine structure, and the 2 S -1 S interval) has reached a precision of order 1 MHz. Vigorous ongoing efforts to improve the experimental results motivate the calculation of the positronium energy levels at order m α7. In this Letter, we present the result for a complete class of such contributions—those involving virtual annihilation of positronium to three photons in an intermediate state. We find an energy shift of 2.6216 (11 )m α7/(n π )3=11.5 /n3 kHz for the spin-triplet S state with principal quantum number n . The corresponding energy shift for true muonium (the μ+μ- bound state) is 2.38 /n3 MHz with an additional -5.33 /n3 MHz coming from electronic vacuum polarization.

Controlling charge balance and exciton recombination by bipolar host in single-layer organic light-emitting diodes

NASA Astrophysics Data System (ADS)

Qiao, Xianfeng; Tao, Youtian; Wang, Qiang; Ma, Dongge; Yang, Chuluo; Wang, Lixiang; Qin, Jingui; Wang, Fosong

2010-08-01

Highly efficient single-layer organic light-emitting diodes with reduced efficiency roll-off are demonstrated by using a bipolar host material of 2,5-bis(2-(9H-carbazol-9-yl)phenyl)-1,3,4-oxadiazole (o-CzOXD) doped with iridium complexes as the emissive layer. For example, the green single-layer device, employing fac-tris(2-phenylpyridine)iridium Ir(ppy)3 as dopant, shows a peak current efficiency of 45.57 cd A-1, corresponding to external quantum efficiency (EQE) of 12.42%, and still exhibits efficiencies of 45.26 cd A-1 and 40.42 cd A-1 at luminance of 1000 and 10 000 cd m-2, respectively. In addition, the yellow and red single-layer devices, with bis(2-(9,9- diethyl-9H-fluoren-2-yl)-1-phenyl-1H-benzoimidazol-N ,C3)iridium(acetylacetonate) (fbi)2Ir(acac) and bis(1-phenylisoquinolinolato-C2,N)iridium(acetylacetonate) (piq)2Ir(acac) as emitter, also show high EQE of 7.04% and 7.28%, respectively. The transport properties of o-CzOXD film are well investigated by current-voltage measurement, from which both hole and electron mobility are determined. It is found that the o-CzOXD shows appealing bipolar transport character, which is favor for the balanced charge distribution in the whole doped zone. More importantly, the multifunctional role of hole trapping and electron transporting of the iridium complex in o-CzOXD further balances the charge carriers and broadens the recombination zone. As a result, the recombination of electrons and holes is significantly improved and the triplet-triplet annihilation and triplet-polaron quenching processes are effectively suppressed, eventually leading to the high efficiency as well as the reduced efficiency roll-off.

Investigation of Oxygen-Induced Quenching of Phosphorescence in Photoexcited Aromatic Molecules by Positron Annihilation Spectroscopy

NASA Technical Reports Server (NTRS)

Singh, Jag J.; Eftekhari, Abe

1996-01-01

Platinum OctaEthyl Porphyrin (Pt.OEP) is an efficient phosphor under ultraviolet excitation. The phosphorescent triplet state P(T(Sup 1)) is readily quenched by the oxygen O2 molecules. This phenomenon is being utilized as the basis for global air pressure measurements in aerodynamic facilities at various laboratories. The exact mechanism by which O2 molecules quench the P(T(Sup 1) approaches P(S(Sub O)) transitions is still unknown. The diamagnetic singlet states P(S(Sub n)), which feed P(T(Sub 1)) states via intersystem crossings, would presumably not be affected by O2. It must be only the magnetic P(T(Sub 1)) states, which can interact with the paramagnetic O2 molecules, that are affected. However, our positron lifetime and Doppler broadening studies suggest the formation of O2P(S(Sub n)), complexes which can also eventually reduce the population of the P(T(Sub 1)) states (i.e., quench phosphorescence). This reduction is possible because higher triplet states in (Pt.OEP) are admixed with the P(S(Sub 1)), states via spin orbit interactions. The experimental procedures and the results of various measurements are presented in this paper.

Unravelling electronic and structural requisites of triplet-triplet energy transfer by advanced electron paramagnetic resonance and density functional theory

NASA Astrophysics Data System (ADS)

Di Valentin, M.; Salvadori, E.; Barone, V.; Carbonera, D.

2013-10-01

Advanced electron paramagnetic resonance (EPR) techniques, in combination with Density Functional theory (DFT), have been applied to the comparative study of carotenoid triplet states in two major photosynthetic antenna complexes, the Peridinin-chlorophyll a-protein of dinoflagellates and the light-harvesting complex II of higher plants. Carotenoid triplet states are populated by triplet-triplet energy transfer (TTET) from chlorophyll molecules to photoprotect the system from singlet oxygen formation under light-stress conditions. The TTET process is strongly dependent on the relative arrangement and on the electronic properties of the triplet states involved. The proposed spectroscopic approach exploits the concept of spin conservation during TTET, which leads to recognisable spin polarisation effects in the time-resolved and field-swept echo-detected EPR spectra. The electron spin polarisation produced at the carotenoid acceptor site depends on the initial polarisation of the chlorophyll donor and on the relative geometrical arrangement of the donor-acceptor zero-field splitting axes. We have demonstrated that a proper analysis of the spectra in the framework of spin angular momentum conservation allows to derive the pathways of TTET and to gain insight into the structural requirements of this mechanism for those antenna complexes, whose X-ray structure is available. We have further proved that this method, developed for natural antenna complexes of known X-ray structure, can be extended to systems lacking structural information in order to derive the relative arrangement of the partners in the energy transfer process. The structural requirements for efficient TTET, obtained from time-resolved and pulse EPR, have been complemented by a detailed description of the electronic structure of the carotenoid triplet state, provided by pulse Electron-Nuclear DOuble Resonance (ENDOR) experiments. Triplet-state hyperfine couplings of the α- and β-protons of the carotenoid conjugated chain have been assigned with the aid of quantum chemical calculation. DFT predictions of the electronic structure of the carotenoid triplet state, in terms of spin density distribution, frontier orbital description and orbital excitation represent suitable building blocks toward a deeper understanding of electronic requirements for efficient TTET.

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

Xi, Liang; Bird, Matthew; Mauro, Gina

Triplet excitons created in poly-2,7-(9,9-dihexyl)fluorene (pF) chains with end trap groups in solution are efficiently transported to and captured by the end groups. The triplets explore the entire lengths of the chains, even for ~100 nm long chains enabling determination of the completeness of end capping. The results show that the chains continuous: they may contain transient barriers or traps, such as those from fluctuations of dihedral angles, but are free of major defects that stop motion of the triplets. Quantitative determinations are aided by the addition of a strong electron donor, TMPD, which removes absorption bands of the end-trappedmore » triplets. For chains having at least one end trap, triplet capture is quantitative on the 1 µs timescale imposed by the use of the donor. Fractions of chains having no end traps were 0.15 for pF samples with anthraquinone (AQ) end traps and 0.063 with naphthylimide (NI) end traps. These determinations agreed with measurements by NMR for short (<40 polymer repeat units (PRU)) chains, where NMR determinations are accurate. The results find no evidence for traps or barriers to transport of triplets, and places limits on the possible presence of defects as impenetrable barriers to less than one per 300 PRU. The present results present a paradigm different from the current consensus, derived from observations of singlet excitons, that conjugated chains are divided into “segments,” perhaps by some kind of defects. For the present pF chains, the segmentation either does not apply to triplet excitons or is transient so that the defects are healed or surmounted in times much shorter than 1 µs. Triplets on chains without end trap groups transfer to chains with end traps on a slower time scale. Rate constants for these bimolecular triplet transfer reactions were found to increase with the length of the accepting chain, as did rate constants for triplet transfer to the chains from small molecules like biphenyl. As a result, a second set of polyfluorenes with 2-butyloctyl side chains was found to have a much lower completeness of end capping.« less

Galaxy triplets in Sloan Digital Sky Survey Data Release 7 - I. Catalogue

NASA Astrophysics Data System (ADS)

O'Mill, Ana Laura; Duplancic, Fernanda; García Lambas, Diego; Valotto, Carlos; Sodré, Laerte

2012-04-01

We present a new catalogue of galaxy triplets derived from the Sloan Digital Sky Survey (SDSS) Data Release 7. The identification of systems was performed considering galaxies brighter than Mr=-20.5 and imposing constraints over the projected distances, radial velocity differences of neighbouring galaxies and isolation. To improve the identification of triplets, we employed a data pixelization scheme, which allows us to handle large amounts of data as in the SDSS photometric survey. Using spectroscopic and photometric data in the redshift range 0.01 ≤z≤ 0.40, we obtain 5901 triplet candidates. We have used a mock catalogue to analyse the completeness and contamination of our methods. The results show a high level of completeness (˜80 per cent) and low contamination (˜5 per cent). By using photometric and spectroscopic data, we have also addressed the effects of fibre collisions in the spectroscopic sample. We have defined an isolation criterion considering the distance of the triplet brightest galaxy to the closest neighbour cluster, to describe a global environment, as well as the galaxies within a fixed aperture, around the triplet brightest galaxy, to measure the local environment. The final catalogue comprises 1092 isolated triplets of galaxies in the redshift range 0.01 ≤z≤ 0.40. Our results show that photometric redshifts provide very useful information, allowing us to complete the sample of nearby systems whose detection is affected by fibre collisions, as well as extending the detection of triplets to large distances, where spectroscopic redshifts are not available.

Formation of singlet oxygen by decomposition of protein hydroperoxide in photosystem II.

PubMed

Pathak, Vinay; Prasad, Ankush; Pospíšil, Pavel

2017-01-01

Singlet oxygen (1O2) is formed by triplet-triplet energy transfer from triplet chlorophyll to O2 via Type II photosensitization reaction in photosystem II (PSII). Formation of triplet chlorophyll is associated with the change in spin state of the excited electron and recombination of triplet radical pair in the PSII antenna complex and reaction center, respectively. Here, we have provided evidence for the formation of 1O2 by decomposition of protein hydroperoxide in PSII membranes deprived of Mn4O5Ca complex. Protein hydroperoxide is formed by protein oxidation initiated by highly oxidizing chlorophyll cation radical and hydroxyl radical formed by Type I photosensitization reaction. Under highly oxidizing conditions, protein hydroperoxide is oxidized to protein peroxyl radical which either cyclizes to dioxetane or recombines with another protein peroxyl radical to tetroxide. These highly unstable intermediates decompose to triplet carbonyls which transfer energy to O2 forming 1O2. Data presented in this study show for the first time that 1O2 is formed by decomposition of protein hydroperoxide in PSII membranes deprived of Mn4O5Ca complex.

Formation of singlet oxygen by decomposition of protein hydroperoxide in photosystem II

PubMed Central

Pathak, Vinay; Prasad, Ankush

2017-01-01

Singlet oxygen (1O2) is formed by triplet-triplet energy transfer from triplet chlorophyll to O2 via Type II photosensitization reaction in photosystem II (PSII). Formation of triplet chlorophyll is associated with the change in spin state of the excited electron and recombination of triplet radical pair in the PSII antenna complex and reaction center, respectively. Here, we have provided evidence for the formation of 1O2 by decomposition of protein hydroperoxide in PSII membranes deprived of Mn4O5Ca complex. Protein hydroperoxide is formed by protein oxidation initiated by highly oxidizing chlorophyll cation radical and hydroxyl radical formed by Type I photosensitization reaction. Under highly oxidizing conditions, protein hydroperoxide is oxidized to protein peroxyl radical which either cyclizes to dioxetane or recombines with another protein peroxyl radical to tetroxide. These highly unstable intermediates decompose to triplet carbonyls which transfer energy to O2 forming 1O2. Data presented in this study show for the first time that 1O2 is formed by decomposition of protein hydroperoxide in PSII membranes deprived of Mn4O5Ca complex. PMID:28732060

Relativistic potential energy surfaces of initial oxidations of Si(100) by atomic oxygen: The importance of surface dimer triplet state

NASA Astrophysics Data System (ADS)

Kim, Tae-Rae; Shin, Seokmin; Choi, Cheol Ho

2012-06-01

The non-relativistic and relativistic potential energy surfaces (PESs) of the symmetric and asymmetric reaction paths of Si(100)-2×1 oxidations by atomic oxygen were theoretically explored. Although only the singlet PES turned out to exist as a major channel leading to "on-dimer" product, both the singlet and triplet PESs leading to "on-top" products are attractive. The singlet PESs leading to the two surface products were found to be the singlet combinations (open-shell singlet) of the low-lying triplet state of surface silicon dimer and the ground 3P state of atomic oxygen. The triplet state of the "on-top" product can also be formed by the ground singlet state of the surface silicon dimer and the same 3P oxygen. The attractive singlet PESs leading to the "on-dimer" and "on-top" products made neither the intersystem crossings from triplet to singlet PES nor high energy 1D of atomic oxygen necessary. Rather, the low-lying triplet state of surface silicon dimer plays an important role in the initial oxidations of silicon surface.

Long-lived, colour-triplet scalars from unnaturalness

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

Barnard, James; Cox, Peter; Gherghetta, Tony

We study that long-lived, colour-triplet scalars are a generic prediction of unnatural, or split, composite Higgs models where the spontaneous global-symmetry breaking scale f ≳ 10TeV and an unbroken SU(5) symmetry is preserved. Since the triplet scalars are pseudo Nambu- Goldstone bosons they are split from the much heavier composite-sector resonances and are the lightest exotic, coloured states. This makes them ideal to search for at colliders. Due to discrete symmetries the triplet scalar decays via a dimension-six term and given the large suppression scale f is often metastable. We show that existing searches for collider-stable R-hadrons from Run-I atmore » the LHC forbid a triplet scalar mass below 845 GeV, whereas with 300 fb -1 at 13TeV triplet scalar masses up to 1.4TeV can be discovered. For shorter lifetimes displaced-vertex searches provide a discovery reach of up to 1.8TeV. Also, we present exclusion and discovery reaches of future hadron colliders as well as indirect limits that arise from modi cations of the Higgs couplings.« less

Long-lived, colour-triplet scalars from unnaturalness

DOE PAGES

Barnard, James; Cox, Peter; Gherghetta, Tony; ...

2016-03-01

We study that long-lived, colour-triplet scalars are a generic prediction of unnatural, or split, composite Higgs models where the spontaneous global-symmetry breaking scale f ≳ 10TeV and an unbroken SU(5) symmetry is preserved. Since the triplet scalars are pseudo Nambu- Goldstone bosons they are split from the much heavier composite-sector resonances and are the lightest exotic, coloured states. This makes them ideal to search for at colliders. Due to discrete symmetries the triplet scalar decays via a dimension-six term and given the large suppression scale f is often metastable. We show that existing searches for collider-stable R-hadrons from Run-I atmore » the LHC forbid a triplet scalar mass below 845 GeV, whereas with 300 fb -1 at 13TeV triplet scalar masses up to 1.4TeV can be discovered. For shorter lifetimes displaced-vertex searches provide a discovery reach of up to 1.8TeV. Also, we present exclusion and discovery reaches of future hadron colliders as well as indirect limits that arise from modi cations of the Higgs couplings.« less

Laser photolysis studies of ω-bond dissociation in aromatic carbonyls with a C-C triple bond stimulated by triplet sensitization.

PubMed

Yamaji, Minoru; Horimoto, Ami; Marciniak, Bronislaw

2017-07-14

We have prepared three types of carbonyl compounds, benzoylethynylmethyl phenyl sulfide (2@SPh), (p-benzoyl)phenylethynylmethyl phenyl sulfide (3@SPh) and p-(benzoylethynyl)benzyl phenyl sulfide (4@SPh) with benzoyl and phenylthiylmethyl groups, which are interconnected with a C-C triple bond and a phenyl ring. Laser flash photolysis of 3@SPh and 4@SPh in acetonitrile provided the transient absorption spectra of the corresponding triplet states where no chemical reactions were recognized. Upon laser flash photolysis of 2@SPh, the absorption band due to the phenylthiyl radical (PTR) was obtained, indicating that the C-S bond cleaved in the excited state. Triplet sensitization of these carbonyl compounds using acetone and xanthone was conducted using laser photolysis techniques. The formation of triplet 3@SPh was seen in the transient absorption, whereas the PTR formation was observed for 2@SPh and 4@SPh, indicating that the triplet states were reactive for the C-S bond dissociation. The C-S bond dissociation mechanism for 4@SPh upon triplet sensitization is discussed in comparison with those for 2@SPh and 3@SPh.

Controlling Long-Lived Triplet Generation from Intramolecular Singlet Fission in the Solid State

DOE PAGES

Pace, Natalie A.; Zhang, Weimin; Arias, Dylan H.; ...

2017-11-30

The conjugated polymer poly(benzothiophene dioxide) (PBTDO1) has recently been shown to exhibit efficient intramolecular singlet fission in solution. We investigate the role of intermolecular interactions in triplet separation dynamics after singlet fission. We use transient absorption spectroscopy to determine the singlet fission rate and triplet yield in two polymers differing only by side-chain motif in both solution and the solid state. Whereas solid-state films show singlet fission rates identical to those measured in solution, the average lifetime of the triplet population increases dramatically and is strongly dependent on side-chain identity. These results show that it may be necessary to carefullymore » engineer the solid-state microstructure of these 'singlet fission polymers' to produce the long-lived triplets needed to realize efficient photovoltaic devices.« less

Controlling Long-Lived Triplet Generation from Intramolecular Singlet Fission in the Solid State

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

Pace, Natalie A.; Zhang, Weimin; Arias, Dylan H.

The conjugated polymer poly(benzothiophene dioxide) (PBTDO1) has recently been shown to exhibit efficient intramolecular singlet fission in solution. We investigate the role of intermolecular interactions in triplet separation dynamics after singlet fission. We use transient absorption spectroscopy to determine the singlet fission rate and triplet yield in two polymers differing only by side-chain motif in both solution and the solid state. Whereas solid-state films show singlet fission rates identical to those measured in solution, the average lifetime of the triplet population increases dramatically and is strongly dependent on side-chain identity. These results show that it may be necessary to carefullymore » engineer the solid-state microstructure of these 'singlet fission polymers' to produce the long-lived triplets needed to realize efficient photovoltaic devices.« less

Photo-assisted intersystem crossing: The predominant triplet formation mechanism in some isolated polycyclic aromatic molecules excited with pulsed lasers

DOE PAGES

Johnson, Philip M.; Sears, Trevor J.

2015-07-28

Naphthalene, anthracene, and phenanthrene are shown to have very long-lived triplet lifetimes when the isolated molecules are excited with nanosecond pulsed lasers resonant with the lowest singlet state. For naphthalene, triplet state populations are created only during the laser pulse, excluding the possibility of normal intersystem crossing at the one photon level, and all molecules have triplet lifetimes greater than hundreds of microseconds, similar to the behavior previously reported for phenylacetylene. Although containing 7–12 thousand cm⁻¹ of vibrational energy, the triplet molecules have ionization thresholds appropriate to vibrationless T₁ states. The laser power dependences (slopes of log-log power plots) ofmore » the excited singlet and triplet populations are about 0.7 for naphthalene and about 0.5 for anthracene. Kinetic modeling of the power dependences successfully reproduces the experimental results and suggests that the triplet formation mechanism involves an enhanced spin orbit coupling caused by sigma character in states at the 2-photon level. Symmetry Adapted Cluster-Configuration Interaction calculations produced excited state absorption spectra to provide guidance for estimating kinetic rates and the sigma character present in higher electronic states. It is concluded that higher excited state populations are significant when larger molecules are excited with pulsed lasers and need to be taken into account whenever discussing the molecular photodynamics.« less

The Relationship of Assisted Reproductive Technology on Perinatal Outcomes in Triplet Gestations.

PubMed

Shah, Jaimin S; Roman, Tania; Viteri, Oscar A; Haidar, Ziad A; Ontiveros, Alejandra; Sibai, Baha M

2018-06-08

 To assess whether assisted reproductive technology (ART) is associated with increased risk of adverse perinatal outcomes in triplet gestations compared with spontaneous conception.  Secondary analysis of a multicenter randomized trial for the prevention of preterm birth in multiple gestations. Triplets delivered at ≥ 24 weeks were studied. The primary outcome was the rate of composite neonatal morbidity (CNM) that included one or more of the following: bronchopulmonary dysplasia, respiratory distress syndrome, necrotizing enterocolitis, culture proven sepsis, pneumonia, retinopathy of prematurity, intraventricular hemorrhage, periventricular leukomalacia, or perinatal death.  There were 381 triplets (127 women) of which 89 patients conceived via ART and 38 patients spontaneously. Women with ART were more likely to be older, Caucasian, married, nulliparous, have higher level of education, and develop pre-eclampsia. Spontaneously conceived triplets were more likely to delivery at an earlier gestation (31.2 ± 3.5 vs 32.8 ± 2.7 weeks) ( p  = 0.009) with a lower birth weight ( p  < 0.001). After adjusting for confounders, no differences were noted in culture proven sepsis, perinatal death, CNM, respiratory distress syndrome, or Apgar score < 7 at 5 minutes. All remaining perinatal outcomes were similar.  Triplets conceived by ART had similar perinatal outcomes compared with spontaneously conceived triplets. Thieme Medical Publishers 333 Seventh Avenue, New York, NY 10001, USA.

Concentrations of a triplet excited state are enhanced in illuminated ice.

PubMed

Chen, Zeyuan; Anastasio, Cort

2017-01-25

Photochemical reactions influence the fates and lifetimes of organic compounds in snow and ice, both through direct photoreactions and via photoproduced transient species such as hydroxyl radical (˙OH) and, perhaps, triplet excited states of organic compounds (i.e., triplets). While triplets can be important oxidants in atmospheric drops and surface waters, little is known of this class of oxidants in frozen samples. To investigate this, we examined the photoreaction of phenol with the triplet state of 3,4-dimethoxybenzaldehyde ( 3 DMB*), a product from biomass combustion, in illuminated laboratory ices. Our results show that the rate of phenol loss due to 3 DMB* is, on average, increased by a factor of 95 ± 50 in ice compared to the equivalent liquid sample. We find that this experimentally measured freeze concentration factor, F EXP , is independent of total solute concentration and temperature, in contrast to what is expected from a liquid-like region whose composition follows freezing point depression. We also find that F EXP for triplets is independent of pH, although the rates of phenol loss increase with decreasing pH in both solution and ice. The enhancement in the rate of phenol loss in/on ice indicates that concentrations of triplet excited states are enhanced in ice relative to solution and suggests that this class of oxidants might be a significant sink for organics in snow and ice.

Brightened spin-triplet interlayer excitons and optical selection rules in van der Waals heterobilayers

NASA Astrophysics Data System (ADS)

Yu, Hongyi; Liu, Gui-Bin; Yao, Wang

2018-07-01

We investigate the optical properties of spin-triplet interlayer excitons in heterobilayer transition metal dichalcogenides in comparison with the spin-singlet ones. Surprisingly, the optical transition dipole of the spin-triplet exciton is found to be in the same order of magnitude to that of the spin-singlet exciton, in sharp contrast to the monolayer excitons where the spin-triplet species is considered as dark compared to the singlet. Unlike the monolayer excitons whose spin-conserved (spin-flip) transition dipole can only couple to light of in-plane (out-of-plane) polarisation, such restriction is removed for the interlayer excitons due to the breaking of the out-of-plane mirror symmetry. We find that as the interlayer atomic registry changes, the optical transition dipole of interlayer exciton crosses between in-plane ones of opposite circular polarizations and the out-of-plane one for both the spin-triplet and spin-singlet species. As a result, excitons of both species have non-negligible coupling into photon modes of both in-plane and out-of-plane propagations, another sharp difference from the monolayers where the exciton couples predominantly into the out-of-plane propagation channel. At given atomic registry, the spin-triplet and spin-singlet excitons have distinct valley polarisation selection rules, allowing the selective optical addressing of both the valley configuration and the spin-singlet/triplet configuration of interlayer excitons.

Size of Ovulatory Follicles in Cattle Expressing Multiple Ovulations Naturally and Its Influence on Corpus Luteum Development and Fertility

USDA-ARS?s Scientific Manuscript database

Long-term genetic selection of cattle for fraternal twins has increased the frequency of twin and triplet ovulations. Although twin and triplet ovulations increased pregnancy rates initially, ratio of fetal number:ovulation site in pregnant females with twin (0.83) or triplet (0.73) ovulations was <...

Parent-Infant Synchrony and the Social-Emotional Development of Triplets

ERIC Educational Resources Information Center

Feldman, Ruth; Eidelman, Arthur I.

2004-01-01

To study the social-emotional development of triplets, 23 sets of triplets, 23 sets of twins, and 23 singleton infants (N=138) were followed from birth to 2 years. Maternal depression and social support were assessed in the postpartum period, mother-infant and father-infant interaction and the home environment were observed at 3 months, a…

The cognitive, behavioral, and personality profiles of a male monozygotic triplet set discordant for sexual orientation.

PubMed

Hershberger, Scott L; Segal, Nancy L

2004-10-01

The neurohormonal theory of sexual orientation proposes that homosexual men and homosexual women are exposed prenatally to a hormonal environment that is similar to that of the other sex. Prenatal exposure to an opposite-sex hormonal environment may lead the nervous system to develop in a manner consistent with the opposite sex. If this cross-sex exposure occurs, one prediction would be that the cognitive ability profile of homosexual men would be similar to that of heterosexual women. This study examined a set of male monozygotic triplets, aged 21 years, discordant for sexual orientation: 2 of the triplets were heterosexual, 1 was homosexual. The triplets were administered measures of 23 domains of cognitive ability, as well as measures of sexual orientation and masculinity/femininity. On the measures of cognitive ability, the triplets performed similarly, yet consistent differences were found between the 2 heterosexual triplets and the 1 homosexual cotriplet. Differences having the same pattern were found for the number of Schafer homosexuality signs on the Rorschach, and on a homosexuality scale derived from items on the Minnesota Multiphasic Personality Inventory--2 (MMPI-2). Responses from the homosexual triplet were in a more feminine direction than responses from his 2 heterosexual cotriplets on measures of masculinity-femininity, which included measures derived from Rorschach responses, the MMPI-2 Masculinity-Femininity scale, the Bem Sex Role Inventory, and the Boyhood Gender Conformity Scale. Responses to the 16 Personality Factor Questionnaire also distinguished the 1 homosexual triplet from the 2 heterosexual cotriplets. These findings support the view that the prenatal hormonal environment may have enduring effects on selected behavioral traits. Copyright 2004 Springer Science + Business Media, Inc.

On the Importance of Electronic Symmetry for Triplet State Delocalization

DOE PAGES

Richert, Sabine; Bullard, George; Rawson, Jeff; ...

2017-03-29

The influence of electronic symmetry on triplet state delocalization in linear zinc porphyrin oligomers is explored by electron paramagnetic resonance techniques. Using a combination of transient continuous wave and pulse electron nuclear double resonance spectroscopies, it is demonstrated experimentally that complete triplet state delocalization requires the chemical equivalence of all porphyrin units. These results are supported by density functional theory calculations, showing uneven delocalization in a porphyrin dimer in which a terminal ethynyl group renders the two porphyrin units inequivalent. When the conjugation length of the molecule is further increased upon addition of a second terminal ethynyl group that restoresmore » the symmetry of the system, the triplet state is again found to be completely delocalized. Finally, the observations suggest that electronic symmetry is of greater importance for triplet state delocalization than other frequently invoked factors such as conformational rigidity or fundamental length-scale limitations.« less

Chain Length Dependence of Energies of Electron and Triplet Polarons in Oligofluorenes

DOE PAGES

Chen, Hung Cheng; Sreearunothai, Paiboon; Cook, Andrew R.; ...

2017-03-01

Bimolecular equilibria measured the one-electron reduction potentials and triplet free energies (ΔG° T) of oligo(9,9-dihexyl)fluorenes and a polymer with lengths of n = 1–10 and 57 repeat units. We can accurately measure one-electron potentials electrochemically only for the shorter oligomers. Starting at n = 1 the free energies change rapidly with increasing length and become constant for lengths longer than the delocalization length. Both the reduction potentials and triplet energies can be understood as the sum of a free energy for a fixed polaron and a positional entropy. Furthermore, the positional entropy increases gradually with length beyond the delocalization lengthmore » due to the possible occupation sites of the charge or the triplet exciton. Our results reinforce the view that charges and triplet excitons in conjugated chains exist as polarons and find that positional entropy can replace a popular empirical model of the energetics.« less

Dictating photoreactivity through restricted bond rotations: cross-photoaddition of atropisomeric acrylimide derivatives under UV/visible-light irradiation.

PubMed

Iyer, Akila; Jockusch, Steffen; Sivaguru, J

2014-11-13

Nonbiaryl atropisomeric acrylimides underwent facile [2 + 2] photocycloaddition leading to cross-cyclobutane adducts with very high stereospecificity (enantiomeric excess (ee): 99% and diastereomeric excess (de): 99%). The photoreactions proceeded smoothly in isotropic media for both direct and triplet sensitized irradiations. The reactions were also found to be very efficient in the solid state where the same cross-cyclobutane adduct was observed. Photophysical studies enabled us to understand the excited-state photochemistry of acrylimides. The triplet energy was found to be ∼63 kcal/mol. The reactions proceeded predominantly via a singlet excited state upon direct irradiation with very poor intersystem crossing that was ascertained by quantification of the generated singlet oxygen. The reactions progressed smoothly with triplet sensitization with UV or visible-light irradiations. Laser flash photolysis experiments established the triplet transient of atropisomeric acrylimides with a triplet lifetime at room temperature of ∼40 ns.

Ribozyme-catalysed RNA synthesis using triplet building blocks.

PubMed

Attwater, James; Raguram, Aditya; Morgunov, Alexey S; Gianni, Edoardo; Holliger, Philipp

2018-05-15

RNA-catalyzed RNA replication is widely believed to have supported a primordial biology. However, RNA catalysis is dependent upon RNA folding, and this yields structures that can block replication of such RNAs. To address this apparent paradox we have re-examined the building blocks used for RNA replication. We report RNA-catalysed RNA synthesis on structured templates when using trinucleotide triphosphates (triplets) as substrates, catalysed by a general and accurate triplet polymerase ribozyme that emerged from in vitro evolution as a mutualistic RNA heterodimer. The triplets cooperatively invaded and unraveled even highly stable RNA secondary structures, and support non-canonical primer-free and bidirectional modes of RNA synthesis and replication. Triplet substrates thus resolve a central incongruity of RNA replication, and here allow the ribozyme to synthesise its own catalytic subunit '+' and '-' strands in segments and assemble them into a new active ribozyme. © 2018, Attwater et al.

Understanding Singlet and Triplet Excitons in Acene Crystals from First Principles

NASA Astrophysics Data System (ADS)

Rangel Gordillo, Tonatiuh; Sharifzadeh, Sahar; Kronik, Leeor; Neaton, Jeffrey

2014-03-01

Singlet fission, a process in which two triplet excitons are formed from a singlet exciton, has the potential to increase the solar cell efficiencies above 100%. Efficient singlet fission has been reported in larger acene crystals, such as tetracene and pentacene, in part attributable to their low-lying triplet energies. In this work, we use many-body perturbation theory within the GW approximation and the Bethe-Salpeter equation approach to compute quasiparticle gaps, low-lying singlet and and triplet excitations, and optical absorption spectra across the entire acene family of crystals, from benzene to hexacene. We closely examine the degree of localization and charge-transfer character of the low-lying singlets and triplets, and their sensitivity to crystal environment, and discuss implications for the efficiency of singlet fission in this systems. This work supported by DOE and computational resources provided by NERSC.

Laser photolysis study of the exciplex between triplet benzil and triethylamine

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

Encinas, M.V.; Scaiano, J.C.

1979-12-19

Nanosecond laser flash photolysis techniques have been used to examine the triplet decay and radical-ion formation in the triethylamine (TEA) - benzil system in wet acetonitrile. Under conditions of high TEA concentrations yielding short triplet lifetime, the formation of the benzil radical anion was found to be considerably slower than the decay of the triplet state. This effect is attributed to the intermediacy of a relatively stable exciplex whose properties are reported here. Results of a study of optical density of the system with time following laser excitation led to the assignment of a lifetime of 55ns to the exciplexmore » formed between the triplet benzil and TEA. A structure is suggested for the exciplex. Results of experiments with the non-polar medium n-heptane indicated a shorter lifetime exciplex or one with very different properties from the species identified in the polar medium, wet acetonitrile. (BLM)« less

Rabi oscillation and electron-spin-echo envelope modulation of the photoexcited triplet spin system in silicon

NASA Astrophysics Data System (ADS)

Akhtar, Waseem; Sekiguchi, Takeharu; Itahashi, Tatsumasa; Filidou, Vasileia; Morton, John J. L.; Vlasenko, Leonid; Itoh, Kohei M.

2012-09-01

We report on a pulsed electron paramagnetic resonance (EPR) study of the photoexcited triplet state (S=1) of oxygen-vacancy centers in silicon. Rabi oscillations between the triplet sublevels are observed using coherent manipulation with a resonant microwave pulse. The Hahn echo and stimulated echo decay profiles are superimposed with strong modulations known as electron-spin-echo envelope modulation (ESEEM). The ESEEM spectra reveal a weak but anisotropic hyperfine coupling between the triplet electron spin and a 29Si nuclear spin (I=1/2) residing at a nearby lattice site, that cannot be resolved in conventional field-swept EPR spectra.

Large refractive index variations induced by accumulating triplet excitons under photoexcitation at low power

NASA Astrophysics Data System (ADS)

Hori, Tomoe; Totani, Kenro; Hirata, Shuzo; Watanabe, Toshiyuki

2018-07-01

Herein, we present a method for the modification of the refractive index (n), based on employing an organic molecule with a long triplet excited-state lifetime. A host-guest material composed of a cyclic aromatic as the guest and an amorphous steroidal compound as the host was used to modulate n. The guest material exhibited a triplet lifetime longer than 1 s, and a high-density triplet excited-state population was obtained upon excitation with blue-violet light. The refractive index could be changed by 0.002, even when using a relatively low excitation power level of 100 mW cm-2.

High-Fidelity Single-Shot Singlet-Triplet Readout of Precision-Placed Donors in Silicon.

PubMed

Broome, M A; Watson, T F; Keith, D; Gorman, S K; House, M G; Keizer, J G; Hile, S J; Baker, W; Simmons, M Y

2017-07-28

In this work we perform direct single-shot readout of the singlet-triplet states in exchange coupled electrons confined to precision-placed donor atoms in silicon. Our method takes advantage of the large energy splitting given by the Pauli-spin blockaded (2,0) triplet states, from which we can achieve a single-shot readout fidelity of 98.4±0.2%. We measure the triplet-minus relaxation time to be of the order 3 s at 2.5 T and observe its predicted decrease as a function of magnetic field, reaching 0.5 s at 1 T.

High efficient white organic light-emitting diodes with single emissive layer using phosphorescent red, green, and blue dopants

NASA Astrophysics Data System (ADS)

Kim, You-Hyun; Wai Cheah, Kok; Young Kim, Woo

2013-07-01

Phosphorescent white organic light-emitting diodes (PHWOLEDs) with single emissive layer were fabricated by co-doping phosphorescent blue, green, and red emitters with different concentrations. WOLEDs using Ir(piq)3 and Ir(ppy)3 as red and green dopants along with 8% of Firpic as blue dopant with host materials of 4CzPBP in the emissive layer were compared under various doping ratio between Ir(piq)3 and Ir(ppy)3. Triplet-triplet Dexter energy transfer in single emissive PHWOLEDs including three primary colors was saturated from higher triplet energy levels to lower triplet energy levels directly.

Infrared laser spectroscopy of jet-cooled carbon clusters: structure of triplet C6

NASA Technical Reports Server (NTRS)

Hwang, H. J.; Van Orden, A.; Tanaka, K.; Kuo, E. W.; Heath, J. R.; Saykally, R. J.

1993-01-01

We report the first structural characterization of the triplet isomer of C6. Forty-one rovibrational/fine structure transitions in the nu 4(sigma u) antisymmetric stretch fundamental of the C6 cluster have been measured by diode laser absorption spectroscopy of a supersonic carbon cluster beam. The observed spectrum is characteristic of a centrosymmetric linear triplet state with cumulene-type bonding. The measured ground state rotational constant B0 = 0.048 479 (10)cm-1 and the effective bond length r(eff) = 1.2868 (1) angstroms are in good agreement with ab initio predictions for the linear triplet (3 sigma g-) state of C6.

Verification of the electron/proton coupled mechanism for phenolic H-atom transfer using a triplet π,π ∗ carbonyl

NASA Astrophysics Data System (ADS)

Yamaji, Minoru; Oshima, Juro; Hidaka, Motohiko

2009-06-01

Evidence for the coupled electron/proton transfer mechanism of the phenolic H-atom transfer between triplet π,π ∗ 3,3'-carbonylbis(7-diethylaminocoumarin) and phenol derivatives is obtained by using laser photolysis techniques. It was confirmed that the quenching rate constants of triplet CBC by phenols having positive Hammett constants do not follow the Rehm-Weller equation for electron transfer while those by phenols with negative Hammett constants do it. From the viewpoint of thermodynamic parameters for electron transfer, the crucial factors for phenolic H-atom transfer to π,π ∗ triplet are discussed.

Can H-aggregates serve as light-harvesting antennae? Triplet-triplet energy transfer between excited aggregates and monomer thionine in aerosol-OT solutions

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

Das, S.; Kamat, P.V.

1999-01-07

The cationic dye thionine undergoes slow dissolution in aerosol-OT (AOT) containing solutions of heptane and toluene. By controlling the ratio of [dye]/[AOT], it is possible to obtain varying amounts of monomer, dimer, and higher order aggregates (trimer) in dilute dye solutions. The thionine aggregates exhibit characteristic absorption maxima at 565 and 530 nm for the dimer and trimer forms, respectively. The singlet excited states of these dye aggregates are short-lived ({tau} = 40--63 ps) as they undergo efficient intersystem crossing to generate the triplet excited states. Triplet energy transfer from the excited dye aggregates to monomeric thionine molecules was observedmore » upon excitation with a 532 nm laser pulse. Pulse radiolysis experiments, in which the excited triplet states were generated indirectly, also confirm the finding that the triplet energy cascades down from excited trimer to dimer to monomeric dye. These studies demonstrate the possibility of using H-type dye aggregates as antenna molecules to harvest light energy whereby the aggregate molecules absorb light in different spectral regions and subsequently transfer energy to the monomeric dye.« less

Triplet pregnancies: perinatal outcome evolution.

PubMed

Almeida, Patrícia; Domingues, Ana Patrícia; Belo, Adriana; Fonseca, Etelvina; Moura, Paulo

2014-09-01

To evaluate the obstetric and perinatal outcomes evolution of triplet pregnancies. A prospective observational study was conducted in triplet pregnancies delivered over 16 years in a tertiary obstetric center with differentiated perinatal support. Evaluation of demographic factors, obstetric complications, gestational age at delivery, mode of delivery, birth weight and immediate newborn outcome were done over a 16 years period. A global characterization of the sample was performed considering the listed parameters. Variables were categorized in three groups according to year of occurrence: 1996-2000, 2001-2006, 2007-2011, and all parameters were compared. Of the 33 triplets included, 72.7% resulted from induced pregnancies. All except one patient received prenatal corticosteroids and five received tocolytics. All women delivered prenatally and no significant differences were seen in the mean gestational age at delivery or birth weight towards time. There were three intrauterine fetal deaths. Neonatal immediate outcomes were not significantly different over the years. Despite remarkable progresses in perinatal and neonatal cares, no noticeable impact in triplet gestations' outcomes was seen, sustaining that triplets should be avoided due to their great risk of prematurity and neonatal morbidities, either by limiting the numbers of embryos transferred or by fetal reduction.

Density functional theory study of direct and indirect photodegradation mechanisms of sulfameter.

PubMed

Shah, Shaheen; Hao, Ce

2016-10-01

Sulfonamide antibiotics (SAs) have been observed to undergo direct and indirect photodegradation in natural water environments. In this study, the density functional theory (DFT) method was employed for the study of direct and indirect photodegradation mechanisms of sulfameter (SME) with excited triplet states of dissolved organic matter ((3)DOM(*)) and metal ions. SME was adopted as a representative of SAs, and SO2 extrusion product was obtained with different energy paths in the triplet-sensitized photodegradation of the neutral (SME(0)) and the anionic (SME(-)) form of SME. The selected divalent metal ions (Ca(2+), Mg(2+), and Zn(2+)) promoted the triplet-sensitized photodegradation of SME(0) but showed an inhibitory effect in triplet-sensitized photodegradation of SME(-). The triplet-sensitized indirect photodegradation mechanism of SME was investigated with the three DOM analogues, i.e., 2-acetonaphthone (2-AN), fluorenone (FN), and thioxanthone (TN). Results indicated that the selected DOM analogues are highly responsible for the photodegradation via attacking on amine moiety of SME. According to the natural bond orbital (NBO) analysis, the triplet-sensitized photodegradation mechanism of SME(0) with 2-AN, FN, and TN was H-transfer, and the SME(-) was proton plus electron transfer with these DOM analogues.

The photophysics of monomeric bacteriochlorophylls c and d and their derivatives: properties of the triplet state and singlet oxygen photogeneration and quenching

NASA Technical Reports Server (NTRS)

Krasnovsky, A. A. Jr; Cheng, P.; Blankenship, R. E.; Moore, T. A.; Gust, D.

1993-01-01

Measurements of pigment triplet-triplet absorption, pigment phosphorescence and photosensitized singlet oxygen luminescence were carried out on solutions containing monomeric bacteriochlorophylls (Bchl) c and d, isolated from green photosynthetic bacteria, and their magnesium-free and farnesyl-free analogs. The energies of the pigment triplet states fell in the range 1.29-1.34 eV. The triplet lifetimes in aerobic solutions were 200-250 ns; they increased to 280 +/- 70 microseconds after nitrogen purging in liquid solutions and to 0.7-2.1 ms in a solid matrix at ambient or liquid nitrogen temperatures. Rate constants for quenching of the pigment triplet state by oxygen were (2.0-2.5) x 10(9) M-1 s-1, which is close to 1/9 of the rate constant for diffusion-controlled reactions. This quenching was accompanied by singlet oxygen formation. The quantum yields for the triplet state formation and singlet oxygen production were 55-75% in air-saturated solutions. Singlet oxygen quenching by ground-state pigment molecules was observed. Quenching was the most efficient for magnesium-containing pigments, kq = (0.31-1.2) x 10(9) M-1 s-1. It is caused mainly by a physical process of singlet oxygen (1O2) deactivation. Thus, Bchl c and d and their derivatives, as well as chlorophyll and Bchl a, combine a high efficiency of singlet oxygen production with the ability to protect photochemical and photobiological systems against damage by singlet oxygen.

On the He(plus) triplet line intensities

NASA Technical Reports Server (NTRS)

Daltabuit, E.; Cox, D.

1971-01-01

The theoretical calculations of helium triplet line strengths, including collisional enhancement, are compared to astronomical observations. Both are plotted on an I(10830)/I(5876) vs I(5876)/I(4471) plane. It appears that the theory of helium triplet line strengths agrees with present observations, and that the question of an additional depopulation mechanism for the 2 3S population is probably predicted correctly within 30%.

Interactions of NO{sub 2}{sup {minus}} and SO{sub 3}{sup 2{minus}} with organic triplets. Charge transfer versus energy transfer: The role of reorganization energy in triplet-anion interactions and spectroscopic methods for its evaluation

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

Loeff, I.; Treinin, A.; Linschitz, H.

1992-06-25

Charge-transfer (CT) and energy-transfer (NT) interactions of simple anions with organic triplets are reviewed and discussed in connection with new quenching rate constant (K{sub q}) and radical yield measurements for SO{sub 3}{sup 2{minus}} and No{sub 2}{sup {minus}}. In the latter case both processes may occur at high organic triplet energies. Reorganization energies for one-electron oxidations are obtained for several anions, using data on charge-transfer-to-solvent (CTTS) spectra and photoelectron emission thresholds, which like the kinetic parameters of Marcus-Hush theory, also reflect Franck-Condon strains. The results, combined with thermodynamic free energies, give vertical redox potentials which correlate better than do equilibrium potentialsmore » with quenching rates. The theoretical basis for correlation between k{sub q} and Hv{sub CTTS} is discussed in the framework of Marcus rate theory. Assigning the total reorganization energy in the CT quenching reaction to the small anion component of the D-A pair gives reasonable agreement with data on quenching of dye triplets but too slow rates for aryl carbonyl triplets where exciplex formation may possibly occur. The optical reorganization energy for NO{sub 2}{sup {minus}} leads to values of the thermal self-exchange rate agreeing with those computed from the Marcus-Hush cross-relations, which also neglect bonding effects. The mechanism of NO{sub 2}{sup {minus}} interaction with triplets is discussed in detail, including indirect kinetic evidence for quenching of a short-lived exciplex by NO{sub 2}{sup {minus}} without radical formation. The possibility of reduction by triplet NO{sub 2}{sup {minus}} formed by initial NT from the organic triplet is also considered. Finally, a scheme is presented involving an equilibrium between CT and NT states and relating the free energy difference between these states to radical yields. 54 refs., 8 figs., 3 tabs.« less

Long-Lived Triplet Excited States of Bent-Shaped Pentacene Dimers by Intramolecular Singlet Fission.

PubMed

Sakuma, Takao; Sakai, Hayato; Araki, Yasuyuki; Mori, Tadashi; Wada, Takehiko; Tkachenko, Nikolai V; Hasobe, Taku

2016-03-24

Intramolecular singlet fission (ISF) is a promising photophysical process to construct more efficient light energy conversion systems as one excited singlet state converts into two excited triplet states. Herein we synthesized and evaluated bent-shaped pentacene dimers as a prototype of ISF to reveal intrinsic characters of triplet states (e.g., lifetimes of triplet excited states). In this study, meta-phenylene-bridged TIPS-pentacene dimer (PcD-3Ph) and 2,2'-bipheynyl bridged TIPS-pentacene dimer (PcD-Biph) were newly synthesized as bent-shaped dimers. In the steady-state spectroscopy, absorption and emission bands of these dimers were fully characterized, suggesting the appropriate degree of electronic coupling between pentacene moieties in these dimers. In addition, the electrochemical measurements were also performed to check the electronic interaction between two pentacene moieties. Whereas the successive two oxidation peaks owing to the delocalization were observed in a directly linked-pentacene dimer (PcD) by a single bond, the cyclic voltammograms in PcD-Biph and PcD-3Ph implied the weaker interaction compared to that of p-phenylene-bridged TIPS-pentacene dimer (PcD-4Ph) and PcD. The femtosecond and nanosecond transient absorption spectra clearly revealed the slower ISF process in bent-shaped pentacene dimers (PcD-Biph and PcD-3Ph), more notably, the slower relaxation of the excited triplet states in PcD-Biph and PcD-3Ph. Namely, the quantum yields of triplet states (ΦT) by ISF approximately remain constant (ca. 180-200%) in all dimer systems, whereas the lifetimes of the triplet excited states became much longer (up to 360 ns) in PcD-Biph as compared to PcD-4Ph (15 ns). Additionally, the lifetimes of the corresponding triplet states in PcD-Biph and PcD-3Ph were sufficiently affected by solvent viscosity. In particular, the lifetimes of PcD-Biph triplet state in THF/paraffin (1.0 μs) increased up to approximately three times as compared to that in THF (360 ns), whereas those of PcD-4Ph were quite similar in both solvent.

Effect of xenon on the excited states of phototropic receptor flavin in corn seedlings

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

Vierstra, R.D.; Poff, K.L.; Walker, E.B.

1981-05-01

The chemically inert, water-soluble heavy atom gas, xenon, at millimolar concentrations specifically quenches the triplet excited state of flavin in solution without quenching the flavin singlet excited state. The preferential quenching of the flavin triplet over the singlet excited state by Xe has been established by showing that the flavin triplet-sensitized photooxidation of NADH is inhibited while the fluorescence intensity and lifetime of flavin are not affected by Xe. No significant inhibition of phototropism and geotropism by Xe was observed, suggesting that a flavin singlet state is more likely involved than the triplet state in the primary photoprocess of phototropismmore » in corn.« less

Ab Initio Calculations of Singlet and Triplet Excited States of Chlorine Nitrate and Nitric Acid

NASA Technical Reports Server (NTRS)

Grana, Ana M.; Lee, Timothy J.; Head-Gordon, Martin; Langhoff, Stephen R. (Technical Monitor)

1994-01-01

Ab initio calculations of vertical excitations to singlet and triplet excited states of chlorine nitrate and nitric acid are reported. The nature of the electronic transitions are examined by decomposing the difference density into the sum of detachment and attachment densities. Counterparts for the three lowest singlet excited states of nitric acid survive relatively unperturbed in chlorine nitrate, while other low-lying singlet states of chlorine nitrate appear to be directly dissociative in the ClO chromophore. These results suggest an assignment of the two main peaks in the experimental chlorine nitrate absorption spectrum. In addition, triplet vertical excitations and the lowest optimized triplet geometries of both molecules are studied.

Laser photolysis studies of the phenolic H-atom transfer mechanism for a triplet π,π ∗ ketone in solution revisited

NASA Astrophysics Data System (ADS)

Yamaji, Minoru; Aoyama, Yutaka; Furukawa, Takashi; Itoh, Takao; Tobita, Seiji

2006-03-01

The mechanism of the H-atom transfer from phenols or thiophenols to triplet π,π ∗ 5,12-naphthacenequinone (5,12-NQ) has been examined by means of laser flash photolysis at 295 K. Based on the Hammett plots and the Rehm-Weller equation for the quenching rate constants, the phenolic H-atom transfer from phenols or thiophenols to triplet π,π ∗ 5,12-NQ is shown to proceed via the electron transfer followed by proton transfer. The previously proposed mechanism for H-atom transfer of π,π ∗ triplets, that proton transfer is followed by electron transfer, was not verified in the present systems.

A density-functional-theory study of biradicals from benzene to hexacene

NASA Astrophysics Data System (ADS)

Kim, Hyun-Jung; Wang, Xingyong; Ma, Jing; Cho, Jun-Hyung

2011-11-01

The singlet-triplet energy gap of biradicals created in benzene and polyacenes is investigated by density-functional-theory calculations. For the biradicals in benzene, naphthalene, anthracene, tetracene, pentacene, and hexacene, we find that the singlet state is energetically favored over the triplet state by 189, 191, 184, 199, 218, and 244 meV, respectively. The monotonous increase of the singlet-triplet energy gap from anthracene to hexacene is attributed to the enhanced stability of the singlet state for longer polyacenes. Our analysis shows that the spin density of the singlet state is delocalized over all benzene rings, but such a spin delocalization is not present for the triplet state.

Off-Centre Effects in the Triplet Relaxed Excited State of Ga+ Centres in CsBr:Ga Crystal

NASA Astrophysics Data System (ADS)

Kalder, K.; Korrovits, V.; Nagirnyi, V.; Stolovits, A.; Zazubovich, S.; Babin, V.

1997-06-01

Spectra, polarization and decay kinetics of the triplet and singlet emission of Ga+ centres in CsBr:Ga crystals have been studied in the temperature range of 0.1 to 400 K. It has been found that the triplet AX and AT emission bands coincide. Two slow components have been observed in the decay kinetics of each emission at T < 1.5 K and explained by the tunnel splitting of the metastable minima of the corresponding triplet relaxed excited state. It points to the off-centre displacement of a Ga+ ion from a crystal lattice site both in the tetragonal (T) and in the trigonal (X) Jahn-Teller minima.

Revealing the spin–vibronic coupling mechanism of thermally activated delayed fluorescence

PubMed Central

Etherington, Marc K.; Gibson, Jamie; Higginbotham, Heather F.; Penfold, Thomas J.; Monkman, Andrew P.

2016-01-01

Knowing the underlying photophysics of thermally activated delayed fluorescence (TADF) allows proper design of high efficiency organic light-emitting diodes. We have proposed a model to describe reverse intersystem crossing (rISC) in donor–acceptor charge transfer molecules, where spin–orbit coupling between singlet and triplet states is mediated by one of the local triplet states of the donor (or acceptor). This second order, vibronically coupled mechanism describes the basic photophysics of TADF. Through a series of measurements, whereby the energy ordering of the charge transfer (CT) excited states and the local triplet are tuned in and out of resonance, we show that TADF reaches a maximum at the resonance point, substantiating our model of rISC. Moreover, using photoinduced absorption, we show how the populations of both singlet and triplet CT states and the local triplet state change in and out of resonance. Our vibronic coupling rISC model is used to predict this behaviour and describes how rISC and TADF are affected by external perturbation. PMID:27901046

Amplitude control of the spin-triplet supercurrent in S / F / S Josephson junctions

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

Martinez, William M.; Pratt, Jr., W. P.; Birge, Norman O.

Josephson junctions made with conventional s-wave superconductors and containing multiple layers of ferromagnetic materials can carry spin-triplet supercurrent in the presence of certain types of magnetic inhomogeneity. In junctions containing three ferromagnetic layers, the triplet supercurrent is predicted to be maximal when the magnetizations of the adjacent layers are orthogonal, and zero when the magnetizations of any two adjacent layers are parallel. Here we demonstrate on-off control of the spin-triplet supercurrent in such junctions, achieved by rotating the magnetization direction of one of the three layers by 90°. We obtain “on-off” ratios of 5, 7, and 19 for the supercurrentmore » in the three samples that have been studied so far. In conclusion, these observations directly confirm one of the most salient predictions of the theory, and they pave the way for applications of spin-triplet Josephson junctions in the nascent area of “superconducting spintronics”.« less

The origin of efficient triplet state population in sulfur-substituted nucleobases

PubMed Central

Mai, Sebastian; Pollum, Marvin; Martínez-Fernández, Lara; Dunn, Nicholas; Marquetand, Philipp; Corral, Inés; Crespo-Hernández, Carlos E.; González, Leticia

2016-01-01

Elucidating the photophysical mechanisms in sulfur-substituted nucleobases (thiobases) is essential for designing prospective drugs for photo- and chemotherapeutic applications. Although it has long been established that the phototherapeutic activity of thiobases is intimately linked to efficient intersystem crossing into reactive triplet states, the molecular factors underlying this efficiency are poorly understood. Herein we combine femtosecond transient absorption experiments with quantum chemistry and nonadiabatic dynamics simulations to investigate 2-thiocytosine as a necessary step to unravel the electronic and structural elements that lead to ultrafast and near-unity triplet-state population in thiobases in general. We show that different parts of the potential energy surfaces are stabilized to different extents via thionation, quenching the intrinsic photostability of canonical DNA and RNA nucleobases. These findings satisfactorily explain why thiobases exhibit the fastest intersystem crossing lifetimes measured to date among bio-organic molecules and have near-unity triplet yields, whereas the triplet yields of canonical nucleobases are nearly zero. PMID:27703148

On soil textural classifications and soil-texture-based estimations

NASA Astrophysics Data System (ADS)

Ángel Martín, Miguel; Pachepsky, Yakov A.; García-Gutiérrez, Carlos; Reyes, Miguel

2018-02-01

The soil texture representation with the standard textural fraction triplet sand-silt-clay is commonly used to estimate soil properties. The objective of this work was to test the hypothesis that other fraction sizes in the triplets may provide a better representation of soil texture for estimating some soil parameters. We estimated the cumulative particle size distribution and bulk density from an entropy-based representation of the textural triplet with experimental data for 6240 soil samples. The results supported the hypothesis. For example, simulated distributions were not significantly different from the original ones in 25 and 85 % of cases when the sand-silt-clay and very coarse+coarse + medium sand - fine + very fine sand - silt+clay were used, respectively. When the same standard and modified triplets were used to estimate the average bulk density, the coefficients of determination were 0.001 and 0.967, respectively. Overall, the textural triplet selection appears to be application and data specific.

Three-dimensional structure of basal body triplet revealed by electron cryo-tomography

PubMed Central

Li, Sam; Fernandez, Jose-Jesus; Marshall, Wallace F; Agard, David A

2012-01-01

Basal bodies and centrioles play central roles in microtubule (MT)-organizing centres within many eukaryotes. They share a barrel-shaped cylindrical structure composed of nine MT triplet blades. Here, we report the structure of the basal body triplet at 33 Å resolution obtained by electron cryo-tomography and 3D subtomogram averaging. By fitting the atomic structure of tubulin into the EM density, we built a pseudo-atomic model of the tubulin protofilaments at the core of the triplet. The 3D density map reveals additional densities that represent non-tubulin proteins attached to the triplet, including a large inner circular structure in the basal body lumen, which functions as a scaffold to stabilize the entire basal body barrel. We found clear longitudinal structural variations along the basal body, suggesting a sequential and coordinated assembly mechanism. We propose a model in which δ-tubulin and other components participate in the assembly of the basal body. PMID:22157822

Synthesis and Exciton Dynamics of Donor-Orthogonal Acceptor Conjugated Polymers: Reducing the Singlet-Triplet Energy Gap.

PubMed

Freeman, David M E; Musser, Andrew J; Frost, Jarvist M; Stern, Hannah L; Forster, Alexander K; Fallon, Kealan J; Rapidis, Alexandros G; Cacialli, Franco; McCulloch, Iain; Clarke, Tracey M; Friend, Richard H; Bronstein, Hugo

2017-08-16

The presence of energetically low-lying triplet states is a hallmark of organic semiconductors. Even though they present a wealth of interesting photophysical properties, these optically dark states significantly limit optoelectronic device performance. Recent advances in emissive charge-transfer molecules have pioneered routes to reduce the energy gap between triplets and "bright" singlets, allowing thermal population exchange between them and eliminating a significant loss channel in devices. In conjugated polymers, this gap has proved resistant to modification. Here, we introduce a general approach to reduce the singlet-triplet energy gap in fully conjugated polymers, using a donor-orthogonal acceptor motif to spatially separate electron and hole wave functions. This new generation of conjugated polymers allows for a greatly reduced exchange energy, enhancing triplet formation and enabling thermally activated delayed fluorescence. We find that the mechanisms of both processes are driven by excited-state mixing between π-π*and charge-transfer states, affording new insight into reverse intersystem crossing.

Revealing the spin-vibronic coupling mechanism of thermally activated delayed fluorescence

NASA Astrophysics Data System (ADS)

Etherington, Marc K.; Gibson, Jamie; Higginbotham, Heather F.; Penfold, Thomas J.; Monkman, Andrew P.

2016-11-01

Knowing the underlying photophysics of thermally activated delayed fluorescence (TADF) allows proper design of high efficiency organic light-emitting diodes. We have proposed a model to describe reverse intersystem crossing (rISC) in donor-acceptor charge transfer molecules, where spin-orbit coupling between singlet and triplet states is mediated by one of the local triplet states of the donor (or acceptor). This second order, vibronically coupled mechanism describes the basic photophysics of TADF. Through a series of measurements, whereby the energy ordering of the charge transfer (CT) excited states and the local triplet are tuned in and out of resonance, we show that TADF reaches a maximum at the resonance point, substantiating our model of rISC. Moreover, using photoinduced absorption, we show how the populations of both singlet and triplet CT states and the local triplet state change in and out of resonance. Our vibronic coupling rISC model is used to predict this behaviour and describes how rISC and TADF are affected by external perturbation.

Amplitude control of the spin-triplet supercurrent in S / F / S Josephson junctions

DOE PAGES

Martinez, William M.; Pratt, Jr., W. P.; Birge, Norman O.

2016-02-17

Josephson junctions made with conventional s-wave superconductors and containing multiple layers of ferromagnetic materials can carry spin-triplet supercurrent in the presence of certain types of magnetic inhomogeneity. In junctions containing three ferromagnetic layers, the triplet supercurrent is predicted to be maximal when the magnetizations of the adjacent layers are orthogonal, and zero when the magnetizations of any two adjacent layers are parallel. Here we demonstrate on-off control of the spin-triplet supercurrent in such junctions, achieved by rotating the magnetization direction of one of the three layers by 90°. We obtain “on-off” ratios of 5, 7, and 19 for the supercurrentmore » in the three samples that have been studied so far. In conclusion, these observations directly confirm one of the most salient predictions of the theory, and they pave the way for applications of spin-triplet Josephson junctions in the nascent area of “superconducting spintronics”.« less

Supercurrent in ferromagnetic Josephson junctions with heavy metal interlayers

NASA Astrophysics Data System (ADS)

Satchell, Nathan; Birge, Norman O.

2018-06-01

The length scale over which supercurrent from conventional BCS, s -wave superconductors (S ) can penetrate an adjacent ferromagnetic (F ) layer depends on the ability to convert singlet Cooper pairs into triplet Cooper pairs. Spin-aligned triplet Cooper pairs are not dephased by the ferromagnetic exchange interaction and can thus penetrate an F layer over much longer distances than singlet Cooper pairs. These triplet Cooper pairs carry a dissipationless spin current and are the fundamental building block for the fledgling field of superspintronics. Singlet-triplet conversion by inhomogeneous magnetism is well established. Here, we describe an attempt to use spin-orbit coupling as an alternative mechanism to mediate singlet-triplet conversion in S-F-S Josephson junctions. We report that the addition of thin Pt spin-orbit-coupling layers in our Josephson junctions significantly increases supercurrent transmission, however the decay length of the supercurrent is not found to increase. We attribute the increased supercurrent transmission to Pt acting as a buffer layer to improve the growth of the Co F layer.

Photoprotection and triplet energy transfer in higher plants: the role of electronic and nuclear fluctuations.

PubMed

Cupellini, Lorenzo; Jurinovich, Sandro; Prandi, Ingrid G; Caprasecca, Stefano; Mennucci, Benedetta

2016-04-28

Photosynthetic organisms employ several photoprotection strategies to avoid damage due to the excess energy in high light conditions. Among these, quenching of triplet chlorophylls by neighboring carotenoids (Cars) is fundamental in preventing the formation of singlet oxygen. Cars are able to accept the triplets from chlorophylls by triplet energy transfer (TET). We have here studied TET rates in CP29, a minor light-harvesting complex (LHC) of the Photosystem II in plants. A fully atomistic strategy combining classical molecular dynamics of the LHC in its natural environment with a hybrid time-dependent density functional theory/polarizable MM description of the TET is used. We find that the structural fluctuations of the pigment-protein complex can largely enhance the transfer rates with respect to those predicted using the crystal structure, reducing the triplet quenching times in the subnanosecond scale. These findings add a new perspective for the interpretation of the photoprotection function and its relation with structural motions of the LHC.

Organic light-emitting diodes with a spacer enhanced exciplex emission

NASA Astrophysics Data System (ADS)

Yan, Fei; Chen, Rui; Sun, Handong; Wei Sun, Xiao

2014-04-01

By introducing a spacer molecule into the blended exciplex emissive layer, the performance of the bulk heterojunction exciplex organic light-emitting diodes (OLEDs) was improved dramatically; the maximum luminous efficiency was enhanced by about 22% from 7.9 cd/A to 9.7 cd/A, and the luminous efficiency drop was reduced by 28% at 400 mA/cm2. Besides the suppressed annihilation of exciton, the time-resolved photoluminescence measurements indicated that the spacer enhanced the delayed fluorescence through increasing the backward intersystem crossing rate from the triplet to singlet exciplex state. This method is useful for developing high performance exciplex OLEDs.

Generalized Stone-Wales transformation as the possible origin of ferromagnetism in polymeric C60: a density-functional theory study.

PubMed

Ribas-Ariño, J; Novoa, Juan J

2006-11-07

Recently, there has been a proposal [Y.-H. Kim et al., Phys. Rev. B 68, 125420 (2003)] suggesting that ferromagnetic interactions in compressed and heated polymeric-C(60) solids could be due to the existence of triplet open cages resulting from successive generalized Stone-Wales transformations within the C(60) cage. Here, by performing B3LYP3-21G and B3LYP6-31G(d) optimizations, we carried out a systematic investigation of the thermodynamics and kinetics of the mechanism of generation of these open cages in their closed-shell singlet, open-shell singlet, and triplet states. We also computed the magnetic interactions induced by the open cages presenting a triplet ground state. Our results indicate that this mechanism is not appropriate to explain the ferromagnetism found in compressed and heated polymeric C(60) for the following reasons: (a) the formation of the only open cage presenting a triplet ground state requires overpassing a highest energy point of 318 kcal/mol, well above other competitive mechanisms reported in the literature; the triplet open cages formed are not stable against their transformation into a diamagnetic intermediate; (c) the magnetic interactions between two adjacent triplet open cages are antiferromagnetic.

Highly efficient red OLEDs using DCJTB as the dopant and delayed fluorescent exciplex as the host.

PubMed

Zhao, Bo; Zhang, Tianyou; Chu, Bei; Li, Wenlian; Su, Zisheng; Wu, Hairuo; Yan, Xingwu; Jin, Fangming; Gao, Yuan; Liu, Chengyuan

2015-05-29

In this manuscript, we demonstrated a highly efficient DCJTB emission with delayed fluorescent exciplex TCTA:3P-T2T as the host. For the 1.0% DCJTB doped concentration, a maximum luminance, current efficiency, power efficiency and EQE of 22,767 cd m(-2), 22.7 cd A(-1), 21.5 lm W(-1) and 10.15% were achieved, respectively. The device performance is the best compared to either red OLEDs with traditional fluorescent emitter or traditional red phosphor of Ir(piq)3 doped into CBP host. The extraction of so high efficiency can be explained as the efficient triplet excitons up-conversion of TCTA:3P-T2T and the energy transfer from exciplex host singlet state to DCJTB singlet state.

Phylogenetically informed logic relationships improve detection of biological network organization

PubMed Central

2011-01-01

Background A "phylogenetic profile" refers to the presence or absence of a gene across a set of organisms, and it has been proven valuable for understanding gene functional relationships and network organization. Despite this success, few studies have attempted to search beyond just pairwise relationships among genes. Here we search for logic relationships involving three genes, and explore its potential application in gene network analyses. Results Taking advantage of a phylogenetic matrix constructed from the large orthologs database Roundup, we invented a method to create balanced profiles for individual triplets of genes that guarantee equal weight on the different phylogenetic scenarios of coevolution between genes. When we applied this idea to LAPP, the method to search for logic triplets of genes, the balanced profiles resulted in significant performance improvement and the discovery of hundreds of thousands more putative triplets than unadjusted profiles. We found that logic triplets detected biological network organization and identified key proteins and their functions, ranging from neighbouring proteins in local pathways, to well separated proteins in the whole pathway, and to the interactions among different pathways at the system level. Finally, our case study suggested that the directionality in a logic relationship and the profile of a triplet could disclose the connectivity between the triplet and surrounding networks. Conclusion Balanced profiles are superior to the raw profiles employed by traditional methods of phylogenetic profiling in searching for high order gene sets. Gene triplets can provide valuable information in detection of biological network organization and identification of key genes at different levels of cellular interaction. PMID:22172058

Molecular-wire behavior of OLED materials: exciton dynamics in multichromophoric Alq3-oligofluorene-Pt(II)porphyrin triads.

PubMed

Montes, Victor A; Pérez-Bolívar, César; Agarwal, Neeraj; Shinar, Joseph; Anzenbacher, Pavel

2006-09-27

Donor-bridge-acceptor triads consisting of the Alq3 complex, oligofluorene bridge, and PtII tetraphenylporphyrin (PtTPP) were synthesized. The triads were designed to study the energy level/distance-dependence in energy transfer both in a solution and in solid state. The materials show effective singlet transfer from the Alq3-fluorene fluorophore to the porphyrin, while the triplet energy transfer, owing to the shorter delocalization of triplet excitons, appears to take place via a triplet energy cascade. Using femtosecond transient spectroscopy, the rate of the singlet-singlet energy transfer was determined. The exponential dependence of the donor-acceptor distance and the respective energy transfer rates of 7.1 x 1010 to 1.0 x 109 s-1 with the attenuation factor â of 0.21 +/- 0.02 A-1 suggest that the energy transfer proceeds via a mixed incohererent wire/superexchange mechanism. In the OLEDs fabricated using the Alq3-oligofluorene-PtTPP triads with better triplet level alignment, the order of a magnitude increase in efficacy appears to be due to facile triplet energy transfer. The devices, where the triplet-triplet energy transfer is of paramount importance, showed high color purity emission (CIE X,Y: 0.706, 0.277), which is almost identical to the emission from thin films. Most importantly, we believe that the design principles demonstrated above are general and may be used to prepare OLED materials with enhanced quantum efficacy at lowered operational potentials, being crucial for improved lifespan of OLEDs.

Pauses enhance chunk recognition in song element strings by zebra finches.

PubMed

Spierings, Michelle; de Weger, Anouk; Ten Cate, Carel

2015-07-01

When learning a language, it is crucial to know which syllables of a continuous sound string belong together as words. Human infants achieve this by attending to pauses between words or to the co-occurrence of syllables. It is not only humans that can segment a continuous string. Songbirds learning their song tend to copy 'chunks' from one or more tutors' songs and combine these into their own song. In the tutor songs, these chunks are often separated by pauses and a high co-occurrence of elements, suggesting that these features affect chunking and song learning. We examined experimentally whether the presence of pauses and element co-occurrence affect the ability of adult zebra finches to discriminate strings of song elements. Using a go/no-go design, two groups of birds were trained to discriminate between two strings. In one group (Pause-group), pauses were inserted between co-occurring element triplets in the strings, and in the other group (No-pause group), both strings were continuous. After making a correct discrimination, an individual proceeded to a reversal training using string segments. Segments were element triplets consistent in co-occurrence, triplets that were partly consistent in composition and triplets consisting of elements that did not co-occur in the strings. The Pause-group was faster in discriminating between the two strings. This group also responded differently to consistent triplets in the reversal training, compared to inconsistent triplets. The No-pause group did not differentiate among the triplet types. These results indicate that pauses in strings of song elements aid song discrimination and memorization of co-occurring element groups.

Photo-physical properties and triplet-triplet absorption of platinum(II) acetylides in solid PMMA matrices

NASA Astrophysics Data System (ADS)

Glimsdal, Eirik; Westlund, Robert; Lindgren, Mikael

2009-05-01

Because of their strong nonlinear optical properties, Platinum(II) acetylides are investigated as potential chromophores for optical power limiting (OPL) applications. The strong excited state absorption and efficient intersystem crossing to the triplet states in these materials are desired properties for good OPL performance. We recently reported on OPL and photo-physical properties of Pt(II)-acetylide chromophores in solution, modified with thiophenyl or triazole groups. [R. Westlund et al. J. Mater. Chem. 18, 166 (2008); E. Glimsdal et al. Proc. SPIE 6740, 67400M (2007)] The chromophores were later incorporated into poly(methyl-methacrylate) (PMMA) glasses. A variety of doped organic solids were prepared, reaching concentrations of up to 13 wt% of the guest molecule. Raman spectra of the doped solid devices proved that the chemical structure of the nonlinear dyes remains intact upon the polymerization of the solid matrix. Luminescence spectra confirm that the basic photo-physical properties (absorption, emission and inter-system crossing) observed for the solute molecules in THF are maintained also in the solid state. In particular, the phosphorescence lifetime stays in the order of μs to ms, just as in the oxygen evacuated liquid samples. Also, the wavelength dependence and time-dynamics of the triplet absorption spectra of the dyes, dissolved in THF solution and dispersed in solid PMMA matrices, were investigated and compared. Ground state UV absorption spectra between 300 and 420 nm have corresponding broad band visible triplet-triplet absorption between 400 and 800 nm. The triplet state extinction coefficients were determined to be in the order of 104 M-1cm-1.

Does a triplet birth pose a special risk for infant development? Assessing cognitive development in relation to intrauterine growth and mother-infant interaction across the first 2 years.

PubMed

Feldman, Ruth; Eidelman, Arthur I

2005-02-01

To examine whether a triplet birth per se poses a risk to the development of infants' cognitive competencies and to the mother-infant relationship. Twenty-three sets of triplets were matched with 23 sets of twins and 23 singleton infants (n = 138) with respect to gestational age, birth weight, and medical and demographic features. Infants with perinatal asphyxia, intraventricular hemorrhage of grade 3 or 4, periventricular leukomalacia, or central nervous system infection were excluded from the study. At 6, 12, and 24 months of age, mother-infant interaction was observed and infants' cognitive development was tested with the Bayley II test. Mothers of triplets displayed lower levels of sensitivity at 6, 12, and 24 months and infants were less socially involved at 6 and 24 months, compared with singletons and twins. Triplets scored lower than singletons and twins on the Bayley Mental Developmental Index at 6, 12, and 24 months. A weight discordance of >15% was found for 15 triplet sets (65.2%). The discordant triplets showed decreased cognitive skills at 12 and 24 months, compared with their siblings, and received the lowest scores for maternal sensitivity. Hierarchical multivariate regression analysis revealed that greater medical risk at birth, multiple-birth status, lower maternal sensitivity, and reduced infant social involvement in the first 2 years were each predictive of lower cognitive outcomes at 2 years (R2 = 0.33). Triplets appear to be at higher risk for cognitive delays in the first 2 years of life, and discordant infants are at especially high risk. This delay is related in part to the difficulty of providing sensitive mothering to 3 infants at the same time. The findings may assist practitioners in guiding prenatal and postpartum parental care and management.

T.C.G triplet in an antiparallel purine.purine.pyrimidine DNA triplex. Conformational studies by NMR.

PubMed

Dittrich, K; Gu, J; Tinder, R; Hogan, M; Gao, X

1994-04-12

The antiparallel purine.purine.pyrimidine DNA triplex, RRY6, which contains a T.C.G inverted triplet in the center of the sequence, was examined by proton and phosphorous two-dimensional NMR spectroscopy. The local conformation of the T.C.G triplet (T4.C11.G18) and the effect of this triplet on the global helical structure were analyzed in detail. The formation of the T.C.G triplet is confirmed by a set of cross-strand NOEs, including unusual cross-strand NOEs between the third strand and the pyrimidine strand as opposed to the purine strand of the duplex. NMR data suggest that the T.C.G triplet may be present in an equilibrium between a non-hydrogen-bonded form and a T(O4)-C(NH2) hydrogen-bonded form and that there is a distortion of the in-plane alignment of the three bases. The flanking G.G.C base triplets are well-defined on the 5'-side of T4, but somewhat interrupted on the 3'-side of T4. The effect of the third strand binding on the Watson-Crick duplex was probed by an NMR study of the free duplex RY6. NMR parameters are affected mostly around the T.C.G inversion site. The perturbations extend to at least two adjacent base triplets on either side. The binding of the third purine strand and the accommodation of a central T.C.G inversion in RRY6 does not require a readjustment in sugar pucker, which remains in the range of C2'-endo. 31P resonances of RRY6 distribute over a range of 2.2 ppm. The H-P coupling patterns of the third strand differ from those of the duplex. General spectral patterns defined by the marker protons of the RRY and YRY triplexes are compared.

Determining the Origin of Half-bandgap-voltage Electroluminescence in Bifunctional Rubrene/C60 Devices

PubMed Central

Chen, Qiusong; Jia, Weiyao; Chen, Lixiang; Yuan, De; Zou, Yue; Xiong, Zuhong

2016-01-01

Lowering the driving voltage of organic light-emitting diodes (OLEDs) is an important approach to reduce their energy consumption. We have fabricated a series of bifunctional devices (OLEDs and photovoltaics) using rubrene and fullerene (C60) as the active layer, in which the electroluminescence threshold voltage(~1.1 V) was half the value of the bandgap of rubrene. Magneto-electroluminescence (MEL) response of planner heterojunction diodes exhibited a small increase in response to a low magnetic field strength (<20 mT); however, a very large decay was observed at a high magnetic field strength (>20 mT). When a hole-transport layer with a low mobility was included in these devices, the MEL response reversed in shape, and simultaneously, the EL threshold voltage became larger than the bandgap voltage. When bulk heterojunction device was examined, the amplitude of MEL curves presented an anomalous voltage-dependence. Following an analysis of the MEL responses of these devices, we proposed that the EL of half-bandgap-voltage device originated from bimolecular triplet-triplet annihilation in the rubrene film, rather than from singlet excitons that formed via an interface auger recombination. This work provides critical insight into the mechanisms of OLED emission and will help advance the applications of bifunctional devices. PMID:27142285

Efficient HOMO-LUMO separation by multiple resonance effect toward ultrapure blue thermally activated delayed fluorescence

NASA Astrophysics Data System (ADS)

Hatakeyama, Takuji; Ikuta, Toshiaki; Shiren, Kazushi; Nakajima, Kiichi; Nomura, Shintaro; Ni, Jingping

2016-09-01

Organic light-emitting diodes (OLEDs) play an important role in the new generation of flat-panel displays. Conventional OLEDs employing fluorescent materials together with triplet-triplet annihilation suffer from a relatively low internal quantum efficiency (IQE) of 62.5%. On the other hand, the IQE of OLEDs employing phosphorescent or thermally activated delayed fluorescence (TADF) materials can reach 100%. However, these materials exhibit very broad peaks with a full-width at half-maximum (FWHM) of 70-100 nm and cannot satisfy the color-purity requirements for displays. Therefore, the latest commercial OLED displays employ blue fluorescent materials with a relatively low IQE, and efficient blue emitters with a small FWHM are highly needed. In our manuscript, we present organic molecules that exhibit ultrapure blue fluorescence based on TADF. These molecules consist of three benzene rings connected by one boron and two nitrogen atoms, which establish a rigid polycyclic framework and significant localization of the highest occupied and lowest unoccupied molecular orbitals by a multiple resonance effect. An OLED device based on the new emitter exhibits ultrapure blue emission at 467 nm with an FWHM of 28 nm, Commission Internationale de l'Eclairage (CIE) coordinates of (0.12, 0.13), and an IQE of 100%, which represent record-setting performance for blue OLED devices.

Model studies of hydrogen atom addition and abstraction processes involving ortho-, meta-, and para-benzynes.

PubMed

Clark, A E; Davidson, E R

2001-10-31

H-atom addition and abstraction processes involving ortho-, meta-, and para-benzyne have been investigated by multiconfigurational self-consistent field methods. The H(A) + H(B)...H(C) reaction (where r(BC) is adjusted to mimic the appropriate singlet-triplet energy gap) is shown to effectively model H-atom addition to benzyne. The doublet multiconfiguration wave functions are shown to mix the "singlet" and "triplet" valence bond structures of H(B)...H(C) along the reaction coordinate; however, the extent of mixing is dependent on the singlet-triplet energy gap (DeltaE(ST)) of the H(B)...H(C) diradical. Early in the reaction, the ground-state wave function is essentially the "singlet" VB function, yet it gains significant "triplet" VB character along the reaction coordinate that allows H(A)-H(B) bond formation. Conversely, the wave function of the first excited state is predominantly the "triplet" VB configuration early in the reaction coordinate, but gains "singlet" VB character when the H-atom is close to a radical center. As a result, the potential energy surface (PES) for H-atom addition to triplet H(B)...H(C) diradical is repulsive! The H3 model predicts, in agreement with the actual calculations on benzyne, that the singlet diradical electrons are not coupled strongly enough to give rise to an activation barrier associated with C-H bond formation. Moreover, this model predicts that the PES for H-atom addition to triplet benzyne will be characterized by a repulsive curve early in the reaction coordinate, followed by a potential avoided crossing with the (pi)1(sigma*)1 state of the phenyl radical. In contrast to H-atom addition, large activation barriers characterize the abstraction process in both the singlet ground state and first triplet state. In the ground state, this barrier results from the weakly avoided crossing of the dominant VB configurations in the ground-state singlet (S0) and first excited singlet (S1) because of the large energy gap between S0 and S1 early in the reaction coordinate. Because the S1 state is best described as the combination of the triplet X-H bond and the triplet H(B)...H(C) spin couplings, the activation barrier along the S0 abstraction PES will have much less dependence on the DeltaE(ST) of H(B)...H(C) than previously speculated. For similar reasons, the T1 potential surface is quite comparable to the S0 PES.

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

Norris, J.R.; Budil, D.E.; Gast, P.

The orientation of the principal axes of the primary electron donor triplet state measured in single crystals of photosynthetic reaction centers is compared to the x-ray structures of the bacteria Rhodobacter (Rb.) sphaeroides R-26 and Rhodopseudomonas (Rps.) viridis. The primary donor of Rps. viridis is significantly different from that of Rb. sphaeroides. The measured directions of the axes indicate that triplet excitation is almost completely localized on the L-subunit half of the dimer in Rps. viridis but is more symmetrically distributed on the dimeric donor in Rb. sphaeroides R-26. The large reduction of the zero field splitting parameters relative tomore » monomeric bacteriochlorophyll triplet in vitro suggests significant participation of asymmetrical charge transfer electronic configurations in the special pair triplet state of both organisms.« less

DNA Photosensitization by an "Insider": Photophysics and Triplet Energy Transfer of 5-Methyl-2-pyrimidone Deoxyribonucleoside.

PubMed

Bignon, Emmanuelle; Gattuso, Hugo; Morell, Christophe; Dumont, Elise; Monari, Antonio

2015-08-03

The main chromophore of (6-4) photoproducts, namely, 5-methyl-2-pyrimidone (Pyo), is an artificial noncanonical nucleobase. This chromophore has recently been reported as a potential photosensitizer that induces triplet damage in thymine DNA. In this study, we investigate the spectroscopic properties of the Pyo unit embedded in DNA by means of explicit solvent molecular-dynamics simulations coupled to time-dependent DFT and quantum-mechanics/molecular-mechanics techniques. Triplet-state transfer from the Pyo to the thymine unit was monitored in B-DNA by probing the propensity of this photoactive pyrimidine analogue to induce a Dexter-type triplet photosensitization and subsequent DNA damage. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Triplet supertree heuristics for the tree of life

PubMed Central

Lin, Harris T; Burleigh, J Gordon; Eulenstein, Oliver

2009-01-01

Background There is much interest in developing fast and accurate supertree methods to infer the tree of life. Supertree methods combine smaller input trees with overlapping sets of taxa to make a comprehensive phylogenetic tree that contains all of the taxa in the input trees. The intrinsically hard triplet supertree problem takes a collection of input species trees and seeks a species tree (supertree) that maximizes the number of triplet subtrees that it shares with the input trees. However, the utility of this supertree problem has been limited by a lack of efficient and effective heuristics. Results We introduce fast hill-climbing heuristics for the triplet supertree problem that perform a step-wise search of the tree space, where each step is guided by an exact solution to an instance of a local search problem. To realize time efficient heuristics we designed the first nontrivial algorithms for two standard search problems, which greatly improve on the time complexity to the best known (naïve) solutions by a factor of n and n2 (the number of taxa in the supertree). These algorithms enable large-scale supertree analyses based on the triplet supertree problem that were previously not possible. We implemented hill-climbing heuristics that are based on our new algorithms, and in analyses of two published supertree data sets, we demonstrate that our new heuristics outperform other standard supertree methods in maximizing the number of triplets shared with the input trees. Conclusion With our new heuristics, the triplet supertree problem is now computationally more tractable for large-scale supertree analyses, and it provides a potentially more accurate alternative to existing supertree methods. PMID:19208181

Triplet correlation functions in liquid water

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

Dhabal, Debdas; Chakravarty, Charusita, E-mail: charus@chemistry.iitd.ac.in; Singh, Murari

Triplet correlations have been shown to play a crucial role in the transformation of simple liquids to anomalous tetrahedral fluids [M. Singh, D. Dhabal, A. H. Nguyen, V. Molinero, and C. Chakravarty, Phys. Rev. Lett. 112, 147801 (2014)]. Here we examine triplet correlation functions for water, arguably the most important tetrahedral liquid, under ambient conditions, using configurational ensembles derived from molecular dynamics (MD) simulations and reverse Monte Carlo (RMC) datasets fitted to experimental scattering data. Four different RMC data sets with widely varying hydrogen-bond topologies fitted to neutron and x-ray scattering data are considered [K. T. Wikfeldt, M. Leetmaa, M.more » P. Ljungberg, A. Nilsson, and L. G. M. Pettersson, J. Phys. Chem. B 113, 6246 (2009)]. Molecular dynamics simulations are performed for two rigid-body effective pair potentials (SPC/E and TIP4P/2005) and the monatomic water (mW) model. Triplet correlation functions are compared with other structural measures for tetrahedrality, such as the O–O–O angular distribution function and the local tetrahedral order distributions. In contrast to the pair correlation functions, which are identical for all the RMC ensembles, the O–O–O triplet correlation function can discriminate between ensembles with different degrees of tetrahedral network formation with the maximally symmetric, tetrahedral SYM dataset displaying distinct signatures of tetrahedrality similar to those obtained from atomistic simulations of the SPC/E model. Triplet correlations from the RMC datasets conform closely to the Kirkwood superposition approximation, while those from MD simulations show deviations within the first two neighbour shells. The possibilities for experimental estimation of triplet correlations of water and other tetrahedral liquids are discussed.« less

Quenching of chlorophyll a singlets and triplets by carotenoids in light-harvesting complex of photosystem II: comparison of aggregates with trimers

NASA Astrophysics Data System (ADS)

Naqvi, K. Razi; Melø, T. B.; Raju, B. Bangar; Jávorfi, Tamás; Simidjiev, Ilian; Garab, Gyözö

1997-12-01

Laser-induced changes in the absorption spectra of isolated light-harvesting chlorophyll a/ b complex (LHC II) associated with photosystem II of higher plants have been recorded under anaerobic conditions and at ambient temperature by using multichannel detection with sub-microsecond time resolution. Difference spectra (Δ A) of LHC II aggregates have been found to differ from the corresponding spectra of trimers on two counts: (i) in the aggregates, the carotenoid (Car) triplet-triplet absorption band (Δ A>0) is red-shifted and broader; and (ii) the features attributable to the perturbation of the Qy band of a chlorophyll a (Chl a) by a nearby Car triplet are more pronounced, than in trimers. Aggregation, which is known to be accompanied by a reduction in the fluorescence yield of Chl a, is shown to cause a parallel decline in the triplet formation yield of Chl a; on the other hand, the efficiency (100%) of Chl a-to-Car transfer of triplet energy and the lifetime (9.3 μs) of Car triplets are not affected by aggregation. These findings are rationalized by postulating that the antenna Cars transact, besides light-harvesting and photoprotection, a third process: energy dissipation within the antenna. The suggestion is advanced that luteins, which are buried inside the LHC II monomers, as well as the other, peripheral, xanthophylls (neoxanthin and violaxanthin) quench the excited singlet state of Chl a by catalyzing internal conversion, a decay channel that competes with fluorescence and intersystem crossing; support for this explanation is presented by recalling reports of similar behaviour in bichromophoric model compounds in which one moiety is a Car and the other a porphyrin or a pyropheophorbide.

Probing the triplet correlation function in liquid water by experiments and molecular simulations.

PubMed

Dhabal, Debdas; Wikfeldt, Kjartan Thor; Skinner, Lawrie B; Chakravarty, Charusita; Kashyap, Hemant K

2017-01-25

Despite very significant developments in scattering experiments like X-ray and neutron diffraction, it has been challenging to elucidate the nature of tetrahedral molecular configurations in liquid water. A key question is whether the pair correlation functions, which can be obtained from scattering experiments, are sufficient to describe the tetrahedral ordering of water molecules. In our previous study (Dhabal et al., J. Chem. Phys., 2014, 141, 174504), using data-sets generated from reverse Monte Carlo and molecular dynamics simulations, we showed that the triplet correlation functions contain important information on the tetrahedrality of water in the liquid state. In the present study, X-ray scattering experiments and molecular dynamics (MD) simulations are used to link the isothermal pressure derivative of the structure factor with the triplet correlation functions for water. Triplet functions are determined for water up to 3.3 kbar at 298 K to display the effect of pressure on the water structure. The results suggest that triplet functions (H[combining tilde](q)) obtained using a rigid-body TIP4P/2005 water model are consistent with the experimental results. The triplet functions obtained in experiment as well as in simulations evince that in the case of tetrahedral liquids, exertion of higher pressure leads to a better agreement with the Kirkwood superposition approximation (KSA). We further validate this observation using the triplet correlation functions (g (3) (r,s,t)) calculated directly from simulation trajectory, revealing that both H[combining tilde](q) in q-space and g (3) (r,s,t) in real-space contain similar information on the tetrahedrality of liquids. This study demonstrates that the structure factor, even though it has only pair correlation information of the liquid structure, can shed light on three-body correlations in liquid water through its isothermal pressure derivative term.

Characterization of the low-temperature triplet state of chlorophyll in photosystem II core complexes: Application of phosphorescence measurements and Fourier transform infrared spectroscopy.

PubMed

Zabelin, Alexey A; Neverov, Konstantin V; Krasnovsky, Alexander A; Shkuropatova, Valentina A; Shuvalov, Vladimir A; Shkuropatov, Anatoly Ya

2016-06-01

Phosphorescence measurements at 77 K and light-induced FTIR difference spectroscopy at 95 K were applied to study of the triplet state of chlorophyll a ((3)Chl) in photosystem II (PSII) core complexes isolated from spinach. Using both methods, (3)Chl was observed in the core preparations with doubly reduced primary quinone acceptor QA. The spectral parameters of Chl phosphorescence resemble those in the isolated PSII reaction centers (RCs). The main spectral maximum and the lifetime of the phosphorescence corresponded to 955±1 nm and of 1.65±0.05 ms respectively; in the excitation spectrum, the absorption maxima of all core complex pigments (Chl, pheophytin a (Pheo), and β-carotene) were observed. The differential signal at 1667(-)/1628(+)cm(-1) reflecting a downshift of the stretching frequency of the 13(1)-keto C=O group of Chl was found to dominate in the triplet-minus-singlet FTIR difference spectrum of core complexes. Based on FTIR results and literature data, it is proposed that (3)Chl is mostly localized on the accessory chlorophyll that is in triplet equilibrium with P680. Analysis of the data suggests that the Chl triplet state responsible for the phosphorescence and the FTIR difference spectrum is mainly generated due to charge recombination in the reaction center radical pair P680(+)PheoD1(-), and the energy and temporal parameters of this triplet state as well as the molecular environment and interactions of the triplet-bearing Chl molecule are similar in the PSII core complexes and isolated PSII RCs. Copyright © 2016 Elsevier B.V. All rights reserved.

Phenol and terpene quenching of singlet- and triplet-excited states of riboflavin in relation to light-struck flavor formation in beer.

PubMed

Cardoso, Daniel R; Olsen, Karsten; Møller, Jens K S; Skibsted, Leif H

2006-07-26

Phenolic compounds present in beer were shown by fluorescence spectroscopy and laser flash photolysis to deactivate both singlet- and triplet-excited states of riboflavin with bimolecular rate constants close to the diffusion control ranging from 2.8x10(9) to 1.1x10(10) M-1 s-1 and from 1.1x10(9) to 2.6x10(9) M-1 s-1, respectively. Enthalpies of activation were low (up to 33.2 kJ mol-1), and entropies of activation were positive, ranging from 17 to 92 J mol-1 K-1, as derived from temperature dependence, indicating a compensation effect. From a Stern-Volmer analysis of the singlet-excited riboflavin quenching by phenols it was found that high amounts of phenolic compounds (>0.3 M) would be needed to hinder triplet-excited riboflavin generation. On the other hand, a phenolic content of 0.36 mM is likely to quench 90% of the triplet-excited state. Phenol photodegradation was found to be complex, and using ESI-MS analysis it was not possible to identify specific photooxidation products of the phenolic compounds; only the photoproducts of riboflavin could be detected and structurally assigned. The rate of reaction of triplet-excited riboflavin with phenolic compounds in acetonitrile/citrate buffer (pH 4.6, 10 mM) is 550 times faster than the reaction with iso-alpha-acids from hops, indicating that triplet-excited quenchers such as phenols may be involved in the early steps in light-struck flavor formation in beer through radical formation. Terpenes present in herb-flavored beers were found to be nonreactive toward singlet- and triplet-excited-state riboflavin, and any protection depends on other mechanisms.

The fine tuning of carotenoid-chlorophyll interactions in light-harvesting complexes: an important requisite to guarantee efficient photoprotection via triplet-triplet energy transfer in the complex balance of the energy transfer processes

NASA Astrophysics Data System (ADS)

Di Valentin, Marilena; Carbonera, Donatella

2017-08-01

Triplet-triplet energy transfer (TTET) from the chlorophyll to the carotenoid triplet state is the process exploited by photosynthetic systems to protect themselves from singlet oxygen formation under light-stress conditions. A deep comprehension of the molecular strategies adopted to guarantee TTET efficiency, while at the same time maintaining minimal energy loss and efficient light-harvesting capability, is still lacking. The paramagnetic nature of the triplet state makes electron paramagnetic resonance (EPR) the method of choice when investigating TTET. In this review, we focus on our extended comparative study of two photosynthetic antenna complexes, the Peridinin-chlorophyll a-protein of dinoflagellates and the light-harvesting complex II of higher plants, in order to point out important aspects of the molecular design adopted in the photoprotection strategy. We have demonstrated that a proper analysis of the EPR data allows one to identify the pigments involved in TTET and, consequently, gain an insight into the structure of the photoprotective sites. The structural information has been complemented by a detailed description of the electronic structure provided by hyperfine spectroscopy. All these elements represent the fundamental building blocks toward a deeper understanding of the requirements for efficient photoprotection, which is fundamental to guarantee the prolonged energy conversion action of photosynthesis.

Photodissociation of N2O: triplet states and triplet channel.

PubMed

Schinke, R; Schmidt, J A; Johnson, M S

2011-11-21

The role of triplet states in the UV photodissociation of N(2)O is investigated by means of quantum mechanical wave packet calculations. Global potential energy surfaces are calculated for the lowest two (3)A' and the lowest two (3)A'' states at the multi-reference configuration interaction level of electronic structure theory using the augmented valence quadruple zeta atomic basis set. Because of extremely small transition dipole moments with the ground electronic state, excitation of the triplet states has only a marginal effect on the far red tail of the absorption cross section. The calculations do not show any hint of an increased absorption around 280 nm as claimed by early experimental studies. The peak observed in several electron energy loss spectra at 5.4 eV is unambiguously attributed to the lowest triplet state 1(3)A'. Excitation of the 2(1)A' state and subsequent transition to the repulsive branch of the 2(3)A'' state at intermediate NN-O separations, promoted by spin-orbit coupling, is identified as the main pathway to the N(2)((1)Σ(g)(+))+O((3)P) triplet channel. The yield, determined in two-state wave packet calculations employing calculated spin-orbit matrix elements, is 0.002 as compared to 0.005 ± 0.002 measured by Nishida et al. [J. Phys. Chem. A 108, 2451 (2004)].

Triplet-State Dissolved Organic Matter Quantum Yields and Lifetimes from Direct Observation of Aromatic Amine Oxidation.

PubMed

Schmitt, Markus; Erickson, Paul R; McNeill, Kristopher

2017-11-21

Excited triplet state chromophoric dissolved organic matter ( 3 CDOM*) is a short-lived mixture of excited-state species that plays important roles in aquatic photochemical processes. Unlike the study of the triplet states of well-defined molecules, which are amenable to transient absorbance spectroscopy, the study of 3 CDOM* is hampered by it being a complex mixture and its low average intersystem crossing quantum yield (Φ ISC ). This study is an alternative approach to investigating 3 CDOM* using transient absorption laser spectroscopy. The radical cation of N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD), formed through oxidation by 3 CDOM*, was directly observable by transient absorption spectroscopy and was used to probe basic photophysical properties of 3 CDOM*. Quenching and control experiments verified that TMPD •+ was formed from 3 CDOM* under anoxic conditions. Model triplet sensitizers with a wide range of excited triplet state reduction potentials and CDOM oxidized TMPD at near diffusion-controlled rates. This gives support to the idea that a large cross-section of 3 CDOM* moieties are able to oxidize TMPD and that the complex mixture of 3 CDOM* can be simplified to a single signal. Using the TMPD •+ transient, the natural triplet lifetime and Φ ISC for different DOM isolates and natural waters were quantified; values ranged from 12 to 26 μs and 4.1-7.8%, respectively.

Phonon coupling in optical transitions for singlet-triplet pairs of bound excitons in semiconductors

NASA Astrophysics Data System (ADS)

Pistol, M. E.; Monemar, B.

1986-05-01

A model is presented for the observed strong difference in selection rules for coupling of phonons in the one-phonon sideband of optical spectra related to bound excitons in semiconductors. The present treatment is specialized to the case of a closely spaced pair of singlet-triplet character as the lowest electronic states, as is common for bound excitons associated with neutral complexes in materials like GaP and Si. The optical transition for the singlet bound-exciton state is found to couple strongly only to symmetric A1 modes. The triplet state has a similar coupling strength to A1 modes, but in addition strong contributions are found for replicas corresponding to high-density-of-states phonons TAX, LAX, and TOX. This can be explained by a treatment of particle-phonon coupling beyond the ordinary adiabatic approximation. A weak mixing between the singlet and triplet states is mediated by the phonon coupling, as described in first-order perturbation theory. The model derived in this work, for such phonon-induced mixing of closely spaced electronic states, is shown to explain the observed phonon coupling for several bound-exciton systems of singlet-triplet character in GaP. In addition, the observed oscillator strength of the forbidden triplet state may be explained as partly derived from phonon-induced mixing with the singlet state, which has a much larger oscillator strength.

An electron spin polarization study of the interaction of photoexcited triplet molecules with mono- and polynitroxyl stable free radicals

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

Turro, N.J.; Khudyakov, I.V.; Bossmann, S.H.

1993-02-11

Time-resolved electron spin resonance (TR ESR) has been used to investigate the chemically induced dynamic electron polarization (CIDEP) generated by the interaction of stable free radicals with the triplet states of benzophenone, benzil, and 2-acetylnaphthalene. The stable radicals were mono-, di-, tri-, and tetranitroxyl free radicals possessing the 2,2,6,6-tetramethylpiperidine-N-oxyl moiety. All of the stable radical systems investigated were found to be emissively polarized by interaction with the triplet states, and the phase of polarization was independent of the sign of zero-field splitting (D) of the interacting triple molecule. Possible and likely mechanisms of polarization transfer (creation) resulting from the interactionmore » of photoexcited triplet molecules with nitroxyls in the strong electron exchange are discussed. The emissive CIDEP of nitroxyls observed in the interactions with triplet benzil, which has D > 0, provides strong support for the operation of the radical-triplet pair mechanism. Within the time scale of TR ESR experiments ([approximately]10[sup [minus]7]--10[sup [minus]6] s) no significant variation in the shape of the CIDEP spectra of the nitroxyls was observed, either in viscous media or in micelles. It is concluded that intramolecular spin exchange (or conformational change) of polynitroyls occurs much faster than the time resolution of the experiment. 24 refs., 6 figs., 1 tab.« less

Exchange interaction between the triplet exciton and the localized spin in copper-phthalocyanine.

PubMed

Wu, Wei

2014-06-14

Triplet excitonic state in the organic molecule may arise from a singlet excitation and the following inter-system crossing. Especially for a spin-bearing molecule, an exchange interaction between the triplet exciton and the original spin on the molecule can be expected. In this paper, such exchange interaction in copper-phthalocyanine (CuPc, spin-½) was investigated from first-principles by using density-functional theory within a variety of approximations to the exchange correlation, ranging from local-density approximation to long-range corrected hybrid-exchange functional. The magnitude of the computed exchange interaction is in the order of meV with the minimum value (1.5 meV, ferromagnetic) given by the long-range corrected hybrid-exchange functional CAM-B3LYP. This exchange interaction can therefore give rise to a spin coherence with an oscillation period in the order of picoseconds, which is much shorter than the triplet lifetime in CuPc (typically tens of nanoseconds). This implies that it might be possible to manipulate the localized spin on Cu experimentally using optical excitation and inter-system crossing well before the triplet state disappears.

Charged excitons in a dilute two-dimensional electron gas in a high magnetic field

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

Wojs, Arkadiusz; Institute of Physics, Wroclaw University of Technology, Wroclaw 50-370,; Quinn, John J.

2000-08-15

A theory of charged excitons X{sup -} in a dilute two-dimensional (2D) electron gas in a high-magnetic field is presented. In contrast to previous calculations, three bound X{sup -} states (one singlet and two triplets) are found in a narrow and symmetric GaAs quantum well. The singlet and a ''bright'' triplet are the two optically active states observed in experiments. The bright triplet has the binding energy of about 1 meV, smaller than the singlet and a ''dark'' triplet. The interaction of bound X{sup -}'s with a dilute 2D electron gas is investigated using exact diagonalization techniques. It is foundmore » that the short-range character of the e-X{sup -} interactions effectively isolates bound X{sup -} states from a dilute e-h plasma. This results in the insensitivity of the photoluminescence spectrum to the filling factor {nu}, and a rapid decrease of the oscillator strength of the dark triplet X{sup -} as a function of {nu}{sup -1}. (c) 2000 The American Physical Society.« less

Triplet Tellurophene-Based Acceptors for Organic Solar Cells.

PubMed

Yang, Lei; Gu, Wenxing; Lv, Lei; Chen, Yusheng; Yang, Yufei; Ye, Pan; Wu, Jianfei; Hong, Ling; Peng, Aidong; Huang, Hui

2018-01-22

Triplet materials have been employed to achieve high-performing organic solar cells (OSCs) by extending the exciton lifetime and diffusion distances, while the triplet non-fullerene acceptor materials have never been reported for bulk heterojunction OSCs. Herein, for the first time, three triplet molecular acceptors based on tellurophene with different degrees of ring fusing were designed and synthesized for OSCs. Significantly, these molecules have long exciton lifetime and diffusion lengths, leading to efficient power conversion efficiency (7.52 %), which is the highest value for tellurophene-based OSCs. The influence of the extent of ring fusing on molecular geometry and OSCs performance was investigated to show the power conversion efficiencies (PCEs) continuously increased along with increasing the extent of ring fusing. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Generation of ultra-wideband triplet pulses based on four-wave mixing and phase-to-intensity modulation conversion.

PubMed

Li, Wei; Wang, Li Xian; Hofmann, Werner; Zhu, Ning Hua; Bimberg, Dieter

2012-08-27

We propose and demonstrate a novel scheme to generate ultra-wideband (UWB) triplet pulses based on four-wave mixing and phase-to-intensity modulation conversion. First a phase-modulated Gaussian doublet pulse is generated by four-wave mixing in a highly nonlinear fiber. Then an UWB triplet pulse is generated by generating the first-order derivative of the phase-modulated Gaussian doublet pulse using an optical filter serving as a frequency discriminator. By locating the optical signal at the linear slope of the optical filter, the phase modulated Gaussian doublet pulse is converted to an intensity-modulated UWB triplet pulse which well satisfies the Federal Communications Commission spectral mask requirements, even in the extremely power-restricted global positioning system band.

Leptogenesis, radiative neutrino masses and inert Higgs triplet dark matter

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

Lu, Wen-Bin; Gu, Pei-Hong

2016-05-18

We extend the standard model by three types of inert fields including Majorana fermion singlets/triplets, real Higgs singlets/triplets and leptonic Higgs doublets. In the presence of a softly broken lepton number and an exactly conserved Z{sub 2} discrete symmetry, these inert fields together can mediate a one-loop diagram for a Majorana neutrino mass generation. The heavier inert fields can decay to realize a successful leptogenesis while the lightest inert field can provide a stable dark matter candidate. As an example, we demonstrate the leptogenesis by the inert Higgs doublet decays. We also perform a systematic study on the inert Higgsmore » triplet dark matter scenario where the interference between the gauge and Higgs portal interactions can significantly affect the dark matter properties.« less

A Search for X-ray Emission in Isolated Compact Triplets

NASA Technical Reports Server (NTRS)

Brown, Beth A.; Williams, Barbara

2006-01-01

We describe preliminary results of an exploratory search for diffuse X-ray emission in a sample of the poorest galaxy groups, i.e., isolated compact triplets of galaxies. These systems represent the simplest forms of galaxy clustering while manifesting all the complexities inherent in other groups. We have selected 20 compact triplets for this initial study. The component galaxies are expected to interact with each other and with the group's intergalactic medium, if present, in complex ways that trigger high-energy processes.

Photochemistry and photooxidation of tetraphenyl-p-dioxin

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

George, M.V.; Kumar, C.V.; Scaiano, J.C.

1979-09-20

Laser flash photolysis studies of tetraphenyl-p-dioxin have led to the characterization of its triplet state. The T-T absorption spectra shows maxima at 350 and 545 nm; the triplet has a lifetime of 535 ns in methanol and can be quenched by di-tert-butyl nitroxide, paraquat dications, oxygen, and di-tert-butyl selenoketone. The interaction of the triplet with oxygen leads to the formation of singlet oxygen which in turn reacts with the title compound to yield benzil.

A model of litter size distribution in cattle.

PubMed

Bennett, G L; Echternkamp, S E; Gregory, K E

1998-07-01

Genetic increases in twinning of cattle could result in increased frequency of triplet or higher-order births. There are no estimates of the incidence of triplets in populations with genetic levels of twinning over 40% because these populations either have not existed or have not been documented. A model of the distribution of litter size in cattle is proposed. Empirical estimates of ovulation rate distribution in sheep were combined with biological hypotheses about the fate of embryos in cattle. Two phases of embryo loss were hypothesized. The first phase is considered to be preimplantation. Losses in this phase occur independently (i.e., the loss of one embryo does not affect the loss of the remaining embryos). The second phase occurs after implantation. The loss of one embryo in this stage results in the loss of all embryos. Fewer than 5% triplet births are predicted when 50% of births are twins and triplets. Above 60% multiple births, increased triplets accounted for most of the increase in litter size. Predictions were compared with data from 5,142 calvings by 14 groups of heifers and cows with average litter sizes ranging from 1.14 to 1.36 calves. The predicted number of triplets was not significantly different (chi2 = 16.85, df = 14) from the observed number. The model also predicted differences in conception rates. A cow ovulating two ova was predicted to have the highest conception rate in a single breeding cycle. As mean ovulation rate increased, predicted conception to one breeding cycle increased. Conception to two or three breeding cycles decreased as mean ovulation increased because late-pregnancy failures increased. An alternative model of the fate of ova in cattle based on embryo and uterine competency predicts very similar proportions of singles, twins, and triplets but different conception rates. The proposed model of litter size distribution in cattle accurately predicts the proportion of triplets found in cattle with genetically high twinning rates. This model can be used in projecting efficiency changes resulting from genetically increasing the twinning rate in cattle.

Highly efficient red OLEDs using DCJTB as the dopant and delayed fluorescent exciplex as the host

PubMed Central

Zhao, Bo; Zhang, Tianyou; Chu, Bei; Li, Wenlian; Su, Zisheng; Wu, Hairuo; Yan, Xingwu; Jin, Fangming; Gao, Yuan; Liu, Chengyuan

2015-01-01

In this manuscript, we demonstrated a highly efficient DCJTB emission with delayed fluorescent exciplex TCTA:3P-T2T as the host. For the 1.0% DCJTB doped concentration, a maximum luminance, current efficiency, power efficiency and EQE of 22,767 cd m−2, 22.7 cd A−1, 21.5 lm W−1 and 10.15% were achieved, respectively. The device performance is the best compared to either red OLEDs with traditional fluorescent emitter or traditional red phosphor of Ir(piq)3 doped into CBP host. The extraction of so high efficiency can be explained as the efficient triplet excitons up-conversion of TCTA:3P-T2T and the energy transfer from exciplex host singlet state to DCJTB singlet state. PMID:26023882

Infrared Spectroscopy of the Mass 31 Cation: Protonated Formaldehyde VS. The Triplet Methoxy Cation

NASA Astrophysics Data System (ADS)

Mosley, J. D.; Cheng, T. C.; Duncan, M. A.

2012-06-01

The m/z=31 cation is produced by ionization and fragmentation of methanol, ethanol, dimethyl ether, etc. Two structures have been proposed, protonated formaldehyde (^1CH_2OH^+) and the triplet methoxy cation (^3CH_3O^+). The infrared spectrum of the mass 31 cation is obtained using infrared photodissociation spectroscopy with Ar tagging. The spectrum reveals the presence of two stable isomers, protonated formaldehyde (^1CH_2OH^+) and the triplet methoxy cation (^3CH_3O^+). The triplet methoxy cation has been studied extensively and is predicted to interconvert to protonated formaldehyde through an essentially barrierless process on a timescale much faster than our experiment (>100 μs). The presence of two structural isomers is verified by comparison of spectra from different precursors and spectra of different temperature ions from the same precursor.

High-performance light-emitting diodes based on carbene-metal-amides

NASA Astrophysics Data System (ADS)

Di, Dawei; Romanov, Alexander S.; Yang, Le; Richter, Johannes M.; Rivett, Jasmine P. H.; Jones, Saul; Thomas, Tudor H.; Abdi Jalebi, Mojtaba; Friend, Richard H.; Linnolahti, Mikko; Bochmann, Manfred; Credgington, Dan

2017-04-01

Organic light-emitting diodes (OLEDs) promise highly efficient lighting and display technologies. We introduce a new class of linear donor-bridge-acceptor light-emitting molecules, which enable solution-processed OLEDs with near-100% internal quantum efficiency at high brightness. Key to this performance is their rapid and efficient utilization of triplet states. Using time-resolved spectroscopy, we establish that luminescence via triplets occurs within 350 nanoseconds at ambient temperature, after reverse intersystem crossing to singlets. We find that molecular geometries exist at which the singlet-triplet energy gap (exchange energy) is close to zero, so that rapid interconversion is possible. Calculations indicate that exchange energy is tuned by relative rotation of the donor and acceptor moieties about the bridge. Unlike other systems with low exchange energy, substantial oscillator strength is sustained at the singlet-triplet degeneracy point.

Controlling the superconducting transition by spin-orbit coupling

NASA Astrophysics Data System (ADS)

Banerjee, N.; Ouassou, J. A.; Zhu, Y.; Stelmashenko, N. A.; Linder, J.; Blamire, M. G.

2018-05-01

Whereas considerable evidence exists for the conversion of singlet Cooper pairs into triplet Cooper pairs in the presence of inhomogeneous magnetic fields, recent theoretical proposals have suggested an alternative way to exert control over triplet generation: intrinsic spin-orbit coupling in a homogeneous ferromagnet coupled to a superconductor. Here, we proximity couple Nb to an asymmetric Pt/Co/Pt trilayer, which acts as an effective spin-orbit-coupled ferromagnet owing to structural inversion asymmetry. Unconventional modulation of the superconducting critical temperature as a function of in-plane and out-of-plane applied magnetic fields suggests the presence of triplets that can be controlled by the magnetic orientation of a single homogeneous ferromagnet. Our studies demonstrate an active role of spin-orbit coupling in controlling the triplets, an important step towards the realization of novel superconducting spintronic devices.

Investigating the intersystem crossing rate and triplet quantum yield of Protoporphyrin IX by means of pulse train fluorescence technique

NASA Astrophysics Data System (ADS)

Gotardo, Fernando; Cocca, Leandro H. Z.; Acunha, Thiago V.; Longoni, Ana; Toldo, Josene; Gonçalves, Paulo F. B.; Iglesias, Bernardo A.; De Boni, Leonardo

2017-04-01

Photophysical investigations of PPIX were described in order to determine the triplet conversion efficiency. Time resolved fluorescence and pulse train fluorescence were employed to characterize the main mechanism responsible for deactivation of the first singlet excited state (excited singlet and triplet states). Single pulse and Z-Scan analysis were employed to measure the singlet excited state absorption cross-sections. Theoretical calculations were performed in order to get some properties of PPIX in ground state, first singlet and triplet excited state. A TD-DFT result shows a great possibility of ISC associated to out-of-plane distortions in porphyrinic ring. Furthermore, the B and Q bands in the calculated spectrum are assigned to the four frontier molecular orbitals as proposed by Gouterman for free-based porphyrins.

Triplet–triplet energy transfer in artificial and natural photosynthetic antennas

DOE PAGES

Ho, Junming; Kish, Elizabeth; Méndez-Hernandez, Dalvin D.; ...

2017-06-26

In photosynthetic organisms, protection against photo-oxidative stress due to singlet oxygen is provided by carotenoid molecules, which quench chlorophyll triplet species before they can sensitize singlet oxygen formation. In anoxygenic photosynthetic organisms, in which exposure to oxygen is low, chlorophyll to carotenoid triplet-triplet energy transfer (T-TET) is slow, in the tens of nanoseconds range, while it is ultrafast in the oxygen-rich chloroplasts of oxygen evolving photosynthetic organisms. In order to better understand the structural features and resulting electronic coupling that leads to T-TET dynamics adapted to ambient oxygen activity, we have carried out experimental and theoretical studies of two isomericmore » carotenoporphyrin molecular dyads having different conformations and therefore different interchromophore electronic interactions. This pair of dyads reproduces the characteristics of fast and slow T-TET including a resonance Raman based spectroscopic marker of strong electronic coupling and fast T-TET that has been observed in photosynthesis. As identified by DFT calculations, the spectroscopic marker associated with fast T-TET is due primarily to a geometrical perturbation of the carotenoid backbone in the triplet state induced by the interchromophore interaction. This is also the case for the natural systems, as demonstrated by the hybrid quantum mechanics/molecular mechanics (QM/MM) simulations of light harvesting proteins from oxygenic (LHCII) and anoxygenic organisms (LH2). In conclusion, both DFT and EPR analysis further indicates that upon T-TET, the triplet wave function is localized on the carotenoid in both dyads.« less

Triplet–triplet energy transfer in artificial and natural photosynthetic antennas

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

Ho, Junming; Kish, Elizabeth; Méndez-Hernandez, Dalvin D.

In photosynthetic organisms, protection against photo-oxidative stress due to singlet oxygen is provided by carotenoid molecules, which quench chlorophyll triplet species before they can sensitize singlet oxygen formation. In anoxygenic photosynthetic organisms, in which exposure to oxygen is low, chlorophyll to carotenoid triplet-triplet energy transfer (T-TET) is slow, in the tens of nanoseconds range, while it is ultrafast in the oxygen-rich chloroplasts of oxygen evolving photosynthetic organisms. In order to better understand the structural features and resulting electronic coupling that leads to T-TET dynamics adapted to ambient oxygen activity, we have carried out experimental and theoretical studies of two isomericmore » carotenoporphyrin molecular dyads having different conformations and therefore different interchromophore electronic interactions. This pair of dyads reproduces the characteristics of fast and slow T-TET including a resonance Raman based spectroscopic marker of strong electronic coupling and fast T-TET that has been observed in photosynthesis. As identified by DFT calculations, the spectroscopic marker associated with fast T-TET is due primarily to a geometrical perturbation of the carotenoid backbone in the triplet state induced by the interchromophore interaction. This is also the case for the natural systems, as demonstrated by the hybrid quantum mechanics/molecular mechanics (QM/MM) simulations of light harvesting proteins from oxygenic (LHCII) and anoxygenic organisms (LH2). In conclusion, both DFT and EPR analysis further indicates that upon T-TET, the triplet wave function is localized on the carotenoid in both dyads.« less

The Trouble with Triplets in Biodiversity Informatics: A Data-Driven Case against Current Identifier Practices

PubMed Central

Guralnick, Robert; Conlin, Tom; Deck, John; Stucky, Brian J.; Cellinese, Nico

2014-01-01

The biodiversity informatics community has discussed aspirations and approaches for assigning globally unique identifiers (GUIDs) to biocollections for nearly a decade. During that time, and despite misgivings, the de facto standard identifier has become the “Darwin Core Triplet”, which is a concatenation of values for institution code, collection code, and catalog number associated with biocollections material. Our aim is not to rehash the challenging discussions regarding which GUID system in theory best supports the biodiversity informatics use case of discovering and linking digital data across the Internet, but how well we can link those data together at this moment, utilizing the current identifier schemes that have already been deployed. We gathered Darwin Core Triplets from a subset of VertNet records, along with vertebrate records from GenBank and the Barcode of Life Data System, in order to determine how Darwin Core Triplets are deployed “in the wild”. We asked if those triplets follow the recommended structure and whether they provide an easy and unambiguous means to track from specimen records to genetic sequence records. We show that Darwin Core Triplets are often riddled with semantic and syntactic errors when deployed and curated in practice, despite specifications about how to construct them. Our results strongly suggest that Darwin Core Triplets that have not been carefully curated are not currently serving a useful role for relinking data. We briefly consider needed next steps to overcome current limitations. PMID:25470125

Interaction of triplet sensitizers with chlorophyll: Formation of singlet chlorophyll

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

Bohne, C.; Scaiano, J.C.

1989-03-29

The interaction of several triplet sensitizers with chlorophyll a (Chla) has been examined using laser techniques. For the carbonyl sensitizers (with triplet energies > 53 kcal/mol) it was possible to measure the quenching rate constants; these were systematically {>=} 10{sup 10} M{sup {minus}1} s{sup {minus}1}. In the cases of acetone, benzophenone, and p-methoxyacetophenone the quenching process leads to the formation of the fluorescent singlet state of Chla. For benzophenone (k{sub q} = 2.4 {times} 10{sup 10} M{sup {minus}1} s{sup {minus}1}) approximately 3% of the quenching events lead to the formation of excited Chla. Several sensitizers (decafluorobenzophenone, benzil, and fluorenone) domore » not induce Chla fluorescence (or do it very inefficiently) in spite of having triplet energies above the S{sub 1} level of Chla. In light of their results the most probable mechanism involves energy transfer from the triplet sensitizer to an upper triple state of Chla ({sup 3}Chla**) which can undergo reverse intersystem crossing to the singlet manifold of Chla and thus induce fluorescence. The inefficient sensitizers are those where electron transfer between the excited singlet of Chla or {sup 3}Chla** and ground-state sensitizers is energetically favorable, leading to rapid in-cage quenching of the initially formed excited states of Chla. Formation of radical-ion pair between the triplet sensitizer and Chla followed by the generation of singlet Chla in the recombination of the radical ions could not be completely discarded.« less

Triplet ultrasound growth parameters.

PubMed

Vora, Neeta L; Ruthazer, Robin; House, Michael; Chelmow, David

2006-03-01

To create ultrasound growth curves for normal growth of fetal triplets using statistical methodology that properly accounts for similarities of growth of fetuses within a mother as well as repeated measurements over time for each fetus. In this longitudinal study, all triplet pregnancies managed at a single tertiary center from 1992-2004 were reviewed. Fetuses with major anomalies, prior selective reduction, or fetal demise were excluded. Data from early and late gestation in which there were fewer than 30 fetal measurements available for analysis were excluded. We used multilevel models to account for variation in growth within a single fetus over time, variations in growth between multiple fetuses within a single mother, and variations in fetal growth between mothers. Medians (50th), 10th, and 90th percentiles were estimated by the creation of multiple quadratic growth models from bootstrap samples adapting a previously published method to compute prediction intervals. Estimated fetal weight was derived from Hadlock's formula. One hundred fifty triplet pregnancies were identified. Twenty-seven pregnancies were excluded for the following reasons: missing records (23), fetal demise (3), and fetal anomaly (1). The study group consisted of 123 pregnancies. The gestational age range was restricted to 14-34 weeks. Figures and tables were developed showing medians, 10th and 90th percentiles for estimated fetal weight, femur length, biparietal diameter, abdominal circumference, and head circumference. Growth curves for triplet pregnancies were derived. These may be useful for identification of abnormal growth in triplet fetuses. III.

Exchange interaction between the triplet exciton and the localized spin in copper-phthalocyanine

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

Wu, Wei, E-mail: wei.wu@ucl.ac.uk

2014-06-14

Triplet excitonic state in the organic molecule may arise from a singlet excitation and the following inter-system crossing. Especially for a spin-bearing molecule, an exchange interaction between the triplet exciton and the original spin on the molecule can be expected. In this paper, such exchange interaction in copper-phthalocyanine (CuPc, spin-1/2 ) was investigated from first-principles by using density-functional theory within a variety of approximations to the exchange correlation, ranging from local-density approximation to long-range corrected hybrid-exchange functional. The magnitude of the computed exchange interaction is in the order of meV with the minimum value (1.5 meV, ferromagnetic) given by themore » long-range corrected hybrid-exchange functional CAM-B3LYP. This exchange interaction can therefore give rise to a spin coherence with an oscillation period in the order of picoseconds, which is much shorter than the triplet lifetime in CuPc (typically tens of nanoseconds). This implies that it might be possible to manipulate the localized spin on Cu experimentally using optical excitation and inter-system crossing well before the triplet state disappears.« less

Efficient triplet harvesting of hybrid white organic light-emitting diodes using thermally activated delayed fluorescence green emitter

NASA Astrophysics Data System (ADS)

Lee, Song Eun; Lee, Ho Won; Baek, Hyun Jung; Yun, Tae Jun; Yun, Geum Jae; Kim, Woo Young; Kim, Young Kwan

2016-10-01

Hybrid white organic light-emitting diodes (WOLEDs) were fabricated by applying triplet harvesting (TH) using a green thermally activated delayed fluorescence (TADF) emitter. The triplet exciton of the green TADF emitter can be upconverted to its singlet state. The TH involved energy transfer of triplet exciton from a blue fluorescent emitter to a green TADF and red phosphorescent emitters, where they can decay radiatively. In addition, the triplet exciton of the green TADF emitter was energy transferred to its singlet state for a reverse intersystem crossing by green emission. Enhanced hybrid WOLEDs were demonstrated using an efficient green TADF emitter combined with red phosphorescent and blue fluorescent emitters. Hybrid WOLEDs were fabricated with various hole-electron recombination zones as changing blue emitting layer thicknesses. Among these, hybrid WOLEDs showed a maximum external quantum efficiency of 11.23%, luminous efficiency of 29.20 cd/A, and a power efficiency of 26.21 lm/W. Moreover, the WOLED exhibited electroluminescence spectra with Commission International de L'Éclairage chromaticity of (0.38, 0.36) at 1000 cd/m2 and a color rendering index of 82 at a practical brightness of 20,000 cd/m2.

Aggressive posterior retinopathy of prematurity in two of the triplets: a case report.

PubMed

Wang, Dan; Zhang, Bo; Dong, Yu; Song, E

2015-02-01

Aggressive posterior retinopathy of prematurity is identified as a rare, rapidly progressing and severe form of retinopathy of prematurity (ROP). Here, we report the diagnosis and treatment of aggressive posterior retinopathy of prematurity (APROP) in two of the triplets born at low birth weight and small gestational age. A case concerning two triplets who were born at 31 weeks' gestational age with low birth weight and reached bilateral threshold APROP was reported. The ROP of triplets A and B had the characteristic features of aggressive diseases, which were posterior location, prominence of plus disease and rapid progression. Low birth weight and small gestational age, multiple pregnancies, pregnancy-induced hypertension and older age of the mother might account for the presentations of APROP. These cases demonstrate the importance of early screening and diagnosis in APROP infants. Prompt and adequate laser photocoagulation with a large number of high-intensity closely performed spots and early retreatment could be effective and safe for preventing the progression of APROP with plus disease in zone 1 or 2 in premature triplets. © The Author(s) 2014 Reprints and permissions: sagepub.co.uk/journalsPermissions.nav.

Observation of direct infrared multiphoton pumping of the triplet manifold of biacetyl

NASA Astrophysics Data System (ADS)

Tsao, Jeffrey Y.; Black, Jerry G.; Yablonovitch, Eli; Burak, Itamar

1980-09-01

Direct collisionless multiphoton (MP) excitation of the triplet vibronic manifold of biacetyl is reported. Following a dye laser pulse which prepares some of the biacetyl molecules in the triplet metastable state, the system is irradiated by an intense 20 ns 9.6μ CO2 pulse. The CO2 radiation induces fast quenching of the phosphorescence emission from the 3Au excited molecules. It also induces an emission signal in the fluorescence spectral region of biacetyl. This signal is related to an inverse electronic relaxation (IER) from excited triplet vibronic levels into isoenergetic singlet 1Au vibronic levels. Analysis of the induced luminescence signals provides information on the collisionless MP prompted vibrational distribution. Excitation with 10.6μ CO2 pulses leads to the simultaneous MP pumping of both the ground and triplet manifolds. The generation of blue emission signals in this experiment bears a close resemblance to recent observations of prompt visible emission due to MP pumping of ground state molecules. General expressions for the emission intensities are derived with special emphasis on the specific features of MP vibrational distributions. The detectability of MP induced emission signals is discussed.

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

Ghosh, H.N.; Pal, H.; Sapre, A.V.

Photoexcitation of complexes between fullerence C[sub 60] and organic amines in benzene solutions is known to result in charge separation (CS) and subsequent charge recombination (CR) reactions, which lead to varying yields of fullerence triplet formation. Picosecond flash photolysis studies are carried out on C[sub 60]-diphenylamine (DPA), C[sub 60]-triethylamine (TEA), C[sub 60]-diazabicyclooctane (DABCO), and C[sub 60]-triphenylamine (TPA) systems to find out mechanistic details of the triplet formation on CR by inducing heavy atom and polarity effects by using suitable solvents. It is found that in the case of C[sub 60]-DPA, C[sub 60]-TEA, and C[sub 60]-DABCO systems proton transfer from themore » amine cation to the C[sub 60] anion in the ion pair state dominates, leading to poor triplet yields, which improve in heavy atom containing solvents. In TPA, proton transfer is not possible and hence fullerene triplet yields are high. Increase of solvent polarity for this system results in decreased C[sub 60] triplet yields with a consequent increase in the ion dissociation yield. A suitable reaction scheme is proposed to explain the results obtained. 34 refs., 5 figs., 2 tabs.« less

1,3-Diphenylisobenzofuran: a Model Chromophore for Singlet Fission

DOE PAGES

Johnson, Justin C.; Michl, Josef

2017-09-11

In this review we first provide an introductory description of the singlet fission phenomenon and then describe the ground and electronically excited states of the parent 1,3-diphenylisobenzofuran chromophore (1) and about a dozen of its derivatives. A discussion of singlet fission in thin polycrystalline layers of these materials follows. The highest quantum yield of triplet formation by singlet fission, 200% at 80 K, is found in one of the two known crystal modification of the parent. In the other modification and in many derivatives, excimer formation competes successfully and triplet yields are low. A description of solution photophysics of covalentmore » dimers is described in the next section. Triplet yields are very low, but interesting phenomena are uncovered. One is an observation of a separated-charges (charge-transfer) intermediate in highly polar solvents. The other is an observation of excitation isomerism in both singlet and triplet states, where in one isomer the excitation is delocalized over both halves of the covalent dimer, whereas in the other it is localized on one of the halves. Finally, in the last section we present the operation of a simple device illustrating the use of triplets generated by singlet fission for charge separation.« less

Field Tolerances for the Triplet Quadrupoles of the LHC High Luminosity Lattice

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

Nosochkov, Yuri; Cai, Y.; Jiao, Y.

2012-06-25

It has been proposed to implement the so-called Achromatic Telescopic Squeezing (ATS) scheme in the LHC high luminosity (HL) lattice to reduce beta functions at the Interaction Points (IP) up to a factor of 8. As a result, the nominal 4.5 km peak beta functions reached in the Inner Triplets (IT) at collision will be increased by the same factor. This, therefore, justifies the installation of new, larger aperture, superconducting IT quadrupoles. The higher beta functions will enhance the effects of the triplet quadrupole field errors leading to smaller beam dynamic aperture (DA). To maintain the acceptable DA, the effectsmore » of the triplet field errors must be re-evaluated, thus specifying new tolerances. Such a study has been performed for the so-called '4444' collision option of the HL-LHC layout version SLHCV3.01, where the IP beta functions are reduced by a factor of 4 in both planes with respect to a pre-squeezed value of 60 cm at two collision points. The dynamic aperture calculations were performed using SixTrack. The impact on the triplet field quality is presented.« less

Venus - Stein Triplet Crater

NASA Image and Video Library

1996-01-29

NASA Magellan synthetic aperture radar SAR imaged this unique triplet crater, or crater field during orbits 418-421 on Sept. 21, 1990. The three craters appear to have relatively steep walls. http://photojournal.jpl.nasa.gov/catalog/PIA00088

VizieR Online Data Catalog: Isolated galaxies, pairs and triplets (Argudo-Fernandez+, 2015)

NASA Astrophysics Data System (ADS)

Argudo-Fernandez, M.; Verley, S.; Bergond, G.; Duarte Puertas, S.; Ramos Carmona, E.; Sabater, J.; Fernandez, Lorenzo M.; Espada, D.; Sulentic, J.; Ruiz, J. E.; Leon, S.

2015-04-01

Catalogues of isolated galaxies, isolated pairs, and isolated triplets in the local Universe with positions, redshifts, and degrees of relation with their physical and large-scale environments. (5 data files).

Ultrabright fluorescent OLEDS using triplet sinks

DOEpatents

Zhang, Yifan; Forrest, Stephen R; Thompson, Mark

2013-06-04

A first device is provided. The first device further comprises an organic light emitting device. The organic light emitting device further comprises an anode, a cathode, and an emissive layer disposed between the anode and the cathode. The emissive layer further comprises an organic host compound, an organic emitting compound capable of fluorescent emission at room temperature, and an organic dopant compound. The triplet energy of the dopant compound is lower than the triplet energy of the host compound. The dopant compound does not strongly absorb the fluorescent emission of the emitting compound.

'Blueberry' Triplets Born in Rock

NASA Technical Reports Server (NTRS)

2004-01-01

This microscopic image, taken at the outcrop region dubbed 'Berry Bowl' near the Mars Exploration Rover Opportunity's landing site, shows the sphere-like grains or 'blueberries' that fill Berry Bowl. Of particular interest is the blueberry triplet, which indicates that these geologic features grew in pre-existing wet sediments. Other sphere-like grains that form in the air, such as impact spherules or ejected volcanic material called lapilli, are unlikely to fuse along a line and form triplets. This image was taken by the rover's microscopic imager on the 46th martian day, or sol, of its mission.

Preferential Nucleosome Assembly at DNA Triplet Repeats from the Myotonic Dystrophy Gene

NASA Astrophysics Data System (ADS)

Wang, Yuh-Hwa; Amirhaeri, Sorour; Kang, Seongman; Wells, Robert D.; Griffith, Jack D.

1994-07-01

The expansion of CTG repeats in DNA occurs in or near genes involved in several human diseases, including myotonic dystrophy and Huntington's disease. Nucleosomes, the basic structural element of chromosomes, consist of 146 base pairs of DNA coiled about an octamer of histone proteins and mediate general transcriptional repression. Electron microscopy was used to examine in vitro the nucleosome assembly of DNA containing repeating CTG triplets. The efficiency of nucleosome formation increased with expanded triplet blocks, suggesting that such blocks may repress transcription through the creation of stable nucleosomes.

A Sommerfeld toolbox for colored dark sectors

NASA Astrophysics Data System (ADS)

El Hedri, Sonia; Kaminska, Anna; de Vries, Maikel

2017-09-01

We present analytical formulas for the Sommerfeld corrections to the annihilation of massive colored particles into quarks and gluons through the strong interaction. These corrections are essential to accurately compute the dark matter relic density for coannihilation with colored partners. Our formulas allow us to compute the Sommerfeld effect, not only for the lowest term in the angular momentum expansion of the amplitude, but for all orders in the partial wave expansion. In particular, we carefully account for the effects of the spin of the annihilating particle on the symmetry of the two-particle wave function. This work focuses on strongly interacting particles of arbitrary spin in the triplet, sextet and octet color representations. For typical velocities during freeze-out, we find that including Sommerfeld corrections on the next-to-leading order partial wave leads to modifications of up to 10 to 20 percent on the total annihilation cross section. Complementary to QCD, we generalize our results to particles charged under an arbitrary unbroken SU( N) gauge group, as encountered in dark glueball models. In connection with this paper a Mathematica notebook is provided to compute the Sommerfeld corrections for colored particles up to arbitrary order in the angular momentum expansion.

Evaluation of facial attractiveness from end-of-treatment facial photographs.

PubMed

Shafiee, Roxanne; Korn, Edward L; Pearson, Helmer; Boyd, Robert L; Baumrind, Sheldon

2008-04-01

Orthodontists typically make judgments of facial attractiveness by examining groupings of profile, full-face, and smiling photographs considered together as a "triplet." The primary objective of this study was to determine the relative contributions of the 3 photographs-each considered separately-to the overall judgment a clinician forms by examining the combination of the 3. End-of-treatment triplet orthodontic photographs of 45 randomly selected orthodontic patients were duplicated. Copies of the profile, full-face, and smiling images were generated, and the images were separated and then pooled by image type for all subjects. Ten judges ranked the 45 photographs of each image type for facial attractiveness in groups of 9 to 12, from "most attractive" to "least attractive." Each judge also ranked the triplet groupings for the same 45 subjects. The mean attractiveness rankings for each type of photograph were then correlated with the mean rankings of each other and the triplets. The rankings of the 3 image types correlated highly with each other and the rankings of the triplets (P <.0001). The rankings of the smiling photographs were most predictive of the rankings of the triplets (r = 0.93); those of the profile photographs were the least predictive (r = 0.76). The difference between these correlations was highly statistically significant (P = .0003). It was also possible to test the extent to which the judges' rankings were influenced by sex, original Angle classification, and extraction status of each patient. No statistically significant preferences were found for sex or Angle classification, and only 1 marginally significant preference was found for extraction pattern. Clinician judges demonstrated a high level of agreement in ranking the facial attractiveness of profile, full-face, and smiling photographs of a group of orthodontically treated patients whose actual differences in physical dimensions were relatively small. The judges' rankings of the smiling photographs were significantly better predictors of their rankings of the triplet of each patient than were their rankings of the profile photographs.

Anthracycline-based triplets do not improve the efficacy of platinum-fluoropyrimidine doublets in first-line treatment of advanced gastric cancer: real-world data from the AGAMEMON National Cancer Registry.

PubMed

Carmona-Bayonas, A; Jiménez-Fonseca, P; Custodio, A; Sánchez Cánovas, M; Hernández, R; Pericay, C; Echavarria, I; Lacalle, A; Visa, L; Rodríguez Palomo, A; Mangas, M; Cano, J M; Buxo, E; Álvarez-Manceñido, F; García, T; Lorenzo, J E; Ferrer-Cardona, M; Viudez, A; Azkarate, A; Ramchandani, A; Arias, D; Longo, F; López, C; Sánchez Bayona, R; Limón, M L; Díaz-Serrano, A; Fernández Montes, A; Sala, P; Cerdá, P; Rivera, F; Gallego, J

2018-01-01

Although anthracycline-based triplets are one of the most widely used schedules to treat advanced gastric cancer (AGC), the benefit of including epirubicin in these therapeutic combinations remains unknown. This study aims to evaluate both the efficacy and tolerance of triplets with epirubicin vs. doublets with platinum-fluoropyrimidine in a national AGC registry. Patients with AGC treated with polychemotherapy without trastuzumab at 28 hospitals in Spain between 2008 and 2016 were included. The effect of anthracycline-based triplets against doublets was evaluated by propensity score matching (PSM) and Cox proportional hazards (PH) regression. A total of 1002 patients were included (doublets, n = 653; anthracycline-based triplets, n = 349). The multivariable Cox PH regression failed to detect significantly increased OS in favor of triplets with anthracyclines: HR 0.90 (95% CI, 0.78-1.05), p = 0.20035. After PSM, the sample contained 325 pairs with similar baseline characteristics. This method was also unable to reveal an increase in OS: 10.5 (95% CI, 9.7-12.3) vs. 9.9 (95% CI, 9.2-11.4) months, HR 0.91 (CI 95%, 0.76-1.083), and (log-rank test, p = 0.226). Response rates (42.1 vs. 33.1%, p = 0.12) and PFS (HR 0.95, CI 95%, 0.80-1.13, log-rank test, p = 0.873) were not significantly higher with epirubicin-based regimens. The triplets were associated with greater grade 3-4 hematological toxicity, and increased hospitalization due to toxicity by 68%. The addition of epirubicin is viable, but 23.7% discontinued treatment because of adverse effects or patient decision. Anthracyclines added to platinum-fluoropyrimidine doublets did not improve the response rate or survival outcomes in patients with AGC but entailed greater toxicity.

Thermodynamic contributions for the incorporation of GTA triplets within canonical TAT/TAT and C+GC/C+GC base-triplet stacks of DNA triplexes.

PubMed

Soto, Ana Maria; Marky, Luis A

2002-10-15

Nucleic acid triple helices may be used in the control of gene expression. One limitation of using triplex-forming oligonucleotides as therapeutic agents is that their target sequences are limited to homopurine tracts. To increase the repertoire of sequences that can be targeted, it has been postulated that a guanine can target a thymidine forming a stable GTA mismatch triplet. In this work, we have used a combination of optical and calorimetric techniques to determine thermodynamic unfolding profiles of two triplexes containing a single GTA triplet, d(A(3)TA(3)C(5)T(3)AT(3)C(5)T(3)GT(3)) (ATA) and d(AGTGAC(5)TCACTC(5)TCGCT) (GTG), and their control triplexes, d(A(7)C(5)T(7)C(5)T(7)) (TAT7) and d(AGAGAC(5)TCTCTC(5)TCTCT) (AG5T). In general, the presence of a GTA mismatch in DNA triplexes is destabilizing; however, this destabilization is greater when placed in a C(+)GC/C(+)GC base-triplet stack than between a TAT/TAT stack. These destabilizations are accompanied by a reduced unfolding enthalpy of approximately 10 kcal/mol, suggesting a decrease in the base stacking contributions surrounding the mismatch. Relative to their corresponding control triplexes, the folding of ATA is accompanied by a lower counterion uptake and a similar proton uptake, while GTG folding is accompanied by an increase in the counterion and proton uptakes. These effects are consistent with the observed decrease in stacking interactions. The overall results indicate that the main difficulty of targeting pyrimidine interruptions is that the decrease in stacking contributions, due to the incorporation of a GTA mismatch, affects the stability of the neighboring base triplets. This suggests that nucleotide analogues that increase the strength of these base-triplet stacks will result in a more effective targeting of pyrimidine interruptions.

"Triplet" polycistronic vectors encoding Gata4, Mef2c, and Tbx5 enhances postinfarct ventricular functional improvement compared with singlet vectors.

PubMed

Mathison, Megumi; Singh, Vivek P; Gersch, Robert P; Ramirez, Maricela O; Cooney, Austin; Kaminsky, Stephen M; Chiuchiolo, Maria J; Nasser, Ahmed; Yang, Jianchang; Crystal, Ronald G; Rosengart, Todd K

2014-10-01

The in situ reprogramming of cardiac fibroblasts into induced cardiomyocytes by the administration of gene transfer vectors encoding Gata4 (G), Mef2c (M), and Tbx5 (T) has been shown to improve ventricular function in myocardial infarction models. The efficacy of this strategy could, however, be limited by the need for fibroblast targets to be infected 3 times--once by each of the 3 transgene vectors. We hypothesized that a polycistronic "triplet" vector encoding all 3 transgenes would enhance postinfarct ventricular function compared with use of "singlet" vectors. After validation of the polycistronic vector expression in vitro, adult male Fischer 344 rats (n=6) underwent coronary ligation with or without intramyocardial administration of an adenovirus encoding all 3 major vascular endothelial growth factor (VEGF) isoforms (AdVEGF-All6A positive), followed 3 weeks later by the administration to AdVEGF-All6A-positive treated rats of singlet lentivirus encoding G, M, or T (1×10(5) transducing units each) or the same total dose of a GMT "triplet" lentivirus vector. Western blots demonstrated that triplet and singlet vectors yielded equivalent GMT transgene expression, and fluorescence activated cell sorting demonstrated that triplet vectors were nearly twice as potent as singlet vectors in generating induced cardiomyocytes from cardiac fibroblasts. Echocardiography demonstrated that GMT triplet vectors were more effective than the 3 combined singlet vectors in enhancing ventricular function from postinfarct baselines (triplet, 37%±10%; singlet, 13%±7%; negative control, 9%±5%; P<.05). These data have confirmed that the in situ administration of G, M, and T induces postinfarct ventricular functional improvement and that GMT polycistronic vectors enhance the efficacy of this strategy. Copyright © 2014 The American Association for Thoracic Surgery. Published by Elsevier Inc. All rights reserved.

Phosphorescent cyclometalated complexes for efficient blue organic light-emitting diodes

PubMed Central

Suzuri, Yoshiyuki; Oshiyama, Tomohiro; Ito, Hiroto; Hiyama, Kunihisa; Kita, Hiroshi

2014-01-01

Phosphorescent emitters are extremely important for efficient organic light-emitting diodes (OLEDs), which attract significant attention. Phosphorescent emitters, which have a high phosphorescence quantum yield at room temperature, typically contain a heavy metal such as iridium and have been reported to emit blue, green and red light. In particular, the blue cyclometalated complexes with high efficiency and high stability are being developed. In this review, we focus on blue cyclometalated complexes. Recent progress of computational analysis necessary to design a cyclometalated complex is introduced. The prediction of the radiative transition is indispensable to get an emissive cyclometalated complex. We summarize four methods to control phosphorescence peak of the cyclometalated complex: (i) substituent effect on ligands, (ii) effects of ancillary ligands on heteroleptic complexes, (iii) design of the ligand skeleton, and (iv) selection of the central metal. It is considered that novel ligand skeletons would be important to achieve both a high efficiency and long lifetime in the blue OLEDs. Moreover, the combination of an emitter and a host is important as well as the emitter itself. According to the dependences on the combination of an emitter and a host, the control of exciton density of the triplet is necessary to achieve both a high efficiency and a long lifetime, because the annihilations of the triplet state cause exciton quenching and material deterioration. PMID:27877712

Phosphorescent cyclometalated complexes for efficient blue organic light-emitting diodes

NASA Astrophysics Data System (ADS)

Suzuri, Yoshiyuki; Oshiyama, Tomohiro; Ito, Hiroto; Hiyama, Kunihisa; Kita, Hiroshi

2014-10-01

Phosphorescent emitters are extremely important for efficient organic light-emitting diodes (OLEDs), which attract significant attention. Phosphorescent emitters, which have a high phosphorescence quantum yield at room temperature, typically contain a heavy metal such as iridium and have been reported to emit blue, green and red light. In particular, the blue cyclometalated complexes with high efficiency and high stability are being developed. In this review, we focus on blue cyclometalated complexes. Recent progress of computational analysis necessary to design a cyclometalated complex is introduced. The prediction of the radiative transition is indispensable to get an emissive cyclometalated complex. We summarize four methods to control phosphorescence peak of the cyclometalated complex: (i) substituent effect on ligands, (ii) effects of ancillary ligands on heteroleptic complexes, (iii) design of the ligand skeleton, and (iv) selection of the central metal. It is considered that novel ligand skeletons would be important to achieve both a high efficiency and long lifetime in the blue OLEDs. Moreover, the combination of an emitter and a host is important as well as the emitter itself. According to the dependences on the combination of an emitter and a host, the control of exciton density of the triplet is necessary to achieve both a high efficiency and a long lifetime, because the annihilations of the triplet state cause exciton quenching and material deterioration.

Effects of triplet Higgs bosons in long baseline neutrino experiments

NASA Astrophysics Data System (ADS)

Huitu, K.; Kärkkäinen, T. J.; Maalampi, J.; Vihonen, S.

2018-05-01

The triplet scalars (Δ =Δ++,Δ+,Δ0) utilized in the so-called type-II seesaw model to explain the lightness of neutrinos, would generate nonstandard interactions (NSI) for a neutrino propagating in matter. We investigate the prospects to probe these interactions in long baseline neutrino oscillation experiments. We analyze the upper bounds that the proposed DUNE experiment might set on the nonstandard parameters and numerically derive upper bounds, as a function of the lightest neutrino mass, on the ratio the mass MΔ of the triplet scalars, and the strength |λϕ| of the coupling ϕ ϕ Δ of the triplet Δ and conventional Higgs doublet ϕ . We also discuss the possible misinterpretation of these effects as effects arising from a nonunitarity of the neutrino mixing matrix and compare the results with the bounds that arise from the charged lepton flavor violating processes.

Ion-Pair States in Triplet Molecular Hydrogen

NASA Astrophysics Data System (ADS)

Setzer, W.; Baker, B. C.; Ashman, S.; Morgan, T. J.

2016-05-01

An experimental search is underway to observe the long range triplet ionic states H+ H- of molecular hydrogen. Resonantly enhanced multi-photon ionization of the metastable c 3∏u- 2 pπ state is used access to the R(1)nd1 n = 21 Rydberg state that serves as an intermediate stepping stone state to probe the energy region above the ionization limit with a second tunable laser photon. The metastable state is prepared by electron capture of 6 keV H2+ions in potassium in a molecular beam. Formation of the H+ H- triplet configuration involves triplet excited states of the H- ion, especially the 2p23Pe state, the second bound state of H- predicted to exist with a lifetime long compared to typical auto ionization lifetimes but not yet observed experimentally. Details of the experiment and preliminary results to date will be presented at the conference.

Optical image encryption using triplet of functions

NASA Astrophysics Data System (ADS)

Yatish; Fatima, Areeba; Nishchal, Naveen Kumar

2018-03-01

We propose an image encryption scheme that brings into play a technique using a triplet of functions to manipulate complex-valued functions. Optical cryptosystems using this method are an easier approach toward the ciphertext generation that avoids the use of holographic setup to record phase. The features of this method were shown in the context of double random phase encoding and phase-truncated Fourier transform-based cryptosystems using gyrator transform. In the first step, the complex function is split into two matrices. These matrices are separated, so they contain the real and imaginary parts. In the next step, these two matrices and a random distribution function are acted upon by one of the functions in the triplet. During decryption, the other two functions in the triplet help us retrieve the complex-valued function. The simulation results demonstrate the effectiveness of the proposed idea. To check the robustness of the proposed scheme, attack analyses were carried out.

Mapping the Complete Reaction Path of a Complex Photochemical Reaction.

PubMed

Smith, Adam D; Warne, Emily M; Bellshaw, Darren; Horke, Daniel A; Tudorovskya, Maria; Springate, Emma; Jones, Alfred J H; Cacho, Cephise; Chapman, Richard T; Kirrander, Adam; Minns, Russell S

2018-05-04

We probe the dynamics of dissociating CS_{2} molecules across the entire reaction pathway upon excitation. Photoelectron spectroscopy measurements using laboratory-generated femtosecond extreme ultraviolet pulses monitor the competing dissociation, internal conversion, and intersystem crossing dynamics. Dissociation occurs either in the initially excited singlet manifold or, via intersystem crossing, in the triplet manifold. Both product channels are monitored and show that, despite being more rapid, the singlet dissociation is the minor product and that triplet state products dominate the final yield. We explain this by a consideration of accurate potential energy curves for both the singlet and triplet states. We propose that rapid internal conversion stabilizes the singlet population dynamically, allowing for singlet-triplet relaxation via intersystem crossing and the efficient formation of spin-forbidden dissociation products on longer timescales. The study demonstrates the importance of measuring the full reaction pathway for defining accurate reaction mechanisms.

Mapping the Complete Reaction Path of a Complex Photochemical Reaction

NASA Astrophysics Data System (ADS)

Smith, Adam D.; Warne, Emily M.; Bellshaw, Darren; Horke, Daniel A.; Tudorovskya, Maria; Springate, Emma; Jones, Alfred J. H.; Cacho, Cephise; Chapman, Richard T.; Kirrander, Adam; Minns, Russell S.

2018-05-01

We probe the dynamics of dissociating CS2 molecules across the entire reaction pathway upon excitation. Photoelectron spectroscopy measurements using laboratory-generated femtosecond extreme ultraviolet pulses monitor the competing dissociation, internal conversion, and intersystem crossing dynamics. Dissociation occurs either in the initially excited singlet manifold or, via intersystem crossing, in the triplet manifold. Both product channels are monitored and show that, despite being more rapid, the singlet dissociation is the minor product and that triplet state products dominate the final yield. We explain this by a consideration of accurate potential energy curves for both the singlet and triplet states. We propose that rapid internal conversion stabilizes the singlet population dynamically, allowing for singlet-triplet relaxation via intersystem crossing and the efficient formation of spin-forbidden dissociation products on longer timescales. The study demonstrates the importance of measuring the full reaction pathway for defining accurate reaction mechanisms.

Pulsed electron nuclear double resonance studies of the photoexcited triplet state of pentacene in p-terphenyl crystals at room temperature.

PubMed

Yago, Tomoaki; Link, Gerhard; Kothe, Gerd; Lin, Tien-Sung

2007-09-21

Pulsed electron nuclear double resonance (ENDOR) using a modified Davies-type [Phys. Lett. 47A, 1 (1974)] sequence is employed to study the hyperfine (HF) structure of the photoexcited triplet state of pentacene dispersed in protonated and deuterated p-terphenyl single crystals. The strong electron spin polarization and long phase memory time of triplet pentacene enable us to perform the ENDOR measurements on the S=1 spin system at room temperature. Proton HF tensor elements and spin density values of triplet pentacene are extracted from a detailed angular-dependent study in which the orientation of the magnetic field is varied systematically in two different pentacene planes. Analysis reveals that the pentacene molecule is no longer planar in the p-terphenyl host lattice. The distortion is more pronounced in the deuterated crystal where the unit cell dimensions are slightly smaller than those of the protonated crystal.

Triplet excited state spectra and dynamics of carotenoids from the thermophilic purple photosynthetic bacterium Thermochromatium tepidum

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

Niedzwiedzki, Dariusz; Kobayashi, Masayuki; Blankenship, R. E.

Light-harvesting complex 2 from the anoxygenic phototrophic purple bacterium Thermochromatium tepidum was purified and studied by steady-state absorption, fluorescence and flash photolysis spectroscopy. Steady-state absorption and fluorescence measurements show that carotenoids play a negligible role as supportive energy donors and transfer excitation to bacteriochlorophyll-a with low energy transfer efficiency of ~30%. HPLC analysis determined that the dominant carotenoids in the complex are rhodopin and spirilloxanthin. Carotenoid excited triplet state formation upon direct (carotenoid) or indirect (bacteriochlorophyll-a Q{sub x} band) excitation shows that carotenoid triplets are mostly localized on spirilloxanthin. In addition, no triplet excitation transfer between carotenoids was observed. Suchmore » specific carotenoid composition and spectroscopic results strongly suggest that this organism optimized carotenoid composition in the light-harvesting complex 2 in order to maximize photoprotective capabilities of carotenoids but subsequently drastically suppressed their supporting role in light-harvesting process.« less

Electron impact excitation of the electronic states of N2. III - Transitions in the 12.5-14.2-eV energy-loss region at incident energies of 40 and 60 eV

NASA Technical Reports Server (NTRS)

Chutjian, A.; Trajmar, S.; Cartwright, D. C.

1977-01-01

Analysis of electron energy-loss data at incident electron energies of 40 and 60 eV has led to the determination of normalized absolute differential cross sections for electron-impact excitation of five optically-allowed singlet states, two known triplet states, and two unknown triplet-like states of N2, lying in the energy-loss range 12.5-14.2 eV. The range of scattering angles was 5 to 138 deg. The optically allowed transitions and the known triplet excitations are identified. Cross sections for excitation to two unidentified triplet-like states at 13.155 and 13.395 eV were also obtained. The relationship of the generalized oscillator strength for the dipole-allowed states obtained from the described data to known optical oscillator strengths is discussed.

Implications of a electroweak triplet scalar leptoquark on the ultra-high energy neutrino events at IceCube

NASA Astrophysics Data System (ADS)

Mileo, Nicolas; de la Puente, Alejandro; Szynkman, Alejandro

2016-11-01

We study the production of scalar leptoquarks at IceCube, in particular, a particle transforming as a triplet under the weak interaction. The existence of electroweak-triplet scalars is highly motivated by models of grand unification and also within radiative seesaw models for neutrino mass generation. In our framework, we extend the Standard Model by a single colored electroweak-triplet scalar leptoquark and analyze its implications on the excess of ultra-high energy neutrino events observed by the IceCube collaboration. We consider only couplings between the leptoquark to first generation of quarks and first and second generations of leptons, and carry out a statistical analysis to determine the parameters that best describe the IceCube data as well as set 95% CL upper bounds. We analyze whether this study is still consistent with most up-to-date LHC data and various low energy observables.

Peccei-Quinn symmetry for Dirac seesaw and leptogenesis

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

Gu, Pei-Hong

We extend the DFSZ invisible axion model to simultaneously explain small Dirac neutrino masses and cosmic matter-antimatter asymmetry. After the Peccei-Quinn and electroweak symmetry breaking, the effective Yukawa couplings of the Dirac neutrinos to the standard model Higgs scalar can be highly suppressed by the ratio of the vacuum expectation value of an iso-triplet Higgs scalar over the masses of some heavy gauge-singlet fermions, iso-doublet Higgs scalars or iso-triplet fermions. The iso-triplet fields can carry a zero or nonzero hypercharge. Through the decays of the heavy gauge-singlet fermions, iso-doublet scalars or iso-triplet fermions, we can obtain a lepton asymmetry inmore » the left-handed leptons and an opposite lepton asymmetry in the right-handed neutrinos. Since the right-handed neutrinos do not participate in the sphaleron processes, the left-handed lepton asymmetry can be partially converted to a baryon asymmetry.« less

Creation of Spin-Triplet Cooper Pairs in the Absence of Magnetic Ordering

NASA Astrophysics Data System (ADS)

Breunig, Daniel; Burset, Pablo; Trauzettel, Björn

2018-01-01

In superconducting spintronics, it is essential to generate spin-triplet Cooper pairs on demand. Up to now, proposals to do so concentrate on hybrid structures in which a superconductor (SC) is combined with a magnetically ordered material (or an external magnetic field). We, instead, identify a novel way to create and isolate spin-triplet Cooper pairs in the absence of any magnetic ordering. This achievement is only possible because we drive a system with strong spin-orbit interaction—the Dirac surface states of a strong topological insulator (TI)-out of equilibrium. In particular, we consider a bipolar TI-SC-TI junction, where the electrochemical potentials in the outer leads differ in their overall sign. As a result, we find that nonlocal singlet pairing across the junction is completely suppressed for any excitation energy. Hence, this junction acts as a perfect spin-triplet filter across the SC, generating equal-spin Cooper pairs via crossed Andreev reflection.

Creation of Spin-Triplet Cooper Pairs in the Absence of Magnetic Ordering.

PubMed

Breunig, Daniel; Burset, Pablo; Trauzettel, Björn

2018-01-19

In superconducting spintronics, it is essential to generate spin-triplet Cooper pairs on demand. Up to now, proposals to do so concentrate on hybrid structures in which a superconductor (SC) is combined with a magnetically ordered material (or an external magnetic field). We, instead, identify a novel way to create and isolate spin-triplet Cooper pairs in the absence of any magnetic ordering. This achievement is only possible because we drive a system with strong spin-orbit interaction-the Dirac surface states of a strong topological insulator (TI)-out of equilibrium. In particular, we consider a bipolar TI-SC-TI junction, where the electrochemical potentials in the outer leads differ in their overall sign. As a result, we find that nonlocal singlet pairing across the junction is completely suppressed for any excitation energy. Hence, this junction acts as a perfect spin-triplet filter across the SC, generating equal-spin Cooper pairs via crossed Andreev reflection.

Photoluminescence-detected magnetic-resonance study of fullerene-doped π-conjugated polymers

NASA Astrophysics Data System (ADS)

Lane, P. A.; Shinar, J.; Yoshino, K.

1996-10-01

X-band photoluminescence (PL)-detected magnetic resonance (PLDMR) spectra of C60- and C70-doped 2,5-dihexoxy poly(p-phenylenevinylene) (DHO-PPV), 2,5-dibutoxy poly(p-phenylene ethynylene) (DBO-PPE), and poly(3-dodecylthiophene) (P3DT) are described and discussed. While light doping of DHO-PPV by both fullerenes quenches the PL, both the polaron and triplet exciton resonances are dramatically enhanced. This is attributed to the creation of conformational defects which enhance the fission of 11Bu singlet excitons to polaron pairs and intersystem crossing to 13Bu triplet excitons. The triplet resonance in all polymers is quenched at relatively low doping levels of C60 and C70, which is attributed to quenching of triplets by positive polarons injected onto the polymer chain. Increased doping by C60, but not C70, quenches the polaron resonance, also due to photoinduced charge transfer.

Intermolecular interaction approach for TADF (Conference Presentation)

NASA Astrophysics Data System (ADS)

Wong, Ken-Tsung

2016-09-01

Materials with thermally activated delayed fluorescence (TADF) have recently emerged as new fluorescent emitters for highly efficient organic light-emitting diodes (OLEDs). Molecule with TADF behavior needs to have a small singlet-triplet energy difference (ΔES-T) that allows the up-conversion from nonradiative triplet state (T1) to radiative singlet state (S1) via reverse intersystem crossing (RISC) process. Generally, molecules with small ΔES-T can be obtained via carefully manipulate the degree of "intramolecular" charge transfer (ICT) between electron-donating and -accepting components, such that the electron exchange energy that contributes to ΔES-T, can be minimized. Alternatively, excited state with small ΔES-T can be feasibly realized via "intermolecular" charge transfer occurring at the interface between spatially separating donor (D) and acceptor (A) molecules. Because the exchange energy decreases as the HOMO-LUMO separation distance increases, theoretically, the intermolecular D/A charge transfer state (or exciplex) should have rather small ΔES-T, leading to efficient TADF. However, it is still a challenge to access highly efficient exciplex systems. This is mainly because exciplex formation is commonly accompanied with a large red shift of emission spectra and long radiative lifetime, which tend to diminish photoluminescence quantum yield (PLQY) as well as electroluminescence (EL) performance. Until now, exciplex-based OLEDs with external quantum efficiency (EQE) above 10% are still limited. By judicious selection of donor and acceptor, the formation of efficient exciplex can be feasibly achieved. In this conference, our recent efforts on highly efficient exciplexes using C3-symmetry triazine acceptors and various donors, and their device characteristics will be presented.

Reactive carbon-chain molecules: synthesis of 1-diazo-2,4-pentadiyne and spectroscopic characterization of triplet pentadiynylidene (H-C[triple bond]C-:C-C[triple bond]C-H).

PubMed

Bowling, Nathan P; Halter, Robert J; Hodges, Jonathan A; Seburg, Randal A; Thomas, Phillip S; Simmons, Christopher S; Stanton, John F; McMahon, Robert J

2006-03-15

1-Diazo-2,4-pentadiyne (6a), along with both monodeuterio isotopomers 6b and 6c, has been synthesized via a route that proceeds through diacetylene, 2,4-pentadiynal, and 2,4-pentadiynal tosylhydrazone. Photolysis of diazo compounds 6a-c (lambda > 444 nm; Ar or N2, 10 K) generates triplet carbenes HC5H (1) and HC5D (1-d), which have been characterized by IR, EPR, and UV/vis spectroscopy. Although many resonance structures contribute to the resonance hybrid for this highly unsaturated carbon-chain molecule, experiment and theory reveal that the structure is best depicted in terms of the dominant resonance contributor of penta-1,4-diyn-3-ylidene (diethynylcarbene, H-C[triple bond]C-:C-C[triple bond]C-H). Theory predicts an axially symmetric (D(infinity h)) structure and a triplet electronic ground state for 1 (CCSD(T)/ANO). Experimental IR frequencies and isotope shifts are in good agreement with computed values. The triplet EPR spectrum of 1 (absolute value(D/hc) = 0.6157 cm(-1), absolute value(E/hc) = 0.0006 cm(-1)) is consistent with an axially symmetric structure, and the Curie law behavior confirms that the triplet state is the ground state. The electronic absorption spectrum of 1 exhibits a weak transition near 400 nm with extensive vibronic coupling. Chemical trapping of triplet HC5H (1) in an O2-doped matrix affords the carbonyl oxide 16 derived exclusively from attack at the central carbon.

Masticatory motor patterns in ungulates: a quantitative assessment of jaw-muscle coordination in goats, alpacas and horses.

PubMed

Williams, Susan H; Vinyard, Christopher J; Wall, Christine E; Hylander, William L

2007-04-01

We investigated patterns of jaw-muscle coordination during rhythmic mastication in three species of ungulates displaying the marked transverse jaw movements typical of many large mammalian herbivores. In order to quantify consistent motor patterns during chewing, electromyograms were recorded from the superficial masseter, deep masseter, posterior temporalis and medial pterygoid muscles of goats, alpacas and horses. Timing differences between muscle pairs were evaluated in the context of an evolutionary model of jaw-muscle function. In this model, the closing and food reduction phases of mastication are primarily controlled by two distinct muscle groups, triplet I (balancing-side superficial masseter and medial pterygoid and working-side posterior temporalis) and triplet II (working-side superficial masseter and medial pterygoid and balancing-side posterior temporalis), and the asynchronous activity of the working- and balancing-side deep masseters. The three species differ in the extent to which the jaw muscles are coordinated as triplet I and triplet II. Alpacas, and to a lesser extent, goats, exhibit the triplet pattern whereas horses do not. In contrast, all three species show marked asynchrony of the working-side and balancing-side deep masseters, with jaw closing initiated by the working-side muscle and the balancing-side muscle firing much later during closing. However, goats differ from alpacas and horses in the timing of the balancing-side deep masseter relative to the triplet II muscles. This study highlights interspecific differences in the coordination of jaw muscles to influence transverse jaw movements and the production of bite force in herbivorous ungulates.

Singlet-to-Triplet Excitations in the Unconventional Spin-Peierls System TiOBr

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

Clancy, James P; Gaulin, Bruce D.; Adams, Carl P

2011-01-01

We have performed time-of-flight neutron scattering measurements on powder samples of the unconventional spin-Peierls compound TiOBr using the fine-resolution Fermi chopper spectrometer (SEQUOIA) at the SNS. These measurements reveal two branches of magnetic excitations within the commensurate and incommensurate spin-Peierls phases, which we associate with n = 1 and n = 2 triplet excitations out of the singlet ground state. These measurements represent the first direct measure of the singlet-triplet energy gap in TiOBr, which is found to have a value of Eg 21 meV.

Long-Lived Ultracold Molecules with Electric and Magnetic Dipole Moments.

PubMed

Rvachov, Timur M; Son, Hyungmok; Sommer, Ariel T; Ebadi, Sepehr; Park, Juliana J; Zwierlein, Martin W; Ketterle, Wolfgang; Jamison, Alan O

2017-10-06

We create fermionic dipolar ^{23}Na^{6}Li molecules in their triplet ground state from an ultracold mixture of ^{23}Na and ^{6}Li. Using magnetoassociation across a narrow Feshbach resonance followed by a two-photon stimulated Raman adiabatic passage to the triplet ground state, we produce 3×10^{4} ground state molecules in a spin-polarized state. We observe a lifetime of 4.6 s in an isolated molecular sample, approaching the p-wave universal rate limit. Electron spin resonance spectroscopy of the triplet state was used to determine the hyperfine structure of this previously unobserved molecular state.

Long-Lived Ultracold Molecules with Electric and Magnetic Dipole Moments

NASA Astrophysics Data System (ADS)

Rvachov, Timur M.; Son, Hyungmok; Sommer, Ariel T.; Ebadi, Sepehr; Park, Juliana J.; Zwierlein, Martin W.; Ketterle, Wolfgang; Jamison, Alan O.

2017-10-01

We create fermionic dipolar 23Na 6Li molecules in their triplet ground state from an ultracold mixture of 23Na and 6Li. Using magnetoassociation across a narrow Feshbach resonance followed by a two-photon stimulated Raman adiabatic passage to the triplet ground state, we produce 3 ×1 04 ground state molecules in a spin-polarized state. We observe a lifetime of 4.6 s in an isolated molecular sample, approaching the p -wave universal rate limit. Electron spin resonance spectroscopy of the triplet state was used to determine the hyperfine structure of this previously unobserved molecular state.

Evidence for triplet superconductivity in a superconductor-ferromagnet spin valve.

PubMed

Leksin, P V; Garif'yanov, N N; Garifullin, I A; Fominov, Ya V; Schumann, J; Krupskaya, Y; Kataev, V; Schmidt, O G; Büchner, B

2012-08-03

We have studied the dependence of the superconducting (SC) transition temperature on the mutual orientation of magnetizations of Fe1 and Fe2 layers in the spin valve system CoO(x)/Fe1/Cu/Fe2/Pb. We find that this dependence is nonmonotonic when passing from the parallel to the antiparallel case and reveals a distinct minimum near the orthogonal configuration. The analysis of the data in the framework of the SC triplet spin valve theory gives direct evidence for the long-range triplet superconductivity arising due to noncollinearity of the two magnetizations.

Efficient triplet harvesting by fluorescent molecules through exciplexes for high efficiency organic light-emitting diodes

NASA Astrophysics Data System (ADS)

Park, Young-Seo; Kim, Kwon-Hyeon; Kim, Jang-Joo

2013-04-01

Efficient triplet harvesting from exciplexes by reverse intersystem crossing (RISC) is reported using a fluorescent molecular system composed of the 4,4',4″-tris(N-carbazolyl)-triphenylamine and bis-4,6-(3,5-di-3-pyridylphenyl)-2-methylpyrimidine. The exciplex forming material system shows the efficient delayed fluorescence emission. As a result, almost 100% PL efficiency at 35 K and 10% external quantum efficiency at 195 K are achieved from the exciplex. The delayed fluorescence of the exciplex clearly demonstrates that a significant proportion of the triplet exciplexes is harvested through the RISC.

Ab initio study of C + H3+ reactions

NASA Technical Reports Server (NTRS)

Talbi, D.; DeFrees, D. J.

1991-01-01

The reaction C + H3+ --> CH(+) + H2 is frequently used in models of dense interstellar cloud chemistry with the assumption that it is fast, i.e. there are no potential energy barriers inhibiting it. Ab initio molecular orbital study of the triplet CH3+ potential energy surface (triplet because the reactant carbon atom is a ground state triplet) supports this hypothesis. The reaction product is 3 pi CH+; the reaction is to exothermic even though the product is not in its electronic ground state. No path has been found on the potential energy surface for C + H3+ --> CH2(+) + H reaction.

Bound States in Dimerized and Frustrated Heisenberg Chains

NASA Astrophysics Data System (ADS)

Bouzerar, G.; Sil, S.

Using the Bond-Operator Technique (BOT), we have studied the low energy excitation spectrum of a frustrated dimerized antiferromagnetic Heisenberg chain. In particular, we have compared our analytical results with previous Exact Diagonalization (ED) data. Qualitatively, the BOT results are in good agreement with the ED data. And even a very good quantitative agreement is obtained in some parameter region. It is clearly shown that there is only one elementary excitation branch (lowest triplet branch) and that the two other well defined excitations which appear below the continuum, one singlet and one triplet, are bound states of two elementary triplets.

Effect of H2 binding on the nonadiabatic transition probability between singlet and triplet states of the [NiFe]-hydrogenase active site.

PubMed

Kaliakin, Danil S; Zaari, Ryan R; Varganov, Sergey A

2015-02-12

We investigate the effect of H2 binding on the spin-forbidden nonadiabatic transition probability between the lowest energy singlet and triplet electronic states of [NiFe]-hydrogenase active site model, using a velocity averaged Landau-Zener theory. Density functional and multireference perturbation theories were used to provide parameters for the Landau-Zener calculations. It was found that variation of the torsion angle between the terminal thiolate ligands around the Ni center induces an intersystem crossing between the lowest energy singlet and triplet electronic states in the bare active site and in the active site with bound H2. Potential energy curves between the singlet and triplet minima along the torsion angle and H2 binding energies to the two spin states were calculated. Upon H2 binding to the active site, there is a decrease in the torsion angle at the minimum energy crossing point between the singlet and triplet states. The probability of nonadiabatic transitions at temperatures between 270 and 370 K ranges from 35% to 32% for the active site with bound H2 and from 42% to 38% for the bare active site, thus indicating the importance of spin-forbidden nonadiabatic pathways for H2 binding on the [NiFe]-hydrogenase active site.

Comparison of atmospheric reactions of NH3 and NH2 with hydroxyl radical on the singlet, doublet and triplet potential energy surfaces, kinetic and mechanistic study

NASA Astrophysics Data System (ADS)

Vahedpour, Morteza; Douroudgari, Hamed; Afshar, Sheida; Asgharzade, Somaie

2018-05-01

The NH2 + OH and NH3 + OH reactions on the singlet, doublet and triplet potential energy surfaces carry out using MP2, QCISD, G3MP2, M06-2X, B3LYP, and CCSD(T)//MP2 levels. Three pre-reactive complexes, 1C1, 3C1 and 3C2 were formed among amidogen and hydroxyl radicals. From variety of the 1C1, four types of products are obtained that 1HNO + H2 is thermodynamically stable and three others are being stable after relaxation to triplet state. On the triplet state, five types of adducts are obtained that four of them have enough thermodynamic stability. Two intersystem crossing are presented among triplet and singlet states of the NH2 + OH reaction. 3NH + H2O adduct is spontaneous and exothermic in standard condition. Results lead to different adducts which are playing significant role in the atmospheric and combustion chemistry. The rate constants of selected pathways are calculated at the 300-2500 K temperature range at M06-2X/aug-ccpvqz and CCSD(T)/6-311++G(3df, 3pd) levels of theory.

Direct Detection of Singlet-Triplet Interconversion in OLED Magnetoelectroluminescence with a Metal-Free Fluorescence-Phosphorescence Dual Emitter

NASA Astrophysics Data System (ADS)

Ratzke, Wolfram; Bange, Sebastian; Lupton, John M.

2018-05-01

We demonstrate that a simple phenazine derivative can serve as a dual emitter for organic light-emitting diodes, showing simultaneous luminescence from the singlet and triplet excited states at room temperature without the need of heavy-atom substituents. Although devices made with this emitter achieve only low quantum efficiencies of <0.2 % , changes in fluorescence and phosphorescence intensity on the subpercent scale caused by an external magnetic field of up to 30 mT are clearly resolved with an ultra-low-noise optical imaging technique. The results demonstrate the concept of using simple reporter molecules, available commercially, to optically detect the spin of excited states formed in an organic light-emitting diode and thereby probe the underlying spin statistics of recombining electron-hole pairs. A clear anticorrelation of the magnetic-field dependence of singlet and triplet emission shows that it is the spin interconversion between singlet and triplet which dominates the magnetoluminescence response: the phosphorescence intensity decreases by the same amount as the fluorescence intensity increases. The concurrent detection of singlet and triplet emission as well as device resistance at cryogenic and room temperature constitute a useful tool to disentangle the effects of spin-dependent recombination from spin-dependent transport mechanisms.

Singlet and triplet excitation management in a bichromophoric near-infrared-phosphorescent BODIPY-benzoporphyrin platinum complex

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

Whited, M. T.; Djurovich, P. I.; Roberts, Sean T.

2011-01-12

Multichromophoric arrays provide one strategy for assembling molecules with intense absorptions across the visible spectrum but are generally focused on systems that efficiently produce and manipulate singlet excitations and therefore are burdened by the restrictions of (a) unidirectional energy transfer and (b) limited tunability of the lowest molecular excited state. In contrast, we present here a multichromophoric array based on four boron dipyrrins (BODIPY) bound to a platinum benzoporphyrin scaffold that exhibits intense panchromatic absorption and efficiently generates triplets. The spectral complementarity of the BODIPY and porphryin units allows the direct observation of fast bidirectional singlet and triplet energy transfermore » processes (k ST( 1BDP→ 1Por) = 7.8 × 10 11 s -1, k TT( 3Por→ 3BDP) = 1.0 × 10 10 s -1, k TT( 3BDP→ 3Por) = 1.6 × 10 10 s -1), leading to a long-lived equilibrated [ 3BDP][Por]⇌[BDP][ 3Por] state. This equilibrated state contains approximately isoenergetic porphyrin and BODIPY triplets and exhibits efficient near-infrared phosphorescence (λ em = 772 nm, Φ = 0.26). Taken together, these studies show that appropriately designed triplet-utilizing arrays may overcome fundamental limitations typically associated with core-shell chromophores by tunable redistribution of energy from the core back onto the antennae.« less

What is beta-carotene doing in the photosystem II reaction centre?

PubMed Central

Telfer, Alison

2002-01-01

During photosynthesis carotenoids normally serve as antenna pigments, transferring singlet excitation energy to chlorophyll, and preventing singlet oxygen production from chlorophyll triplet states, by rapid spin exchange and decay of the carotenoid triplet to the ground state. The presence of two beta-carotene molecules in the photosystem II reaction centre (RC) now seems well established, but they do not quench the triplet state of the primary electron-donor chlorophylls, which are known as P(680). The beta-carotenes cannot be close enough to P(680) for triplet quenching because that would also allow extremely fast electron transfer from beta-carotene to P(+)(680), preventing the oxidation of water. Their transfer of excitation energy to chlorophyll, though not very efficient, indicates close proximity to the chlorophylls ligated by histidine 118 towards the periphery of the two main RC polypeptides. The primary function of the beta-carotenes is probably the quenching of singlet oxygen produced after charge recombination to the triplet state of P(680). Only when electron donation from water is disturbed does beta-carotene become oxidized. One beta-carotene can mediate cyclic electron transfer via cytochrome b559. The other is probably destroyed upon oxidation, which might trigger a breakdown of the polypeptide that binds the cofactors that carry out charge separation. PMID:12437882

Triplet repeat RNA structure and its role as pathogenic agent and therapeutic target

PubMed Central

Krzyzosiak, Wlodzimierz J.; Sobczak, Krzysztof; Wojciechowska, Marzena; Fiszer, Agnieszka; Mykowska, Agnieszka; Kozlowski, Piotr

2012-01-01

This review presents detailed information about the structure of triplet repeat RNA and addresses the simple sequence repeats of normal and expanded lengths in the context of the physiological and pathogenic roles played in human cells. First, we discuss the occurrence and frequency of various trinucleotide repeats in transcripts and classify them according to the propensity to form RNA structures of different architectures and stabilities. We show that repeats capable of forming hairpin structures are overrepresented in exons, which implies that they may have important functions. We further describe long triplet repeat RNA as a pathogenic agent by presenting human neurological diseases caused by triplet repeat expansions in which mutant RNA gains a toxic function. Prominent examples of these diseases include myotonic dystrophy type 1 and fragile X-associated tremor ataxia syndrome, which are triggered by mutant CUG and CGG repeats, respectively. In addition, we discuss RNA-mediated pathogenesis in polyglutamine disorders such as Huntington's disease and spinocerebellar ataxia type 3, in which expanded CAG repeats may act as an auxiliary toxic agent. Finally, triplet repeat RNA is presented as a therapeutic target. We describe various concepts and approaches aimed at the selective inhibition of mutant transcript activity in experimental therapies developed for repeat-associated diseases. PMID:21908410

The spectral properties of DNA and RNA macromolecules at low temperatures: fundamental and applied aspects

NASA Astrophysics Data System (ADS)

Yashchuk, Valeriy M.; Kudrya, Vladislav Yu

2017-03-01

This paper summarizes the results of studies of the spectral properties—optical absorption, fluorescence and phosphorescence—of DNA and RNA macromolecules and synthetic poly-, oligo- and mono-nucleotides, which have been carried out in our laboratory. The system of first excited singlet and triplet energy levels for DNA and RNA is evaluated using low-temperature (4.2 K-77 K) luminescent measurements. The traps of the singlet and triplet electronic excitations in these compounds are identified. An important self-protection mechanism against photo-damage of DNA and RNA by UV photons or penetrative radiation based on the capture of triplet electronic-energy excitations by the most photostable centers—in DNA, the complex formed by neighboring adenosine (A) and thymidine (T) links; in RNA, the adenosine links—is described. It is confirmed that despite similarities in the chemical and partly energy structures DNA is more stable than RNA. The spectral manifestation of the telomeres (the important functional system) in DNA macromolecules is examined. The results obtained on telomere fragments provide the possibility of finding the configuration peculiarities of the triplet excitations traps in DNA macromolecules. The resulting spreading length of the migrating singlet (l s) and triplet (l t) excitations for DNA and RNA macromolecules are evaluated.

Triplet firing origin in human motor units: emerging hypotheses.

PubMed

Kudina, Lydia P; Andreeva, Regina E

2016-03-01

A specific feature of motor unit (MU) firing behaviour is rhythmic trains of single discharges at low rate resulting from the prolonged motoneuronal afterhyperpolarization. However, some MUs exhibit occasional doublets with uniquely short interspike intervals (2.5-20.0 ms). Motoneuronal delayed depolarization is commonly accepted to be doublet underlying mechanism. Apart from doublets, much scarcer MU triple discharges were described, but their mechanisms are disputable. The aim of the present study was to analyse MU triplet firing origin in healthy humans. MU triple discharges occasionally arising during gentle voluntary muscle contractions were compared with those arising in axons during motor nerve stimulation. Firing pattern was analysed in 109 MUs of four muscles: the tibialis anterior, the flexor carpi ulnaris, the abductor pollicis brevis, and the abductor digiti minimi. Our findings present evidence that during voluntary contractions two kinds of MU triplet firing can be occasionally observed: "true" motoneuronal triplets (interspike intervals of 3.6-17.3 ms) with the delayed depolarization as the possible underlying mechanism and axonal triple discharges including the M-response and F-wave. The findings can be useful not only for understanding mechanisms of the very rare motoneuronal firing in healthy humans but also for estimation of pathological triplet firing origin.

Efficient Generation of Long-Lived Triplet Excitons in 2D Hybrid Perovskite.

PubMed

Younts, Robert; Duan, Hsin-Sheng; Gautam, Bhoj; Saparov, Bayrammurad; Liu, Jie; Mongin, Cedric; Castellano, Felix N; Mitzi, David B; Gundogdu, Kenan

2017-03-01

Triplet excitons form in quasi-2D hybrid inorganic-organic perovskites and diffuse over 100 nm before radiating with >11% photoluminescence quantum efficiency (PLQE) at low temperatures. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hund's Multiplicity Rule Revisited

ERIC Educational Resources Information Center

Rioux, Frank

2007-01-01

The plausible and frequently used explanation of the singlet and triplet wave functions for a two-electron system is presented. Its findings reveal that the antisymmetric triplet spatial wave function keeps electrons apart, while the symmetric singlet spatial wave function permits electrons to be close together.

Controllable rogue waves in the nonautonomous nonlinear system with a linear potential

NASA Astrophysics Data System (ADS)

Dai, C. Q.; Zheng, C. L.; Zhu, H. P.

2012-04-01

Based on the similarity transformation connected the nonautonomous nonlinear Schrödinger equation with the autonomous nonlinear Schrödinger equation, we firstly derive self-similar rogue wave solutions (rational solutions) for the nonautonomous nonlinear system with a linear potential. Then, we investigate the controllable behaviors of one-rogue wave, two-rogue wave and rogue wave triplets in a soliton control system. Our results demonstrate that the propagation behaviors of rogue waves, including postpone, sustainment, recurrence and annihilation, can be manipulated by choosing the relation between the maximum value of the effective propagation distance Z m and the parameter Z 0. Moreover, the excitation time of controllable rogue waves is decided by the parameter T 0.

Towards a global model of spin-orbit coupling in the halocarbenes

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

Nyambo, Silver; Karshenas, Cyrus; Reid, Scott A., E-mail: scott.reid@marquette.edu, E-mail: dawesr@mst.edu

We report a global analysis of spin-orbit coupling in the mono-halocarbenes, CH(D)X, where X = Cl, Br, and I. These are model systems for examining carbene singlet-triplet energy gaps and spin-orbit coupling. Over the past decade, rich data sets collected using single vibronic level emission spectroscopy and stimulated emission pumping spectroscopy have yielded much information on the ground vibrational level structure and clearly demonstrated the presence of perturbations involving the low-lying triplet state. To model these interactions globally, we compare two approaches. First, we employ a diabatic treatment of the spin-orbit coupling, where the coupling matrix elements are written inmore » terms of a purely electronic spin-orbit matrix element which is independent of nuclear coordinates, and an integral representing the overlap of the singlet and triplet vibrational wavefunctions. In this way, the structures, harmonic frequencies, and normal mode displacements from ab initio calculations were used to calculate the vibrational overlaps of the singlet and triplet state levels, including the full effects of Duschinsky mixing. These calculations have allowed many new assignments to be made, particularly for CHI, and provided spin-orbit coupling parameters and values for the singlet-triplet gaps. In a second approach, we have computed and fit full geometry dependent spin-orbit coupling surfaces and used them to compute matrix elements without the product form approximation. Those matrix elements were used in similar fits varying the anharmonic constants and singlet-triplet gap to reproduce the experimental levels. The derived spin-orbit parameters for carbenes CHX (X = Cl, Br, and I) show an excellent linear correlation with the atomic spin-orbit constant of the corresponding halogen, indicating that the spin-orbit coupling in the carbenes is consistently around 14% of the atomic value.« less

Study of rare encounters in a membrane using quenching of cascade reaction between triplet and photochrome probes with nitroxide radicals.

PubMed

Medvedeva, Nataly; Papper, Vladislav; Likhtenshtein, Gertz I

2005-09-21

Measurements of active encounters between molecules in native membranes containing ingredients, including proteins, are of prime importance. To estimate rare encounters in a high range of rate constants (rate coefficients) and distances between interacting molecules in membranes, a cascade of photochemical reactions for molecules diffusing in multilamellar liposomes was investigated. The sensitised cascade triplet cis-trans photoisomerisation of the excited stilbene involves the use of a triplet sensitiser (Erythrosin B), a photochrome stilbene-derivative probe (4-dimethylamino-4'-aminostilbene) exhibiting the phenomenon of trans-cis photoisomerisation, and nitroxide radicals (5-doxyl stearic acid) to quench the excited triplet state of the sensitiser. Measurement of the phosphorescence lifetime of Erythrosin B and the fluorescence enhancement of the stilbene-derivative photochrome probe, at various concentrations of the nitroxide probe, made it possible to calculate the quenching rate constant k(q)= 1.1 x 10(15) cm2 M(-1) s(-1) and the rate constant of the triplet-triplet energy transfer between the sensitiser and stilbene probe k(T)= 1.0 x 10(12) cm2 M(-1) s(-1). These values, together with the data on diffusion rate constant, obtained by methods utilising various theoretical characteristic times of about seven orders of magnitude and the experimental rate constants of about five orders of magnitude, were found to be in good agreement with the advanced theory of diffusion-controlled reactions in two dimensions. Because the characteristic time of the proposed cascade method is relatively large (0.1 s), it is possible to follow rare collisions between molecules and free radicals in model and biological membranes with a very sensitive fluorescence spectroscopy technique, using a relatively low concentration of probes.

Spectral diffusion in poly(para-phenylene)-type polymers with different energetic disorder

NASA Astrophysics Data System (ADS)

Hoffmann, Sebastian T.; Bässler, Heinz; Koenen, Jan-Moritz; Forster, Michael; Scherf, Ullrich; Scheler, Esther; Strohriegl, Peter; Köhler, Anna

2010-03-01

We have employed quasicontinuous fluorescence and phosphorescence spectroscopy within a temperature range between 10 and 500 K to monitor the spectral diffusion of singlet and triplet excitons in a series of π -conjugated polymers. We investigated (i) how spectral diffusion is controlled by the degree of energetic disorder present in the amorphous film (that is reflected by the inhomogeneous broadening of the photoluminescence spectra) and (ii) how this process depends on the range of the electronic coupling (by comparing singlet exciton diffusion via long-range Förster transfer against triplet exciton diffusion by short-range Dexter transfer). For singlets, we find that the fluorescence spectra bear out a bathochromic shift upon cooling the sample down to a critical temperature below which the shift saturates. This bathochromic shift is a signature of spectral relaxation. Random-walk theory applied to excitation transport within a Gaussian density-of-states distribution is both necessary and sufficient to rationalize the experimental results in a quantitative fashion. The same behavior is observed for triplets in weakly disordered systems, such as in a polymer containing platinum in the main chain and a ladder-type polyphenylene. In contrast we observe a hypsochromic shift of the phosphorescence spectra below a characteristic temperature for triplets in systems with at least moderate energetic disorder. The hypsochromic shift proves that triplet exciton relaxation becomes frustrated because thermally activated exciton jumps that otherwise promote spectral diffusion become progressively frozen out. The frustration effect is controlled by the jump distance and thus it is specific for triplet excitations that migrate via short-range coupling among strongly localized states as compared to singlet excitons.

Photochemistry of furyl- and thienyldiazomethanes: spectroscopic characterization of triplet 3-thienylcarbene.

PubMed

Pharr, Caroline R; Kopff, Laura A; Bennett, Brian; Reid, Scott A; McMahon, Robert J

2012-04-11

Photolysis (λ > 543 nm) of 3-thienyldiazomethane (1), matrix isolated in Ar or N(2) at 10 K, yields triplet 3-thienylcarbene (13) and α-thial-methylenecyclopropene (9). Carbene 13 was characterized by IR, UV/vis, and EPR spectroscopy. The conformational isomers of 3-thienylcarbene (s-E and s-Z) exhibit an unusually large difference in zero-field splitting parameters in the triplet EPR spectrum (|D/hc| = 0.508 cm(-1), |E/hc| = 0.0554 cm(-1); |D/hc| = 0.579 cm(-1), |E/hc| = 0.0315 cm(-1)). Natural Bond Orbital (NBO) calculations reveal substantially differing spin densities in the 3-thienyl ring at the positions adjacent to the carbene center, which is one factor contributing to the large difference in D values. NBO calculations also reveal a stabilizing interaction between the sp orbital of the carbene carbon in the s-Z rotamer of 13 and the antibonding σ orbital between sulfur and the neighboring carbon-an interaction that is not observed in the s-E rotamer of 13. In contrast to the EPR spectra, the electronic absorption spectra of the rotamers of triplet 3-thienylcarbene (13) are indistinguishable under our experimental conditions. The carbene exhibits a weak electronic absorption in the visible spectrum (λ(max) = 467 nm) that is characteristic of triplet arylcarbenes. Although studies of 2-thienyldiazomethane (2), 3-furyldiazomethane (3), or 2-furyldiazomethane (4) provided further insight into the photochemical interconversions among C(5)H(4)S or C(5)H(4)O isomers, these studies did not lead to the spectroscopic detection of the corresponding triplet carbenes (2-thienylcarbene (11), 3-furylcarbene (23), or 2-furylcarbene (22), respectively). © 2012 American Chemical Society

Zeaxanthin Protects Plant Photosynthesis by Modulating Chlorophyll Triplet Yield in Specific Light-harvesting Antenna Subunits*

PubMed Central

Dall'Osto, Luca; Holt, Nancy E.; Kaligotla, Shanti; Fuciman, Marcel; Cazzaniga, Stefano; Carbonera, Donatella; Frank, Harry A.; Alric, Jean; Bassi, Roberto

2012-01-01

Plants are particularly prone to photo-oxidative damage caused by excess light. Photoprotection is essential for photosynthesis to proceed in oxygenic environments either by scavenging harmful reactive intermediates or preventing their accumulation to avoid photoinhibition. Carotenoids play a key role in protecting photosynthesis from the toxic effect of over-excitation; under excess light conditions, plants accumulate a specific carotenoid, zeaxanthin, that was shown to increase photoprotection. In this work we genetically dissected different components of zeaxanthin-dependent photoprotection. By using time-resolved differential spectroscopy in vivo, we identified a zeaxanthin-dependent optical signal characterized by a red shift in the carotenoid peak of the triplet-minus-singlet spectrum of leaves and pigment-binding proteins. By fractionating thylakoids into their component pigment binding complexes, the signal was found to originate from the monomeric Lhcb4–6 antenna components of Photosystem II and the Lhca1–4 subunits of Photosystem I. By analyzing mutants based on their sensitivity to excess light, the red-shifted triplet-minus-singlet signal was tightly correlated with photoprotection in the chloroplasts, suggesting the signal implies an increased efficiency of zeaxanthin in controlling chlorophyll triplet formation. Fluorescence-detected magnetic resonance analysis showed a decrease in the amplitude of signals assigned to chlorophyll triplets belonging to the monomeric antenna complexes of Photosystem II upon zeaxanthin binding; however, the amplitude of carotenoid triplet signal does not increase correspondingly. Results show that the high light-induced binding of zeaxanthin to specific proteins plays a major role in enhancing photoprotection by modulating the yield of potentially dangerous chlorophyll-excited states in vivo and preventing the production of singlet oxygen. PMID:23066020

Bright triplet excitons in caesium lead halide perovskites

NASA Astrophysics Data System (ADS)

Becker, Michael A.; Vaxenburg, Roman; Nedelcu, Georgian; Sercel, Peter C.; Shabaev, Andrew; Mehl, Michael J.; Michopoulos, John G.; Lambrakos, Samuel G.; Bernstein, Noam; Lyons, John L.; Stöferle, Thilo; Mahrt, Rainer F.; Kovalenko, Maksym V.; Norris, David J.; Rainò, Gabriele; Efros, Alexander L.

2018-01-01

Nanostructured semiconductors emit light from electronic states known as excitons. For organic materials, Hund’s rules state that the lowest-energy exciton is a poorly emitting triplet state. For inorganic semiconductors, similar rules predict an analogue of this triplet state known as the ‘dark exciton’. Because dark excitons release photons slowly, hindering emission from inorganic nanostructures, materials that disobey these rules have been sought. However, despite considerable experimental and theoretical efforts, no inorganic semiconductors have been identified in which the lowest exciton is bright. Here we show that the lowest exciton in caesium lead halide perovskites (CsPbX3, with X = Cl, Br or I) involves a highly emissive triplet state. We first use an effective-mass model and group theory to demonstrate the possibility of such a state existing, which can occur when the strong spin-orbit coupling in the conduction band of a perovskite is combined with the Rashba effect. We then apply our model to CsPbX3 nanocrystals, and measure size- and composition-dependent fluorescence at the single-nanocrystal level. The bright triplet character of the lowest exciton explains the anomalous photon-emission rates of these materials, which emit about 20 and 1,000 times faster than any other semiconductor nanocrystal at room and cryogenic temperatures, respectively. The existence of this bright triplet exciton is further confirmed by analysis of the fine structure in low-temperature fluorescence spectra. For semiconductor nanocrystals, which are already used in lighting, lasers and displays, these excitons could lead to materials with brighter emission. More generally, our results provide criteria for identifying other semiconductors that exhibit bright excitons, with potential implications for optoelectronic devices.

Efficacy and safety of olanzapine combined with aprepitant, palonosetron, and dexamethasone for preventing nausea and vomiting induced by cisplatin-based chemotherapy in gynecological cancer: KCOG-G1301 phase II trial.

PubMed

Abe, Masakazu; Hirashima, Yasuyuki; Kasamatsu, Yuka; Kado, Nobuhiro; Komeda, Satomi; Kuji, Shiho; Tanaka, Aki; Takahashi, Nobutaka; Takekuma, Munetaka; Hihara, Hanako; Ichikawa, Yoshikazu; Itonaga, Yui; Hirakawa, Tomoko; Nasu, Kaei; Miyagi, Kanoko; Murakami, Junko; Ito, Kimihiko

2016-02-01

Olanzapine is effective in chemotherapy-induced nausea and vomiting (CINV). In patients receiving highly emetogenic chemotherapy (HEC), its efficacy was reported as rescue therapy for breakthrough emesis refractory to triplet therapy (palonosetron, aprepitant, and dexamethasone). However, its preventive effects with triplet therapy for CINV are unknown. This study aimed to investigate efficacy and safety of preventive use of olanzapine with triplet therapy for CINV of HEC. This study is a prospective multicenter study conducted by Kansai Clinical Oncology Group. Forty chemo-naïve gynecological cancer patients receiving HEC with cisplatin (≥50 mg/m(2)) were enrolled. Oral olanzapine (5 mg) was administered with triplet therapy a day prior to cisplatin administration and on days 1-5. The primary endpoint was complete response (no vomiting and no rescue) rate for the overall phase (0-120 h post-chemotherapy). Secondary endpoints were complete response rate for acute phase (0-24 h post-chemotherapy) and delayed phase (24-120 h post-chemotherapy) and complete control (no vomiting, no rescue, and no significant nausea) rate and total control (no vomiting, no rescue, and no nausea) rate for each phase. These endpoints were evaluated during the first cycle of chemotherapy. Complete response rates for acute, delayed, and overall phases were 97.5, 95.0, and 92.5 %, respectively. Complete control rates were 92.5, 87.5, and 82.5 %, respectively. Total control rates were 87.5, 67.5, and 67.5 %, respectively. There were no grade 3 or 4 adverse events. Preventive use of olanzapine combined with triplet therapy gives better results than those from previously reported studies of triplet therapy.

Twin and Triplet Drugs in Opioid Research

NASA Astrophysics Data System (ADS)

Fujii, Hideaki

Twin and triplet drugs are defined as compounds that contain respectively two and three pharmacophore components exerting pharmacological effects in a molecule. The twin drug bearing the same pharmacophores is a "symmetrical twin drug", whereas that possessing different pharmacophores is a "nonsymmetrical twin drug." In general, the symmetrical twin drug is expected to produce more potent and/or selective pharmacological effects, whereas the nonsymmetrical twin drug is anticipated to show both pharmacological activities stemming from the individual pharmacophores (dual action). On the other hand, nonsymmetrical triplet drugs, which have two of the same pharmacophores and one different moiety, are expected to elicit both increased pharmacological action and dual action. The two identical portions could bind the same receptor sites simultaneously while the third portion could bind a different receptor site or enzyme. This review will mainly focus on the twin and triplet drugs with an evaluation of their in vivo pharmacological effects, and will also include a description of their pharmacology and synthesis.

Thermal transport in topological-insulator-based superconducting hybrid structures with mixed singlet and triplet pairing states.

PubMed

Li, Hai; Zhao, Yuan Yuan

2017-11-22

In the framework of the Bogoliubov-de Gennes equation, we investigate the thermal transport properties in topological-insulator-based superconducting hybrid structures with mixed spin-singlet and spin-triplet pairing states, and emphasize the different manifestations of the spin-singlet and spin-triplet pairing states in the thermal transport signatures. It is revealed that the temperature-dependent differential thermal conductance strongly depends on the components of the pairing state, and the negative differential thermal conductance only occurs in the spin-singlet pairing state dominated regime. It is also found that the thermal conductance is profoundly sensitive to the components of the pairing state. In the spin-singlet pairing state controlled regime, the thermal conductance obviously oscillates with the phase difference and junction length. With increasing the proportion of the spin-triplet pairing state, the oscillating characteristic of the thermal conductance fades out distinctly. These results suggest an alternative route for distinguishing the components of pairing states in topological-insulator-based superconducting hybrid structures.

Polaron pair mediated triplet generation in polymer/fullerene blends

PubMed Central

Dimitrov, Stoichko D.; Wheeler, Scot; Niedzialek, Dorota; Schroeder, Bob C.; Utzat, Hendrik; Frost, Jarvist M.; Yao, Jizhong; Gillett, Alexander; Tuladhar, Pabitra S.; McCulloch, Iain; Nelson, Jenny; Durrant, James R.

2015-01-01

Electron spin is a key consideration for the function of organic semiconductors in light-emitting diodes and solar cells, as well as spintronic applications relying on organic magnetoresistance. A mechanism for triplet excited state generation in such systems is by recombination of electron-hole pairs. However, the exact charge recombination mechanism, whether geminate or nongeminate and whether it involves spin-state mixing is not well understood. In this work, the dynamics of free charge separation competing with recombination to polymer triplet states is studied in two closely related polymer-fullerene blends with differing polymer fluorination and photovoltaic performance. Using time-resolved laser spectroscopic techniques and quantum chemical calculations, we show that lower charge separation in the fluorinated system is associated with the formation of bound electron-hole pairs, which undergo spin-state mixing on the nanosecond timescale and subsequent geminate recombination to triplet excitons. We find that these bound electron-hole pairs can be dissociated by electric fields. PMID:25735188

Renormalization of the Higgs sector in the triplet model

NASA Astrophysics Data System (ADS)

Aoki, Mayumi; Kanemura, Shinya; Kikuchi, Mariko; Yagyu, Kei

2012-08-01

We study radiative corrections to the mass spectrum and the triple Higgs boson coupling in the model with an additional Y = 1 triplet field. In this model, the vacuum expectation value for the triplet field is strongly constrained from the electroweak precision data, under which characteristic mass spectrum appear at the tree level; i.e., mH++2 - mH+2 ≃ mH+2 - mA2 and mA2 ≃ mH2, where the CP-even (H), the CP-odd (A) and the doubly-charged (H±±) as well as the singly-charged (H±) Higgs bosons are the triplet-like. We evaluate how the tree-level formulae are modified at the one-loop level. The hhh coupling for the standard model-like Higgs boson (h) is also calculated at the one-loop level. One-loop corrections to these quantities can be large enough for identification of the model by future precision data at the LHC or the International Linear Collider.

Formation of Triplet Positron-helium Bound State by Stripping of Positronium Atoms in Collision with Ground State Helium

NASA Technical Reports Server (NTRS)

Drachman, Richard J.

2006-01-01

Formation of triplet positron-helium bound state by stripping of positronium atoms in collision with ground state helium JOSEPH DI RlENZI, College of Notre Dame of Maryland, RICHARD J. DRACHMAN, NASA/Goddard Space Flight Center - The system consisting of a positron and a helium atom in the triplet state e(+)He(S-3)(sup e) was conjectured long ago to be stable [1]. Its stability has recently been established rigorously [2], and the values of the energies of dissociation into the ground states of Ps and He(+) have also been reported [3] and [4]. We have evaluated the cross-section for this system formed by radiative attachment of a positron in triplet He state and found it to be small [5]. The mechanism of production suggested here should result in a larger cross-section (of atomic size) which we are determining using the Born approximation with simplified initial and final wave functions.

The interaction of the excited states of safranine-O with low generation carboxyl terminated PAMAM dendrimers in an aqueous medium.

PubMed

Militello, M Paula; Altamirano, Marcela S; Bertolotti, Sonia G; Previtali, Carlos M

2018-05-16

The interaction of the singlet and triplet excited states of the synthetic dye safranine-O with carboxyl-terminated poly(amidoamine) (PAMAM) dendrimers was investigated in a buffer solution at pH 8. Low half-generation PAMAM dendrimers (G -0.5; G +0.5: G 1.5) were employed. The UV-vis absorption spectrum of the dye presents only a very small red shift in the presence of dendrimers. Fluorescence quenching was detected and it was interpreted by a static mechanism in terms of the association of the dye with the dendrimer. Laser flash photolysis experiments were carried out and transient absorption spectra of the triplet and radicals were obtained. The triplet state is quenched by the dendrimers with rate constants well below the diffusional limit. The quenching process was characterized as an electron transfer process and the quantum yield of radicals was estimated. It was found that radicals are formed with a high efficiency in the triplet quenching reaction.

Minimum triplet covers of binary phylogenetic X-trees.

PubMed

Huber, K T; Moulton, V; Steel, M

2017-12-01

Trees with labelled leaves and with all other vertices of degree three play an important role in systematic biology and other areas of classification. A classical combinatorial result ensures that such trees can be uniquely reconstructed from the distances between the leaves (when the edges are given any strictly positive lengths). Moreover, a linear number of these pairwise distance values suffices to determine both the tree and its edge lengths. A natural set of pairs of leaves is provided by any 'triplet cover' of the tree (based on the fact that each non-leaf vertex is the median vertex of three leaves). In this paper we describe a number of new results concerning triplet covers of minimum size. In particular, we characterize such covers in terms of an associated graph being a 2-tree. Also, we show that minimum triplet covers are 'shellable' and thereby provide a set of pairs for which the inter-leaf distance values will uniquely determine the underlying tree and its associated branch lengths.

Does the concept of Clar's aromatic sextet work for dicationic forms of polycyclic aromatic hydrocarbons?--testing the model against charged systems in singlet and triplet states.

PubMed

Dominikowska, Justyna; Palusiak, Marcin

2011-07-07

The concept of Clar's π-electron aromatic sextet was tested against a set of polycyclic aromatic hydrocarbons in neutral and doubly charged forms. Systems containing different types of rings (in the context of Clar's concept) were chosen, including benzene, naphthalene, anthracene, phenanthrene and triphenylene. In the case of dicationic structures both singlet and triplet states were considered. It was found that for singlet state dicationic structures the concept of aromatic sextet could be applied and the local aromaticity could be discussed in the context of that model, whereas in the case of triplet state dicationic structures Clar's model rather failed. Different aromaticity indices based on various properties of molecular systems were applied for the purpose of the studies. The discussion about the interdependence between the values of different aromaticity indices applied to neutral and charged systems in singlet and triplet states is also included. This journal is © the Owner Societies 2011

Measurement of the dipole moments of excited states and photochemical transients by microwave dielectric absorption

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

Fessenden, R.W.; Carton, P.M.; Shimamori, H.

1982-09-16

Time-resolved changes in microwave dielectric absorption have been used to study transients formed by laser flash photolysis. Details of the method and apparatus are given. Applications both to the measurements of the dipole moments of transients and to decay kinetics are given. The dipole moments of the lowest triplet states of a number of aromatic compounds (mostly ketones) have been measured in benzene solution at room temperature. States of n..pi..* character generally possess smaller dipole moments than the corresponding ground states while states of ..pi pi..* character (for example, fluorenone) have larger values than the ground state. The triplets ofmore » 4-(dimethylamino)benzaldehyde and 4,4'-bis(dimethylamino)benzophenone have rather high values of dipole moment (10.5 and 8.4 D, respectively) showing their charge-transfer character. The triplet state of benzil was found to have zero or near-zero dipole moment, thus confirming that the triplet state is of a transstructure. 7 figures, 1 table.« less

Accurate adiabatic singlet-triplet gaps in atoms and molecules employing the third-order spin-flip algebraic diagrammatic construction scheme for the polarization propagator

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

Lefrancois, Daniel; Dreuw, Andreas, E-mail: dreuw@uni-heidelberg.de; Rehn, Dirk R.

For the calculation of adiabatic singlet-triplet gaps (STG) in diradicaloid systems the spin-flip (SF) variant of the algebraic diagrammatic construction (ADC) scheme for the polarization propagator in third order perturbation theory (SF-ADC(3)) has been applied. Due to the methodology of the SF approach the singlet and triplet states are treated on an equal footing since they are part of the same determinant subspace. This leads to a systematically more accurate description of, e.g., diradicaloid systems than with the corresponding non-SF single-reference methods. Furthermore, using analytical excited state gradients at ADC(3) level, geometry optimizations of the singlet and triplet states weremore » performed leading to a fully consistent description of the systems, leading to only small errors in the calculated STGs ranging between 0.6 and 2.4 kcal/mol with respect to experimental references.« less

A first detection of singlet to triplet conversion from the 1 1B u- to the 1 3A g state and triplet internal conversion from the 1 3A g to the 1 3B u state in carotenoids: dependence on the conjugation length

NASA Astrophysics Data System (ADS)

Rondonuwu, Ferdy S.; Watanabe, Yasutaka; Fujii, Ritsuko; Koyama, Yasushi

2003-07-01

Subpicosecond time-resolved absorption spectra were recorded in the visible region for a set of photosynthetic carotenoids having different numbers of conjugated double bonds ( n), which include neurosporene ( n=9), spheroidene ( n=10), lycopene ( n=11), anhydrorhodovibrin ( n=12) and spirilloxanthin ( n=13). Singular-value decomposition and global fitting of the spectral-data matrices lead us to a branched relaxation scheme including both (1) the singlet internal conversion in the sequence of 1 1B u+ → 1 1B u- → 2 1A g- → 1 1A g-(ground), and (2) the singlet-to-triplet conversion of 1 1B u- → 1 3A g followed by triplet internal conversion of 1 3A g → 1 3B u.

Exploring the hyperchargeless Higgs triplet model up to the Planck scale

NASA Astrophysics Data System (ADS)

Khan, Najimuddin

2018-04-01

We examine an extension of the SM Higgs sector by a Higgs triplet taking into consideration the discovery of a Higgs-like particle at the LHC with mass around 125 GeV. We evaluate the bounds on the scalar potential through the unitarity of the scattering matrix. Considering the cases with and without Z_2-symmetry of the extra triplet, we derive constraints on the parameter space. We identify the region of the parameter space that corresponds to the stability and metastability of the electroweak vacuum. We also show that at large field values the scalar potential of this model is suitable to explain inflation.

Quantum Yield of Cyclobutane Pyrimidine Dimer Formation Via the Triplet Channel Determined by Photosensitization.

PubMed

Liu, Lizhe; Pilles, Bert M; Gontcharov, Julia; Bucher, Dominik B; Zinth, Wolfgang

2016-01-21

UV-induced formation of the cyclobutane pyrimidine dimer (CPD) lesion is investigated by stationary and time-resolved photosensitization experiments. The photosensitizer 2'-methoxyacetophenone with high intersystem crossing efficiency and large absorption cross-section in the UV-A range was used. A diffusion controlled reaction model is presented. Time-resolved experiments confirmed the validity of the reaction model and provided information on the dynamics of the triplet sensitization process. With a series of concentration dependent stationary illumination experiments, we determined the quantum efficiency for CPD formation from the triplet state of the thymine dinucleotide TpT to be 4 ± 0.2%.

Sequence specificity of the hammerhead ribozyme revisited; the NHH rule.

PubMed Central

Kore, A R; Vaish, N K; Kutzke, U; Eckstein, F

1998-01-01

The sequence specificity of hammerhead ribozyme cleavage has been re-evaluated with respect to the NUH rule. Contrary to previous reports it was found that substrates with GAC triplets were also cleaved. This was established in three different sequence contexts. The rate of cleavage under single turnover conditions was between 3 and 7% that of cleavage 3' of GUC. Specificity of cleavage of substrates containing a central A in the cleavable triplet can be described as NAH, where N can be any nucleotide and H any nucleotide but G. As cleavage 3' of NCH triplets has recently been described, the NUH rule can be reformulated to NHH. PMID:9722629

The protective effect of salicylic acid on lysozyme against riboflavin-mediated photooxidation

NASA Astrophysics Data System (ADS)

Li, Kun; Wang, Hongbao; Cheng, Lingli; Zhu, Hui; Wang, Mei; Wang, Shi-Long

2011-06-01

As a metabolite of aspirin in vivo, salicylic acid was proved to protect lysozyme from riboflavin-mediated photooxidation in this study. The antioxidative properties of salicylic acid were further studied by using time-resolved laser flash photolysis of 355 nm. It can quench the triplet state of riboflavin via electron transfer from salicylic acid to the triplet state of riboflavin with a reaction constant of 2.25 × 10 9 M -1 s -1. Mechanism of antioxidant activities of salicylic acid on lysozyme oxidation was discussed. Salicylic acid can serve as a potential antioxidant to quench the triplet state of riboflavin and reduce oxidative pressure.

Photophysical properties of hexyl diethylaminohydroxybenzoylbenzoate (Uvinul A Plus), a UV-A absorber.

PubMed

Shamoto, Yuta; Yagi, Mikio; Oguchi-Fujiyama, Nozomi; Miyazawa, Kazuyuki; Kikuchi, Azusa

2017-09-13

Hexyl diethylaminohydroxybenzoylbenzoate (DHHB, Uvinul A Plus) is a photostable UV-A absorber. The photophysical properties of DHHB have been studied by obtaining the transient absorption, total emission, phosphorescence and electron paramagnetic resonance spectra. DHHB exhibits an intense phosphorescence in a hydrogen-bonding solvent (e.g., ethanol) at 77 K, whereas it is weakly phosphorescent in a non-hydrogen-bonding solvent (e.g., 3-methylpentane). The triplet-triplet absorption and EPR spectra for the lowest excited triplet state of DHHB were observed in ethanol, while they were not observed in 3-methylpentane. These results are explained by the proposal that in the benzophenone derivatives possessing an intramolecular hydrogen bond, intramolecular proton transfer is an efficient mechanism of the very fast radiationless decay from the excited singlet state. The energy level of the lowest excited triplet state of DHHB is higher than those of the most widely used UV-B absorbers, octyl methoxycinnamate (OMC) and octocrylene (OCR). DHHB may act as a triplet energy donor for OMC and OCR in the mixtures of UV-A and UV-B absorbers. The bimolecular rate constant for the quenching of singlet oxygen by DHHB was determined by measuring the near-IR phosphorescence of singlet oxygen. The photophysical properties of diethylaminohydroxybenzoylbenzoic acid (DHBA) have been studied for comparison. It is a closely related building block to assist in interpreting the observed data.

Local CC2 response method for triplet states based on Laplace transform: excitation energies and first-order properties.

PubMed

Freundorfer, Katrin; Kats, Daniel; Korona, Tatiana; Schütz, Martin

2010-12-28

A new multistate local CC2 response method for calculating excitation energies and first-order properties of excited triplet states in extended molecular systems is presented. The Laplace transform technique is employed to partition the left/right local CC2 eigenvalue problems as well as the linear equations determining the Lagrange multipliers needed for the properties. The doubles part in the equations can then be inverted on-the-fly and only effective equations for the singles part must be solved iteratively. The local approximation presented here is adaptive and state-specific. The density-fitting method is utilized to approximate the electron-repulsion integrals. The accuracy of the new method is tested by comparison to canonical reference values for a set of 12 test molecules and 62 excited triplet states. As an illustrative application example, the lowest four triplet states of 3-(5-(5-(4-(bis(4-(hexyloxy)phenyl)amino)phenyl)thiophene-2-yl)thiophene-2-yl)-2-cyanoacrylic acid, an organic sensitizer for solar-cell applications, are computed in the present work. No triplet charge-transfer states are detected among these states. This situation contrasts with the singlet states of this molecule, where the lowest singlet state has been recently found to correspond to an excited state with a pronounced charge-transfer character having a large transition strength.

Magnetoanisotropic spin-triplet Andreev reflection in ferromagnet-Ising superconductor junctions

NASA Astrophysics Data System (ADS)

Lv, Peng; Zhou, Yan-Feng; Yang, Ning-Xuan; Sun, Qing-Feng

2018-04-01

We theoretically study the electronic transport through a ferromagnet-Ising superconductor junction. A tight-binding Hamiltonian describing the Ising superconductor is presented. Then by combining the nonequilibrium Green's function method, the expressions of Andreev reflection coefficient and conductance are obtained. A strong magnetoanisotropic spin-triplet Andreev reflection is shown, and the magnetoanisotropic period is π instead of 2 π as in the conventional magnetoanisotropic system. We demonstrate a significant increase of the spin-triplet Andreev reflection for the single-band Ising superconductor. Furthermore, the dependence of the Andreev reflection on the incident energy and incident angle are also investigated. A complete Andreev reflection can occur when the incident energy is equal to the superconducting gap, regardless of the Fermi energy (spin polarization) of the ferromagnet. For the suitable oblique incidence, the spin-triplet Andreev reflection can be strongly enhanced. In addition, the conductance spectroscopies of both zero bias and finite bias are studied, and the influence of gate voltage, exchange energy, and spin-orbit coupling on the conductance spectroscopy are discussed in detail. The conductance exhibits a strong magnetoanisotropy with period π as the Andreev reflection coefficient. When the magnetization direction is parallel to the junction plane, a large conductance peak always emerges at the superconducting gap. This work offers a comprehensive and systematic study of the spin-triplet Andreev reflection and has an underlying application of π -periodic spin valve in spintronics.

Translational initiation in Leishmania tarentolae and Phytomonas serpens (Kinetoplastida) is strongly influenced by pre-ATG triplet and its 5' sequence context.

PubMed

Lukes, Julius; Paris, Zdenek; Regmi, Sandesh; Breitling, Reinhard; Mureev, Sergey; Kushnir, Susanna; Pyatkov, Konstantin; Jirků, Milan; Alexandrov, Kirill A

2006-08-01

To investigate the influence of sequence context of translation initiation codon on translation efficiency in Kinetoplastida, we constructed a library of expression plasmids randomized in the three nucleotides prefacing ATG of a reporter gene encoding enhanced green fluorescent protein (EGFP). All 64 possible combinations of pre-ATG triplets were individually stably integrated into the rDNA locus of Leishmania tarentolae and the resulting cell lines were assessed for EGFP expression. The expression levels were quantified directly by measuring the fluorescence of EGFP protein in living cells and confirmed by Western blotting. We observed a strong influence of the pre-ATG triplet on the level of protein expression over a 20-fold range. To understand the degree of evolutionary conservation of the observed effect, we transformed Phytomonas serpens, a trypanosomatid parasite of plants, with a subset of the constructs. The pattern of translational efficiency mediated by individual pre-ATG triplets in this species was similar to that observed in L. tarentolae. However, the pattern of translational efficiency of two other proteins (red fluorescent protein and tetracycline repressor) containing selected pre-ATG triplets did not correlate with either EGFP or each other. Thus, we conclude that a conserved mechanism of translation initiation site selection exists in kinetoplastids that is strongly influenced not only by the pre-ATG sequences but also by the coding region of the gene.

Relative Pose Estimation Using Image Feature Triplets

NASA Astrophysics Data System (ADS)

Chuang, T. Y.; Rottensteiner, F.; Heipke, C.

2015-03-01

A fully automated reconstruction of the trajectory of image sequences using point correspondences is turning into a routine practice. However, there are cases in which point features are hardly detectable, cannot be localized in a stable distribution, and consequently lead to an insufficient pose estimation. This paper presents a triplet-wise scheme for calibrated relative pose estimation from image point and line triplets, and investigates the effectiveness of the feature integration upon the relative pose estimation. To this end, we employ an existing point matching technique and propose a method for line triplet matching in which the relative poses are resolved during the matching procedure. The line matching method aims at establishing hypotheses about potential minimal line matches that can be used for determining the parameters of relative orientation (pose estimation) of two images with respect to the reference one; then, quantifying the agreement using the estimated orientation parameters. Rather than randomly choosing the line candidates in the matching process, we generate an associated lookup table to guide the selection of potential line matches. In addition, we integrate the homologous point and line triplets into a common adjustment procedure. In order to be able to also work with image sequences the adjustment is formulated in an incremental manner. The proposed scheme is evaluated with both synthetic and real datasets, demonstrating its satisfactory performance and revealing the effectiveness of image feature integration.

Can Baird's and Clar's Rules Combined Explain Triplet State Energies of Polycyclic Conjugated Hydrocarbons with Fused 4nπ- and (4n + 2)π-Rings?

PubMed

Ayub, Rabia; Bakouri, Ouissam El; Jorner, Kjell; Solà, Miquel; Ottosson, Henrik

2017-06-16

Compounds that can be labeled as "aromatic chameleons" are π-conjugated compounds that are able to adjust their π-electron distributions so as to comply with the different rules of aromaticity in different electronic states. We used quantum chemical calculations to explore how the fusion of benzene rings onto aromatic chameleonic units represented by biphenylene, dibenzocyclooctatetraene, and dibenzo[a,e]pentalene modifies the first triplet excited states (T 1 ) of the compounds. Decreases in T 1 energies are observed when going from isomers with linear connectivity of the fused benzene rings to those with cis- or trans-bent connectivities. The T 1 energies decreased down to those of the parent (isolated) 4nπ-electron units. Simultaneously, we observe an increased influence of triplet state aromaticity of the central 4n ring as given by Baird's rule and evidenced by geometric, magnetic, and electron density based aromaticity indices (HOMA, NICS-XY, ACID, and FLU). Because of an influence of triplet state aromaticity in the central 4nπ-electron units, the most stabilized compounds retain the triplet excitation in Baird π-quartets or octets, enabling the outer benzene rings to adapt closed-shell singlet Clar π-sextet character. Interestingly, the T 1 energies go down as the total number of aromatic cycles within a molecule in the T 1 state increases.

The NIR Ca ii triplet at low metallicity. Searching for extremely low-metallicity stars in classical dwarf galaxies

NASA Astrophysics Data System (ADS)

Starkenburg, E.; Hill, V.; Tolstoy, E.; González Hernández, J. I.; Irwin, M.; Helmi, A.; Battaglia, G.; Jablonka, P.; Tafelmeyer, M.; Shetrone, M.; Venn, K.; de Boer, T.

2010-04-01

The NIR Ca ii triplet absorption lines have proven to be an important tool for quantitative spectroscopy of individual red giant branch stars in the Local Group, providing a better understanding of metallicities of stars in the Milky Way and dwarf galaxies and thereby an opportunity to constrain their chemical evolution processes. An interesting puzzle in this field is the significant lack of extremely metal-poor stars, below [Fe/H] = -3, found in classical dwarf galaxies around the Milky Way using this technique. The question arises whether these stars are really absent, or if the empirical Ca ii triplet method used to study these systems is biased in the low-metallicity regime. Here we present results of synthetic spectral analysis of the Ca ii triplet, that is focused on a better understanding of spectroscopic measurements of low-metallicity giant stars. Our results start to deviate strongly from the widely-used and linear empirical calibrations at [Fe/H] < -2. We provide a new calibration for Ca ii triplet studies which is valid for -0.5 ≥ [Fe/H] ≥ -4. We subsequently apply this new calibration to current data sets and suggest that the classical dwarf galaxies are not so devoid of extremely low-metallicity stars as was previously thought. Using observations collected at the European Organisation for Astronomical Research in the Southern Hemisphere, Chile proposal 171.B-0588.

Density Functional Theory and ab Initio Computational Evidence for Nitrosamine Photoperoxides: Hammett Substituent Effects in the Photogeneration of the Nitrooxide Intermediate.

PubMed

Greer, Edyta M; Kwon, Kitae

2018-05-20

Little attention has been focused on diradical and zwitterionic photoperoxides formed from nitrosamine compounds. Here, an attempt is made to probe the electronic character of the nitrooxide intermediate formed in photochemical reactions with triplet oxygen ( 3 O 2 ). Theoretical studies have been conducted to screen para-substituted phenyl nitrosamines. In particular, we find that electron-withdrawing substituents produce low-lying triplet nitrooxide diradicals. A clear electronic dependence in the S 0 - T 1 and S 0 - S 1 energy gaps of nitrooxides was found using Hammett plots. Computed geometries show a twisted diradical triplet nitrooxide moiety, which contrasts to the nearly flat singlet zwitterionic ground-state nitrooxide moiety; analyses of charges (natural bond order), molecular orbitals (HOMO/LUMO), and spin densities enable these assignments. Calculations predict the former triplet species is photogenerated initially from nitrosamine with O 2 . The conversion of the triplet nitrooxide diradical to the singlet ground state is an example where longer-lived zwitterionic nitrooxide structures become possible. The reaction mechanism is consistent with a zwitterionic ground-state nitrooxide playing an important role in the bimolecular oxygen-transfer reaction with phosphine and phosphite trapping agents as has been observed experimentally. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

Doped luminescent materials and particle discrimination using same

DOEpatents

Doty, F. Patrick; Allendorf, Mark D; Feng, Patrick L

2014-10-07

Doped luminescent materials are provided for converting excited triplet states to radiative hybrid states. The doped materials may be used to conduct pulse shape discrimination (PSD) using luminescence generated by harvested excited triplet states. The doped materials may also be used to detect particles using spectral shape discrimination (SSD).

One Interesting Family of Diophantine Triplets

ERIC Educational Resources Information Center

Deshpande, M. N.

2002-01-01

In this note properties of two sequences generated by the recurrence relation G[subscript n] +2 = 4 G[subscript n] +1 - G[subscript n], are studied. It is shown that one of the sequences leads to a family of diophantine triplets. Some interesting properties of these sequences are also established.

A Versatile Molecular Design for High-Performance Nondoped OLEDs with ~100% Exciton Utilization and Negligible Efficiency Roll-Off.

PubMed

Liu, Huijun; Zeng, Jiajie; Guo, Jingjing; Nie, Han; Zhao, Zujin; Tang, Ben Zhong

2018-06-01

Nondoped organic light-emitting diodes (OLEDs) possess merits of higher stability and easier fabrication than doped devices. However, luminescent materials with high exciton utilization are generally unsuitable for nondoped OLEDs because of severe emission quenching and exciton annihilation in neat films. Herein, we wish to report a novel molecular design of integrating aggregation-induced delayed fluorescence (AIDF) moiety within host materials to explore efficient luminogens for nondoped OLEDs. By grafting 4-(phenoxazin-10-yl)benzoyl to common host materials, we develop a series of new luminescent materials with prominent AIDF property. Their neat films fluoresce strongly and can fully harvest both singlet and triplet excitons with suppressed exciton annihilation. Nondoped OLEDs of these AIDF luminogens exhibit excellent luminance (~100000 cd m-2), outstanding external quantum efficiencies (22.1-22.6%), negligible efficiency roll-off and improved operational stability. To the best of our knowledge, these are the most efficient nondoped OLEDs reported so far. This convenient and versatile molecular design is of high significance for the advance of nondoped OLEDs. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Remote modulation of singlet-triplet gaps in carbenes

NASA Astrophysics Data System (ADS)

Alkorta, Ibon; Montero-Campillo, M. Merced; Elguero, José

2018-02-01

The modulation of the singlet-triplet (S/T) gap of phenyl-carbene derivatives by hydrogen bond formation has been studied using the G4(MP2) computational method. The complexation of the aromatic ring substituents (-NH2, -OH, -PH2, -SH) in meta- and para-positions with water and the protonation or deprotonation of such groups have a remarkable influence on the S/T gaps, reaching S/T gap variations from 25.7 to 93.7 kJ mol-1. This variation is linearly related to the binding energy difference of the S/T configurations. Importantly, the triplet and singlet electronic configurations are systematically favored in the protonated and deprotonated forms, respectively, in all cases.

Phototautomerization of 3-hydroxyflavone in the lowest triplet state

NASA Astrophysics Data System (ADS)

Tokumura, Kunihiro; Kurauchi, Mutsuo; Yagata, Nobuo; Itoh, Michiya

1996-08-01

Selective excitation of benzil in the presence of 3-hydroxyflavone (3HF) in fluid solution results in diffusional triplet energy transfer from benzil to 3HF, and the T n←T 1 absorption spectrum of 3HF (acceptor) was determined by transient absorption spectroscopy. It is demonstrated that red probe pulse excitation of the lowest triplet state (T 1) of the normal tautomer yields green fluorescence from the phototautomer in the lowest excited singlet state (S' 1). Generation of S' 1 upon the excitation of T 1 may be ascribed to an efficient T n→T' n proton transfer followed by T n'→T' 2 relaxation and T' 2→S' 1 reverse intersystem crossing.

Influence of an electric field on photostimulated states in NH4BPh4 films

NASA Astrophysics Data System (ADS)

Antonova, O. V.; Nadolinny, V. A.; Il'inchik, E. A.; Trubin, S. V.

2012-10-01

The influence of an electric field on stable photostimulated triplet states of NH4BPh4 at a temperature of 77 K have been studied by EPR spectroscopy. It has been established that, on exposure to UV radiation, electron capture by traps in the band gaps takes place with formation of triplet state. After application of an electric field, triplet states are destructed because, with an increase in the applied voltage, a gradual inclination of energy bands takes place and electrons found in traps on different energy levels are released. The assumption that captured electrons are found in traps on different energy levels is confirmed by earlier studies of thermoluminescence spectra.

Energy deposition studies for the high-luminosity Large Hadron Collider inner triplet magnets

NASA Astrophysics Data System (ADS)

Mokhov, N. V.; Rakhno, I. L.; Tropin, I. S.; Cerutti, F.; Esposito, L. S.; Lechner, A.

2015-05-01

A detailed model of the high-luminosity LHC inner triplet region with new large-aperture Nb3Sn magnets, field maps, corrector packages, and segmented tungsten inner absorbers was built and implemented into the fluka and mars15 codes. Detailed simulations have been performed coherently with the codes on the impact of particle debris from the 14-TeV center-of-mass pp-collisions on the short- and long-term stability of the inner triplet magnets. After optimizing the absorber configuration, the peak power density averaged over the magnet inner cable width is found to be safely below the quench limit at the luminosity of 5 ×1034 cm-2 s-1 . For the anticipated lifetime integrated luminosity of 3000 fb-1 , the peak dose calculated for the innermost magnet insulator ranges from 20 to 35 MGy, a figure close to the commonly accepted limit. Dynamic heat loads to the triplet magnet cold mass are calculated to evaluate the cryogenic capability. fluka and mars results on energy deposition are in very good agreement.

Time-resolved fluorescence and FCS studies of dye-doped DNA

NASA Astrophysics Data System (ADS)

Nicolaou, N.; Marsh, R. J.; Blacker, T.; Armoogum, D. A.; Bain, A. J.

2009-08-01

Fluorescence lifetime, anisotropy and intensity dependent single molecule fluorescence correlation spectroscopy (I-FCS) are used to investigate the mechanism of fluorescence saturation in a free and nucleotide bound fluorophore (NR6104) in an antioxidising ascorbate buffer. Nucleotide attachment does not appreciably affect the fluorescence lifetime of the probe and there is a decrease in the rate of intersystem crossing relative to that of triplet state deactivation. The triplet state fraction is seen to plateau at 72% (G-attached) and 80% (free fluorophore) in agreement with these observations. Measurements of translational diffusion times show no intensity dependence for excitation intensities between 1 and 105kW cm-2 and photobleaching is therefore negligible. The dominant mechanism of fluorescence saturation is thus triplet state formation. I-FCS measurements for Rhodamine 6G in water were compared with those in the ascorbate buffer. In water the triplet fraction was saturated at considerably higher powers (45% at ca. 1.5 × 103kW cm-2) than in the ascorbate buffer (55%ca. 1 1kW cm-2)

Dynamics of Singlet Fission and Electron Injection in Self-Assembled Acene Monolayers on Titanium Dioxide

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

Johnson, Justin C; Pace, Natalie A; Arias, Dylan H

We employ a combination of linear spectroscopy, electrochemistry, and transient absorption spectroscopy to characterize the interplay between electron transfer and singlet fission dynamics in polyacene-based dyes attached to nanostructured TiO2. For triisopropyl silylethynyl (TIPS)-pentacene, we find that the singlet fission time constant increases to 6.5 ps on a nanostructured TiO2 surface relative to a thin film time constant of 150 fs, and that triplets do not dissociate after they are formed. In contrast, TIPS-tetracene singlets quickly dissociate in 2 ps at the molecule/TiO2 interface, and this dissociation outcompetes the relatively slow singlet fission process. The addition of an alumina layermore » slows down electron injection, allowing the formation of triplets from singlet fission in 40 ps. However, the triplets do not inject electrons, which is likely due to a lack of sufficient driving force for triplet dissociation. These results point to the critical balance required between efficient singlet fission and appropriate energetics for interfacial charge transfer.« less

A Comparative Study on the Photophysics and Photochemistry of Xanthene Dyes in the Presence of Polyamidoamine (PAMAM) Dendrimers.

PubMed

Arbeloa, Ernesto Maximiliano; Previtali, Carlos Mario; Bertolotti, Sonia Graciela

2018-04-17

The photophysical and photochemical properties of the xanthene dyes Eosin Y, Erythrosin B, and Rose Bengal are evaluated in the presence of amino-terminated polyamidoamine (PAMAM) dendrimers of relatively high generation (G3-G5) in alkaline aqueous solution. UV/Vis absorption and fluorescence spectra of the dyes show bathochromic shifts, which correlate with the size of the dendrimer. Binding constants (K bind ) are calculated from absorption data. The resulting high K bind values indicate strong interactions between both molecules. Triplet-triplet absorption spectra of the dyes are recorded by laser flash photolysis, and a decrease in the triplet lifetimes is observed in the presence of dendrimers. At the same time, an increase in the absorption of the semireduced form of the dyes is observed. Rate constants for triplet quenching ( 3 k q ) and radical quantum yields (Φ R ) are obtained. The results are explained by a very efficient electron-transfer process from PAMAM to xanthene dyes for all of the dye/dendrimer couples that are evaluated. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solid state photochemistry of polycarbonates

NASA Technical Reports Server (NTRS)

Gupta, A.; Rembaum, A.; Moacanin, J.

1978-01-01

The quantum yield of photoFries rearrangement in a polycarbonate film has been analyzed as a function of temperature and humidity on the basis of previously reported (Koyler and Mann, 1977) experimental data. Results indicate that in the homogeneous amorphous phase, photoFries rearrangement is a concerted process proceeding either from the pi star reversed arrow n singlet, in which case it must be subject to considerable self quenching, or from a triplet, presumably the first triplet since the lifetime of higher triplets is expected to be very short in the solid phase. If the parent excited state is the first triplet, chain scission is possibly an independent process, probably occurring from the pi star reversed arrow n singlet. Evidence of chain scission on photodegradation in the solid state includes loss of C-O and C-C bond intensities revealed in the Fourier transform infrared spectra, gel permeation chromotography elution profiles of degraded film samples dissolved in CHCl3, and a decrease in tensile strength and T sub g as photodegradation proceeds. Chain scission is apparently inhibited as photoFries products accumulate.

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 .

Vibronically coherent ultrafast triplet-pair formation and subsequent thermally activated dissociation control efficient endothermic singlet fission

NASA Astrophysics Data System (ADS)

Stern, Hannah L.; Cheminal, Alexandre; Yost, Shane R.; Broch, Katharina; Bayliss, Sam L.; Chen, Kai; Tabachnyk, Maxim; Thorley, Karl; Greenham, Neil; Hodgkiss, Justin M.; Anthony, John; Head-Gordon, Martin; Musser, Andrew J.; Rao, Akshay; Friend, Richard H.

2017-12-01

Singlet exciton fission (SF), the conversion of one spin-singlet exciton (S1) into two spin-triplet excitons (T1), could provide a means to overcome the Shockley-Queisser limit in photovoltaics. SF as measured by the decay of S1 has been shown to occur efficiently and independently of temperature, even when the energy of S1 is as much as 200 meV less than that of 2T1. Here we study films of triisopropylsilyltetracene using transient optical spectroscopy and show that the triplet pair state (TT), which has been proposed to mediate singlet fission, forms on ultrafast timescales (in 300 fs) and that its formation is mediated by the strong coupling of electronic and vibrational degrees of freedom. This is followed by a slower loss of singlet character as the excitation evolves to become only TT. We observe the TT to be thermally dissociated on 10-100 ns timescales to form free triplets. This provides a model for 'temperature-independent' efficient TT formation and thermally activated TT separation.

The role of secondary processes in kinetics of triplet states of a hydrogen molecule in an ECR discharge

NASA Astrophysics Data System (ADS)

Shakhatov, V. A.; Lebedev, Yu A.; Lacoste, A.; Bechu, S.

2017-11-01

An electronic state sensitive semiempirical collision-radiative model of hydrogen plasma of ECR-discharge is used to analyze the applicability of emission of triplet states of molecular hydrogen for plasma diagnostics. It is shown that secondary processes make the greatest contribution to the kinetics of population-depopulation of triplet states {a}3{{Σ }}}g+,{c}3{{{\\Pi }}}u,{d}3{{{\\Pi }}}u,{e}3{{{Σ }}}u+,{g}3{{{Σ }}}g+,{h}3{{{Σ }}}g+, i 3Πg and r 3Πg. The secondary processes give the smallest contribution to the excitation and deactivation of triplet states {f}3{{{Σ }}}u+ {\\unicode{x00438;} {k}3{{{\\Pi }}}u. Thus a simplified coronal model (electron impact excitation followed by radiative decay) can be used to process the intensities of the dipole allowed {f}3{{{Σ }}}u+ \\to {a}3{{{Σ }}}g+,{g}3{{{Σ }}}g+ and {k}3{{{\\Pi }}}u \\to {a}3{{{Σ }}}g+ transitions. The complicated collision-radiative model should be used for other transitions.

Singlet-triplet energy differences in divalent five membered cyclic conjugated Arduengo-type carbenes XC2HN2M (M = C, Si, Ge, Sn, and Pb; X = F, Cl, Br, and I)

NASA Astrophysics Data System (ADS)

Vessally, Esmail; Dehbandi, Behnam; Ahmadi, Elaheh

2016-09-01

Singlet-triplet energy differences in Arduengo-type carbenes XC2HN2C compared and contrasted with their sila, germa, stana and plumba analogues; at B3LYP/6-311++G** level of theory. Free Gibbs energy differences between triplet (t) and singlet (s) states (Δ G(t-s)) change in the following order: plumbylenes > stannylenes > germylenes > silylenes > carbenes. The singlet states in XC2HN2C are generally more stable when the electron withdrawing groups such as-F was used at β-position. However, the singlet states in XC2N2HM (M = Si, Ge, Sn, and Pb) are generally more stable when the withdrawing groups such as-F was placed. The puckering energy is investigated for each the singlet and triplet states. The DFT calculations found the linear correlation to size of the group 14 divalent element (M), the ∠N-M-N angle, and the Δ(LUMO-HOMO) of XC2HN2M.

Delayed Triplet-State Formation through Hybrid Charge Transfer Exciton at Copper Phthalocyanine/GaAs Heterojunction.

PubMed

Lim, Heeseon; Kwon, Hyuksang; Kim, Sang Kyu; Kim, Jeong Won

2017-10-05

Light absorption in organic molecules on an inorganic substrate and subsequent electron transfer to the substrate create so-called hybrid charge transfer exciton (HCTE). The relaxation process of the HCTE states largely determines charge separation efficiency or optoelectronic device performance. Here, the study on energy and time-dispersive behavior of photoelectrons at the hybrid interface of copper phthalocyanine (CuPc)/p-GaAs(001) upon light excitation of GaAs reveals a clear pathway for HCTE relaxation and delayed triplet-state formation. According to the ground-state energy level alignment at the interface, CuPc/p-GaAs(001) shows initially fast hole injection from GaAs to CuPc. Thus, the electrons in GaAs and holes in CuPc form an unusual HCTE state manifold. Subsequent electron transfer from GaAs to CuPc generates the formation of the triplet state in CuPc with a few picoseconds delay. Such two-step charge transfer causes delayed triplet-state formation without singlet excitation and subsequent intersystem crossing within the CuPc molecules.

Electronic Interactions of Michler's Ketone with DNA Bases in Synthetic Hairpins.

PubMed

Jalilov, Almaz S; Young, Ryan M; Eaton, Samuel W; Wasielewski, Michael R; Lewis, Frederick D

2015-01-01

The mechanism and dynamics of photoinduced electron transfer in two families of DNA hairpins possessing Michler's ketone linkers have been investigated by means of steady state and time-resolved transient absorption and emission spectroscopies. The excited state behavior of the diol linker employed in hairpin synthesis is similar to that of Michler's ketone in methanol solution. Hairpins possessing only a Michler's ketone linker undergo fast singlet state charge separation and charge recombination with an adjacent purine base, attributed to well-stacked ground state conformations, and intersystem crossing to the triplet state, attributed to poorly stacked ground state conformations. The failure of the triplet to undergo electron transfer reactions on the 7 ns time scale of our measurements is attributed to the low triplet energy and reduction potential of the twisted triplet state. Hairpins possessing both a Michler's ketone linker and a perylenediimide base surrogate separated by four base pairs undergo photoinduced hole transport from the diimide to Michler's ketone upon excitation of the diimide. The efficiency of hole transport is dependent upon the sequence of the intervening purine bases. © 2014 The American Society of Photobiology.

Implicit Learning of Predictive Relationships in Three-element Visual Sequences by Young and Old Adults

PubMed Central

Howard, James H.; Howard, Darlene V.; Dennis, Nancy A.; Kelly, Andrew J.

2008-01-01

Knowledge of sequential relationships enables future events to be anticipated and processed efficiently. Research with the serial reaction time task (SRTT) has shown that sequence learning often occurs implicitly without effort or awareness. Here we report four experiments that use a triplet-learning task (TLT) to investigate sequence learning in young and older adults. In the TLT people respond only to the last target event in a series of discrete, three-event sequences or triplets. Target predictability is manipulated by varying the triplet frequency (joint probability) and/or the statistical relationships (conditional probabilities) among events within the triplets. Results revealed that both groups learned, though older adults showed less learning of both joint and conditional probabilities. Young people used the statistical information in both cues, but older adults relied primarily on information in the second cue alone. We conclude that the TLT complements and extends the SRTT and other tasks by offering flexibility in the kinds of sequential statistical regularities that may be studied as well as by controlling event timing and eliminating motor response sequencing. PMID:18763897

Search for neutral color-octet weak-triplet scalar particles in proton-proton collisions at √s = 8 TeV

DOE PAGES

Khachatryan, Vardan

2015-09-29

A search for pair production of neutral color-octet weak-triplet scalar particles (Θ 0) is performed in processes where one Θ 0 decays to a pair of b quark jets and the other to a Z boson plus a jet, with the Z boson decaying to a pair of electrons or muons. The search is performed with data collected by the CMS experiment at the CERN LHC corresponding to an integrated luminosity of 19.7 fb –1 of proton-proton collisions at √s = 8 TeV. The number of observed events is found to be in agreement with the standard model predictions. Themore » 95% confidence level upper limit on the product of the cross section and branching fraction is obtained as a function of the Θ 0 mass. The 95% confidence level lower bounds on the Θ 0 mass are found to be 623 and 426 GeV, for two different octo-triplet theoretical scenarios. These are the first direct experimental bounds on particles predicted by the octo-triplet model.« less

A theoretical study of the photoinduced desorption of I — from a CF3I dimer

NASA Astrophysics Data System (ADS)

Tossell, J. A.

1997-04-01

Ab initio SCF-MO calculations using effective core-potential basis sets are employed to evaluate ionization potentials and electron affinities for CF3I and the geometries and energies of the singlet and triplet states of the CF3I dimer. The calculated geometry of the single state of the dimer is in qualitative agreement with the experimental geometry for condensed phase CF3I. The calculated energy for vertical excitation from the singlet to the triplet state is 4.1 eV at the Hartree-Fock level and 4.5 eV after incorporation of correlation at the Moller-Plesset 2nd-order level, consistent with excitation by 193 nm (6.4 eV) light. The equilibrium geometry of the triplet consists essentially of a CF3I+, CF3I- ion pair, in which the Csbnd I bond distance in the anionic component has increased to 5.5Å, compared with 2.1Åin the neutral molecule. The calculated binding energy of the triplet ion pair is about 4 eV.

Spectral features of the tunneling-induced transparency and the Autler-Townes doublet and triplet in a triple quantum dot.

PubMed

Luo, Xiao-Qing; Li, Zeng-Zhao; Jing, Jun; Xiong, Wei; Li, Tie-Fu; Yu, Ting

2018-02-15

We theoretically investigate the spectral features of tunneling-induced transparency (TIT) and Autler-Townes (AT) doublet and triplet in a triple-quantum-dot system. By analyzing the eigenenergy spectrum of the system Hamiltonian, we can discriminate TIT and double TIT from AT doublet and triplet, respectively. For the resonant case, the presence of the TIT does not exhibit distinguishable anticrossing in the eigenenergy spectrum in the weak-tunneling regime, while the occurrence of double anticrossings in the strong-tunneling regime shows that the TIT evolves to the AT doublet. For the off-resonance case, the appearance of a new detuning-dependent dip in the absorption spectrum leads to double TIT behavior in the weak-tunneling regime due to no distinguished anticrossing occurring in the eigenenergy spectrum. However, in the strong-tunneling regime, a new detuning-dependent dip in the absorption spectrum results in AT triplet owing to the presence of triple anticrossings in the eigenenergy spectrum. Our results can be applied to quantum measurement and quantum-optics devices in solid systems.

Search for neutral color-octet weak-triplet scalar particles in proton-proton collisions at √{s}=8 TeV

NASA Astrophysics Data System (ADS)

Khachatryan, V.; Sirunyan, A. M.; Tumasyan, A.; Adam, W.; Asilar, E.; Bergauer, T.; Brandstetter, J.; Brondolin, E.; Dragicevic, M.; Erö, J.; Flechl, M.; Friedl, M.; Frühwirth, R.; Ghete, V. M.; Hartl, C.; Hörmann, N.; Hrubec, J.; Jeitler, M.; Knünz, V.; König, A.; Krammer, M.; Krätschmer, I.; Liko, D.; Matsushita, T.; Mikulec, I.; Rabady, D.; Rahbaran, B.; Rohringer, H.; Schieck, J.; Schöfbeck, R.; Strauss, J.; Treberer-Treberspurg, W.; Waltenberger, W.; Wulz, C.-E.; Mossolov, V.; Shumeiko, N.; Suarez Gonzalez, J.; Alderweireldt, S.; Cornelis, T.; De Wolf, E. A.; Janssen, X.; Knutsson, A.; Lauwers, J.; Luyckx, S.; Ochesanu, S.; Rougny, R.; Van De Klundert, M.; Van Haevermaet, H.; Van Mechelen, P.; Van Remortel, N.; Van Spilbeeck, A.; Abu Zeid, S.; Blekman, F.; D'Hondt, J.; Daci, N.; De Bruyn, I.; Deroover, K.; Heracleous, N.; Keaveney, J.; Lowette, S.; Moreels, L.; Olbrechts, A.; Python, Q.; Strom, D.; Tavernier, S.; Van Doninck, W.; Van Mulders, P.; Van Onsem, G. P.; Van Parijs, I.; Barria, P.; Caillol, C.; Clerbaux, B.; De Lentdecker, G.; Delannoy, H.; Dobur, D.; Fasanella, G.; Favart, L.; Gay, A. P. R.; Grebenyuk, A.; Léonard, A.; Mohammadi, A.; Perniè, L.; Randleconde, A.; Reis, T.; Seva, T.; Thomas, L.; Vander Velde, C.; Vanlaer, P.; Wang, J.; Zenoni, F.; Zhang, F.; Beernaert, K.; Benucci, L.; Cimmino, A.; Crucy, S.; Fagot, A.; Garcia, G.; Gul, M.; Mccartin, J.; Ocampo Rios, A. A.; Poyraz, D.; Ryckbosch, D.; Salva Diblen, S.; Sigamani, M.; Strobbe, N.; Tytgat, M.; Van Driessche, W.; Yazgan, E.; Zaganidis, N.; Basegmez, S.; Beluffi, C.; Bondu, O.; Bruno, G.; Castello, R.; Caudron, A.; Ceard, L.; Da Silveira, G. G.; Delaere, C.; Favart, D.; Forthomme, L.; Giammanco, A.; Hollar, J.; Jafari, A.; Jez, P.; Komm, M.; Lemaitre, V.; Mertens, A.; Nuttens, C.; Perrini, L.; Pin, A.; Piotrzkowski, K.; Popov, A.; Quertenmont, L.; Selvaggi, M.; Vidal Marono, M.; Beliy, N.; Caebergs, T.; Hammad, G. H.; Aldá Júnior, W. L.; Alves, G. A.; Brito, L.; Correa Martins Junior, M.; Dos Reis Martins, T.; Hensel, C.; Mora Herrera, C.; Moraes, A.; Pol, M. E.; Rebello Teles, P.; Belchior Batista Das Chagas, E.; Carvalho, W.; Chinellato, J.; Custódio, A.; Da Costa, E. M.; De Jesus Damiao, D.; De Oliveira Martins, C.; Fonseca De Souza, S.; Huertas Guativa, L. M.; Malbouisson, H.; Matos Figueiredo, D.; Mundim, L.; Nogima, H.; Prado Da Silva, W. L.; Santoro, A.; Sznajder, A.; Tonelli Manganote, E. J.; Vilela Pereira, A.; Ahuja, S.; Bernardes, C. A.; De Souza Santos, A.; Dogra, S.; Fernandez Perez Tomei, T. R.; Gregores, E. M.; Mercadante, P. G.; Moon, C. S.; Novaes, S. F.; Padula, Sandra S.; Romero Abad, D.; Ruiz Vargas, J. C.; Aleksandrov, A.; Genchev, V.; Hadjiiska, R.; Iaydjiev, P.; Marinov, A.; Piperov, S.; Rodozov, M.; Stoykova, S.; Sultanov, G.; Vutova, M.; Dimitrov, A.; Glushkov, I.; Litov, L.; Pavlov, B.; Petkov, P.; Ahmad, M.; Bian, J. G.; Chen, G. M.; Chen, H. S.; Chen, M.; Cheng, T.; Du, R.; Jiang, C. H.; Plestina, R.; Romeo, F.; Shaheen, S. M.; Tao, J.; Wang, C.; Wang, Z.; Zhang, H.; Asawatangtrakuldee, C.; Ban, Y.; Li, Q.; Liu, S.; Mao, Y.; Qian, S. J.; Wang, D.; Xu, Z.; Zou, W.; Avila, C.; Cabrera, A.; Chaparro Sierra, L. F.; Florez, C.; Gomez, J. P.; Gomez Moreno, B.; Sanabria, J. C.; Godinovic, N.; Lelas, D.; Polic, D.; Puljak, I.; Antunovic, Z.; Kovac, M.; Brigljevic, V.; Kadija, K.; Luetic, J.; Sudic, L.; Attikis, A.; Mavromanolakis, G.; Mousa, J.; Nicolaou, C.; Ptochos, F.; Razis, P. A.; Rykaczewski, H.; Bodlak, M.; Finger, M.; Finger, M.; Ali, A.; Aly, R.; Aly, S.; Elgammal, S.; Ellithi Kamel, A.; Lotfy, A.; Mahmoud, M. A.; Masod, R.; Radi, A.; Calpas, B.; Kadastik, M.; Murumaa, M.; Raidal, M.; Tiko, A.; Veelken, C.; Eerola, P.; Voutilainen, M.; Härkönen, J.; Karimäki, V.; Kinnunen, R.; Lampén, T.; Lassila-Perini, K.; Lehti, S.; Lindén, T.; Luukka, P.; Mäenpää, T.; Pekkanen, J.; Peltola, T.; Tuominen, E.; Tuominiemi, J.; Tuovinen, E.; Wendland, L.; Talvitie, J.; Tuuva, T.; Besancon, M.; Couderc, F.; Dejardin, M.; Denegri, D.; Fabbro, B.; Faure, J. L.; Favaro, C.; Ferri, F.; Ganjour, S.; Givernaud, A.; Gras, P.; Hamel de Monchenault, G.; Jarry, P.; Locci, E.; Machet, M.; Malcles, J.; Rander, J.; Rosowsky, A.; Titov, M.; Zghiche, A.; Baffioni, S.; Beaudette, F.; Busson, P.; Cadamuro, L.; Chapon, E.; Charlot, C.; Dahms, T.; Davignon, O.; Filipovic, N.; Florent, A.; Granier de Cassagnac, R.; Lisniak, S.; Mastrolorenzo, L.; Miné, P.; Naranjo, I. N.; Nguyen, M.; Ochando, C.; Ortona, G.; Paganini, P.; Regnard, S.; Salerno, R.; Sauvan, J. B.; Sirois, Y.; Strebler, T.; Yilmaz, Y.; Zabi, A.; Agram, J.-L.; Andrea, J.; Aubin, A.; Bloch, D.; Brom, J.-M.; Buttignol, M.; Chabert, E. C.; Chanon, N.; Collard, C.; Conte, E.; Fontaine, J.-C.; Gelé, D.; Goerlach, U.; Goetzmann, C.; Le Bihan, A.-C.; Merlin, J. A.; Skovpen, K.; Van Hove, P.; Gadrat, S.; Beauceron, S.; Beaupere, N.; Bernet, C.; Boudoul, G.; Bouvier, E.; Brochet, S.; Carrillo Montoya, C. A.; Chasserat, J.; Chierici, R.; Contardo, D.; Courbon, B.; Depasse, P.; El Mamouni, H.; Fan, J.; Fay, J.; Gascon, S.; Gouzevitch, M.; Ille, B.; Laktineh, I. B.; Lethuillier, M.; Mirabito, L.; Pequegnot, A. L.; Perries, S.; Ruiz Alvarez, J. D.; Sabes, D.; Sgandurra, L.; Sordini, V.; Vander Donckt, M.; Verdier, P.; Viret, S.; Xiao, H.; Lomidze, D.; Autermann, C.; Beranek, S.; Edelhoff, M.; Feld, L.; Heister, A.; Kiesel, M. K.; Klein, K.; Lipinski, M.; Ostapchuk, A.; Preuten, M.; Raupach, F.; Sammet, J.; Schael, S.; Schulte, J. F.; Verlage, T.; Weber, H.; Wittmer, B.; Zhukov, V.; Ata, M.; Brodski, M.; Dietz-Laursonn, E.; Duchardt, D.; Endres, M.; Erdmann, M.; Erdweg, S.; Esch, T.; Fischer, R.; Güth, A.; Hebbeker, T.; Heidemann, C.; Hoepfner, K.; Klingebiel, D.; Knutzen, S.; Kreuzer, P.; Merschmeyer, M.; Meyer, A.; Millet, P.; Olschewski, M.; Padeken, K.; Papacz, P.; Pook, T.; Radziej, M.; Reithler, H.; Rieger, M.; Scheuch, F.; Sonnenschein, L.; Teyssier, D.; Thüer, S.; Cherepanov, V.; Erdogan, Y.; Flügge, G.; Geenen, H.; Geisler, M.; Haj Ahmad, W.; Hoehle, F.; Kargoll, B.; Kress, T.; Kuessel, Y.; Künsken, A.; Lingemann, J.; Nehrkorn, A.; Nowack, A.; Nugent, I. M.; Pistone, C.; Pooth, O.; Stahl, A.; Aldaya Martin, M.; Asin, I.; Bartosik, N.; Behnke, O.; Behrens, U.; Bell, A. J.; Borras, K.; Burgmeier, A.; Cakir, A.; Calligaris, L.; Campbell, A.; Choudhury, S.; Costanza, F.; Diez Pardos, C.; Dolinska, G.; Dooling, S.; Dorland, T.; Eckerlin, G.; Eckstein, D.; Eichhorn, T.; Flucke, G.; Gallo, E.; Garay Garcia, J.; Geiser, A.; Gizhko, A.; Gunnellini, P.; Hauk, J.; Hempel, M.; Jung, H.; Kalogeropoulos, A.; Karacheban, O.; Kasemann, M.; Katsas, P.; Kieseler, J.; Kleinwort, C.; Korol, I.; Lange, W.; Leonard, J.; Lipka, K.; Lobanov, A.; Lohmann, W.; Mankel, R.; Marfin, I.; Melzer-Pellmann, I.-A.; Meyer, A. B.; Mittag, G.; Mnich, J.; Mussgiller, A.; Naumann-Emme, S.; Nayak, A.; Ntomari, E.; Perrey, H.; Pitzl, D.; Placakyte, R.; Raspereza, A.; Ribeiro Cipriano, P. M.; Roland, B.; Sahin, M. Ö.; Salfeld-Nebgen, J.; Saxena, P.; Schoerner-Sadenius, T.; Schröder, M.; Seitz, C.; Spannagel, S.; Trippkewitz, K. D.; Wissing, C.; Blobel, V.; Centis Vignali, M.; Draeger, A. R.; Erfle, J.; Garutti, E.; Goebel, K.; Gonzalez, D.; Görner, M.; Haller, J.; Hoffmann, M.; Höing, R. S.; Junkes, A.; Klanner, R.; Kogler, R.; Lapsien, T.; Lenz, T.; Marchesini, I.; Marconi, D.; Nowatschin, D.; Ott, J.; Pantaleo, F.; Peiffer, T.; Perieanu, A.; Pietsch, N.; Poehlsen, J.; Rathjens, D.; Sander, C.; Schettler, H.; Schleper, P.; Schlieckau, E.; Schmidt, A.; Seidel, M.; Sola, V.; Stadie, H.; Steinbrück, G.; Tholen, H.; Troendle, D.; Usai, E.; Vanelderen, L.; Vanhoefer, A.; Akbiyik, M.; Barth, C.; Baus, C.; Berger, J.; Böser, C.; Butz, E.; Chwalek, T.; Colombo, F.; De Boer, W.; Descroix, A.; Dierlamm, A.; Feindt, M.; Frensch, F.; Giffels, M.; Gilbert, A.; Hartmann, F.; Husemann, U.; Kassel, F.; Katkov, I.; Kornmayer, A.; Lobelle Pardo, P.; Mozer, M. U.; Müller, T.; Müller, Th.; Plagge, M.; Quast, G.; Rabbertz, K.; Röcker, S.; Roscher, F.; Simonis, H. J.; Stober, F. M.; Ulrich, R.; Wagner-Kuhr, J.; Wayand, S.; Weiler, T.; Wöhrmann, C.; Wolf, R.; Anagnostou, G.; Daskalakis, G.; Geralis, T.; Giakoumopoulou, V. A.; Kyriakis, A.; Loukas, D.; Markou, A.; Psallidas, A.; Topsis-Giotis, I.; Agapitos, A.; Kesisoglou, S.; Panagiotou, A.; Saoulidou, N.; Tziaferi, E.; Evangelou, I.; Flouris, G.; Foudas, C.; Kokkas, P.; Loukas, N.; Manthos, N.; Papadopoulos, I.; Paradas, E.; Strologas, J.; Bencze, G.; Hajdu, C.; Hazi, A.; Hidas, P.; Horvath, D.; Sikler, F.; Veszpremi, V.; Vesztergombi, G.; Zsigmond, A. J.; Beni, N.; Czellar, S.; Karancsi, J.; Molnar, J.; Szillasi, Z.; Bartók, M.; Makovec, A.; Raics, P.; Trocsanyi, Z. L.; Ujvari, B.; Mal, P.; Mandal, K.; Sahoo, N.; Swain, S. K.; Bansal, S.; Beri, S. B.; Bhatnagar, V.; Chawla, R.; Gupta, R.; Bhawandeep, U.; Kalsi, A. K.; Kaur, A.; Kaur, M.; Kumar, R.; Mehta, A.; Mittal, M.; Nishu, N.; Singh, J. B.; Walia, G.; Kumar, Ashok; Kumar, Arun; Bhardwaj, A.; Choudhary, B. C.; Garg, R. B.; Kumar, A.; Malhotra, S.; Naimuddin, M.; Ranjan, K.; Sharma, R.; Sharma, V.; Banerjee, S.; Bhattacharya, S.; Chatterjee, K.; Dey, S.; Dutta, S.; Jain, Sa.; Jain, Sh.; Khurana, R.; Majumdar, N.; Modak, A.; Mondal, K.; Mukherjee, S.; Mukhopadhyay, S.; Roy, A.; Roy, D.; Roy Chowdhury, S.; Sarkar, S.; Sharan, M.; Abdulsalam, A.; Chudasama, R.; Dutta, D.; Jha, V.; Kumar, V.; Mohanty, A. K.; Pant, L. M.; Shukla, P.; Topkar, A.; Aziz, T.; Banerjee, S.; Bhowmik, S.; Chatterjee, R. M.; Dewanjee, R. K.; Dugad, S.; Ganguly, S.; Ghosh, S.; Guchait, M.; Gurtu, A.; Kole, G.; Kumar, S.; Mahakud, B.; Maity, M.; Majumder, G.; Mazumdar, K.; Mitra, S.; Mohanty, G. B.; Parida, B.; Sarkar, T.; Sudhakar, K.; Sur, N.; Sutar, B.; Wickramage, N.; Sharma, S.; Bakhshiansohi, H.; Behnamian, H.; Etesami, S. M.; Fahim, A.; Goldouzian, R.; Khakzad, M.; Mohammadi Najafabadi, M.; Naseri, M.; Paktinat Mehdiabadi, S.; Rezaei Hosseinabadi, F.; Safarzadeh, B.; Zeinali, M.; Felcini, M.; Grunewald, M.; Abbrescia, M.; Calabria, C.; Caputo, C.; Chhibra, S. S.; Colaleo, A.; Creanza, D.; Cristella, L.; De Filippis, N.; De Palma, M.; Fiore, L.; Iaselli, G.; Maggi, G.; Maggi, M.; Miniello, G.; My, S.; Nuzzo, S.; Pompili, A.; Pugliese, G.; Radogna, R.; Ranieri, A.; Selvaggi, G.; Sharma, A.; Silvestris, L.; Venditti, R.; Verwilligen, P.; Abbiendi, G.; Battilana, C.; Benvenuti, A. C.; Bonacorsi, D.; Braibant-Giacomelli, S.; Brigliadori, L.; Campanini, R.; Capiluppi, P.; Castro, A.; Cavallo, F. R.; Codispoti, G.; Cuffiani, M.; Dallavalle, G. M.; Fabbri, F.; Fanfani, A.; Fasanella, D.; Giacomelli, P.; Grandi, C.; Guiducci, L.; Marcellini, S.; Masetti, G.; Montanari, A.; Navarria, F. L.; Perrotta, A.; Rossi, A. M.; Rovelli, T.; Siroli, G. P.; Tosi, N.; Travaglini, R.; Cappello, G.; Chiorboli, M.; Costa, S.; Giordano, F.; Potenza, R.; Tricomi, A.; Tuve, C.; Barbagli, G.; Ciulli, V.; Civinini, C.; D'Alessandro, R.; Focardi, E.; Gonzi, S.; Gori, V.; Lenzi, P.; Meschini, M.; Paoletti, S.; Sguazzoni, G.; Tropiano, A.; Viliani, L.; Benussi, L.; Bianco, S.; Fabbri, F.; Piccolo, D.; Calvelli, V.; Ferro, F.; Vetere, M. Lo; Robutti, E.; Tosi, S.; Dinardo, M. E.; Fiorendi, S.; Gennai, S.; Gerosa, R.; Ghezzi, A.; Govoni, P.; Malvezzi, S.; Manzoni, R. A.; Marzocchi, B.; Menasce, D.; Moroni, L.; Paganoni, M.; Pedrini, D.; Ragazzi, S.; Redaelli, N.; Tabarelli de Fatis, T.; Buontempo, S.; Cavallo, N.; Di Guida, S.; Esposito, M.; Fabozzi, F.; Iorio, A. O. M.; Lanza, G.; Lista, L.; Meola, S.; Merola, M.; Paolucci, P.; Sciacca, C.; Thyssen, F.; Azzi, P.; Bacchetta, N.; Bisello, D.; Carlin, R.; Carvalho Antunes De Oliveira, A.; Checchia, P.; Dall'Osso, M.; Dorigo, T.; Gasparini, F.; Gasparini, U.; Gozzelino, A.; Lacaprara, S.; Margoni, M.; Meneguzzo, A. T.; Pazzini, J.; Pozzobon, N.; Ronchese, P.; Sgaravatto, M.; Simonetto, F.; Torassa, E.; Tosi, M.; Vanini, S.; Ventura, S.; Zanetti, M.; Zotto, P.; Zucchetta, A.; Zumerle, G.; Braghieri, A.; Gabusi, M.; Magnani, A.; Ratti, S. P.; Re, V.; Riccardi, C.; Salvini, P.; Vai, I.; Vitulo, P.; Alunni Solestizi, L.; Biasini, M.; Bilei, G. M.; Ciangottini, D.; Fanò, L.; Lariccia, P.; Mantovani, G.; Menichelli, M.; Saha, A.; Santocchia, A.; Spiezia, A.; Androsov, K.; Azzurri, P.; Bagliesi, G.; Bernardini, J.; Boccali, T.; Broccolo, G.; Castaldi, R.; Ciocci, M. A.; Dell'Orso, R.; Donato, S.; Fedi, G.; Foà, L.; Giassi, A.; Grippo, M. T.; Ligabue, F.; Lomtadze, T.; Martini, L.; Messineo, A.; Palla, F.; Rizzi, A.; Savoy-Navarro, A.; Serban, A. T.; Spagnolo, P.; Squillacioti, P.; Tenchini, R.; Tonelli, G.; Venturi, A.; Verdini, P. G.; Barone, L.; Cavallari, F.; D'imperio, G.; Del Re, D.; Diemoz, M.; Gelli, S.; Jorda, C.; Longo, E.; Margaroli, F.; Meridiani, P.; Micheli, F.; Organtini, G.; Paramatti, R.; Preiato, F.; Rahatlou, S.; Rovelli, C.; Santanastasio, F.; Soffi, L.; Traczyk, P.; Amapane, N.; Arcidiacono, R.; Argiro, S.; Arneodo, M.; Bellan, R.; Biino, C.; Cartiglia, N.; Casasso, S.; Costa, M.; Covarelli, R.; Degano, A.; Demaria, N.; Finco, L.; Mariotti, C.; Maselli, S.; Migliore, E.; Monaco, V.; Musich, M.; Obertino, M. M.; Pacher, L.; Pastrone, N.; Pelliccioni, M.; Pinna Angioni, G. L.; Romero, A.; Ruspa, M.; Sacchi, R.; Solano, A.; Staiano, A.; Tamponi, U.; Trapani, P. P.; Belforte, S.; Candelise, V.; Casarsa, M.; Cossutti, F.; Della Ricca, G.; Gobbo, B.; La Licata, C.; Marone, M.; Schizzi, A.; Umer, T.; Zanetti, A.; Chang, S.; Kropivnitskaya, A.; Nam, S. K.; Kim, D. H.; Kim, G. N.; Kim, M. S.; Kong, D. J.; Lee, S.; Oh, Y. D.; Sakharov, A.; Son, D. C.; Kim, H.; Kim, T. J.; Ryu, M. S.; Song, S.; Choi, S.; Go, Y.; Gyun, D.; Hong, B.; Jo, M.; Kim, H.; Kim, Y.; Lee, B.; Lee, K.; Lee, K. S.; Lee, S.; Park, S. K.; Roh, Y.; Yoo, H. D.; Choi, M.; Kim, J. H.; Lee, J. S. H.; Park, I. C.; Ryu, G.; Choi, Y.; Choi, Y. K.; Goh, J.; Kim, D.; Kwon, E.; Lee, J.; Yu, I.; Juodagalvis, A.; Vaitkus, J.; Ibrahim, Z. A.; Komaragiri, J. R.; Ali, M. A. B. Md; Mohamad Idris, F.; Wan Abdullah, W. A. T.; Casimiro Linares, E.; Castilla-Valdez, H.; De La Cruz-Burelo, E.; Heredia-de La Cruz, I.; Hernandez-Almada, A.; Lopez-Fernandez, R.; Ramirez Sanchez, G.; Sanchez-Hernandez, A.; Carrillo Moreno, S.; Vazquez Valencia, F.; Carpinteyro, S.; Pedraza, I.; Salazar Ibarguen, H. A.; Morelos Pineda, A.; Krofcheck, D.; Butler, P. H.; Reucroft, S.; Ahmad, A.; Ahmad, M.; Hassan, Q.; Hoorani, H. R.; Khan, W. A.; Khurshid, T.; Shoaib, M.; Bialkowska, H.; Bluj, M.; Boimska, B.; Frueboes, T.; Górski, M.; Kazana, M.; Nawrocki, K.; Romanowska-Rybinska, K.; Szleper, M.; Zalewski, P.; Brona, G.; Bunkowski, K.; Doroba, K.; Kalinowski, A.; Konecki, M.; Krolikowski, J.; Misiura, M.; Olszewski, M.; Walczak, M.; Bargassa, P.; Beirão Da Cruz E Silva, C.; Di Francesco, A.; Faccioli, P.; Ferreira Parracho, P. G.; Gallinaro, M.; Lloret Iglesias, L.; Nguyen, F.; Rodrigues Antunes, J.; Seixas, J.; Toldaiev, O.; Vadruccio, D.; Varela, J.; Vischia, P.; Afanasiev, S.; Bunin, P.; Gavrilenko, M.; Golutvin, I.; Gorbunov, I.; Kamenev, A.; Karjavin, V.; Konoplyanikov, V.; Lanev, A.; Malakhov, A.; Matveev, V.; Moisenz, P.; Palichik, V.; Perelygin, V.; Shmatov, S.; Shulha, S.; Skatchkov, N.; Smirnov, V.; Toriashvili, T.; Zarubin, A.; Golovtsov, V.; Ivanov, Y.; Kim, V.; Kuznetsova, E.; Levchenko, P.; Murzin, V.; Oreshkin, V.; Smirnov, I.; Sulimov, V.; Uvarov, L.; Vavilov, S.; Vorobyev, A.; Andreev, Yu.; Dermenev, A.; Gninenko, S.; Golubev, N.; Karneyeu, A.; Kirsanov, M.; Krasnikov, N.; Pashenkov, A.; Tlisov, D.; Toropin, A.; Epshteyn, V.; Gavrilov, V.; Lychkovskaya, N.; Popov, V.; Pozdnyakov, I.; Safronov, G.; Spiridonov, A.; Vlasov, E.; Zhokin, A.; Bylinkin, A.; Andreev, V.; Azarkin, M.; Dremin, I.; Kirakosyan, M.; Leonidov, A.; Mesyats, G.; Rusakov, S. V.; Vinogradov, A.; Baskakov, A.; Belyaev, A.; Boos, E.; Dubinin, M.; Dudko, L.; Ershov, A.; Gribushin, A.; Klyukhin, V.; Kodolova, O.; Lokhtin, I.; Myagkov, I.; Obraztsov, S.; Petrushanko, S.; Savrin, V.; Snigirev, A.; Azhgirey, I.; Bayshev, I.; Bitioukov, S.; Kachanov, V.; Kalinin, A.; Konstantinov, D.; Krychkine, V.; Petrov, V.; Ryutin, R.; Sobol, A.; Tourtchanovitch, L.; Troshin, S.; Tyurin, N.; Uzunian, A.; Volkov, A.; Adzic, P.; Ekmedzic, M.; Milosevic, J.; Rekovic, V.; Alcaraz Maestre, J.; Calvo, E.; Cerrada, M.; Chamizo Llatas, M.; Colino, N.; De La Cruz, B.; Delgado Peris, A.; Domínguez Vázquez, D.; Escalante Del Valle, A.; Fernandez Bedoya, C.; Fernández Ramos, J. P.; Flix, J.; Fouz, M. C.; Garcia-Abia, P.; Gonzalez Lopez, O.; Goy Lopez, S.; Hernandez, J. M.; Josa, M. I.; Navarro De Martino, E.; Pérez-Calero Yzquierdo, A.; Puerta Pelayo, J.; Quintario Olmeda, A.; Redondo, I.; Romero, L.; Soares, M. S.; Albajar, C.; de Trocóniz, J. F.; Missiroli, M.; Moran, D.; Brun, H.; Cuevas, J.; Fernandez Menendez, J.; Folgueras, S.; Gonzalez Caballero, I.; Palencia Cortezon, E.; Vizan Garcia, J. M.; Brochero Cifuentes, J. A.; Cabrillo, I. J.; Calderon, A.; Castiñeiras De Saa, J. R.; Duarte Campderros, J.; Fernandez, M.; Gomez, G.; Graziano, A.; Lopez Virto, A.; Marco, J.; Marco, R.; Martinez Rivero, C.; Matorras, F.; Munoz Sanchez, F. J.; Piedra Gomez, J.; Rodrigo, T.; Rodríguez-Marrero, A. Y.; Ruiz-Jimeno, A.; Scodellaro, L.; Vila, I.; Vilar Cortabitarte, R.; Abbaneo, D.; Auffray, E.; Auzinger, G.; Bachtis, M.; Baillon, P.; Ball, A. H.; Barney, D.; Benaglia, A.; Bendavid, J.; Benhabib, L.; Benitez, J. F.; Berruti, G. M.; Bianchi, G.; Bloch, P.; Bocci, A.; Bonato, A.; Botta, C.; Breuker, H.; Camporesi, T.; Cerminara, G.; Colafranceschi, S.; D'Alfonso, M.; d'Enterria, D.; Dabrowski, A.; Daponte, V.; David, A.; De Gruttola, M.; De Guio, F.; De Roeck, A.; De Visscher, S.; Di Marco, E.; Dobson, M.; Dordevic, M.; du Pree, T.; Dupont-Sagorin, N.; Elliott-Peisert, A.; Eugster, J.; Franzoni, G.; Funk, W.; Gigi, D.; Gill, K.; Giordano, D.; Girone, M.; Glege, F.; Guida, R.; Gundacker, S.; Guthoff, M.; Hammer, J.; Hansen, M.; Harris, P.; Hegeman, J.; Innocente, V.; Janot, P.; Kirschenmann, H.; Kortelainen, M. J.; Kousouris, K.; Krajczar, K.; Lecoq, P.; Lourenço, C.; Lucchini, M. T.; Magini, N.; Malgeri, L.; Mannelli, M.; Marrouche, J.; Martelli, A.; Masetti, L.; Meijers, F.; Mersi, S.; Meschi, E.; Moortgat, F.; Morovic, S.; Mulders, M.; Nemallapudi, M. V.; Neugebauer, H.; Orfanelli, S.; Orsini, L.; Pape, L.; Perez, E.; Petrilli, A.; Petrucciani, G.; Pfeiffer, A.; Piparo, D.; Racz, A.; Rolandi, G.; Rovere, M.; Ruan, M.; Sakulin, H.; Schäfer, C.; Schwick, C.; Sharma, A.; Silva, P.; Simon, M.; Sphicas, P.; Spiga, D.; Steggemann, J.; Stieger, B.; Stoye, M.; Takahashi, Y.; Treille, D.; Tsirou, A.; Veres, G. I.; Wardle, N.; Wöhri, H. K.; Zagozdzinska, A.; Zeuner, W. D.; Bertl, W.; Deiters, K.; Erdmann, W.; Horisberger, R.; Ingram, Q.; Kaestli, H. C.; Kotlinski, D.; Langenegger, U.; Rohe, T.; Bachmair, F.; Bäni, L.; Bianchini, L.; Buchmann, M. A.; Casal, B.; Dissertori, G.; Dittmar, M.; Donegà, M.; Dünser, M.; Eller, P.; Grab, C.; Heidegger, C.; Hits, D.; Hoss, J.; Kasieczka, G.; Lustermann, W.; Mangano, B.; Marini, A. C.; Marionneau, M.; Martinez Ruiz del Arbol, P.; Masciovecchio, M.; Meister, D.; Mohr, N.; Musella, P.; Nessi-Tedaldi, F.; Pandolfi, F.; Pata, J.; Pauss, F.; Perrozzi, L.; Peruzzi, M.; Quittnat, M.; Rossini, M.; Starodumov, A.; Takahashi, M.; Tavolaro, V. R.; Theofilatos, K.; Wallny, R.; Weber, H. A.; Aarrestad, T. K.; Amsler, C.; Canelli, M. F.; Chiochia, V.; De Cosa, A.; Galloni, C.; Hinzmann, A.; Hreus, T.; Kilminster, B.; Lange, C.; Ngadiuba, J.; Pinna, D.; Robmann, P.; Ronga, F. J.; Salerno, D.; Taroni, S.; Yang, Y.; Cardaci, M.; Chen, K. H.; Doan, T. H.; Ferro, C.; Konyushikhin, M.; Kuo, C. M.; Lin, W.; Lu, Y. J.; Volpe, R.; Yu, S. S.; Chang, P.; Chang, Y. H.; Chang, Y. W.; Chao, Y.; Chen, K. F.; Chen, P. H.; Dietz, C.; Fiori, F.; Grundler, U.; Hou, W.-S.; Hsiung, Y.; Liu, Y. F.; Lu, R.-S.; Miñano Moya, M.; Petrakou, E.; Tsai, J. f.; Tzeng, Y. M.; Wilken, R.; Asavapibhop, B.; Kovitanggoon, K.; Singh, G.; Srimanobhas, N.; Suwonjandee, N.; Adiguzel, A.; Cerci, S.; Dozen, C.; Girgis, S.; Gokbulut, G.; Guler, Y.; Gurpinar, E.; Hos, I.; Kangal, E. E.; Kayis Topaksu, A.; Onengut, G.; Ozdemir, K.; Ozturk, S.; Tali, B.; Topakli, H.; Vergili, M.; Zorbilmez, C.; Akin, I. V.; Bilin, B.; Bilmis, S.; Gamsizkan, H.; Isildak, B.; Karapinar, G.; Surat, U. E.; Yalvac, M.; Zeyrek, M.; Albayrak, E. A.; Gülmez, E.; Kaya, M.; Kaya, O.; Yetkin, T.; Cankocak, K.; Günaydin, Y. O.; Vardarlı, F. I.; Grynyov, B.; Levchuk, L.; Sorokin, P.; Aggleton, R.; Ball, F.; Beck, L.; Brooke, J. J.; Clement, E.; Cussans, D.; Flacher, H.; Goldstein, J.; Grimes, M.; Heath, G. P.; Heath, H. F.; Jacob, J.; Kreczko, L.; Lucas, C.; Meng, Z.; Newbold, D. M.; Paramesvaran, S.; Poll, A.; Sakuma, T.; Seif El Nasr-storey, S.; Senkin, S.; Smith, D.; Smith, V. J.; Bell, K. W.; Belyaev, A.; Brew, C.; Brown, R. M.; Cockerill, D. J. A.; Coughlan, J. A.; Harder, K.; Harper, S.; Olaiya, E.; Petyt, D.; Shepherd-Themistocleous, C. H.; Thea, A.; Tomalin, I. R.; Williams, T.; Womersley, W. J.; Worm, S. D.; Baber, M.; Bainbridge, R.; Buchmuller, O.; Bundock, A.; Burton, D.; Citron, M.; Colling, D.; Corpe, L.; Cripps, N.; Dauncey, P.; Davies, G.; De Wit, A.; Della Negra, M.; Dunne, P.; Elwood, A.; Ferguson, W.; Fulcher, J.; Futyan, D.; Hall, G.; Iles, G.; Karapostoli, G.; Kenzie, M.; Lane, R.; Lucas, R.; Lyons, L.; Magnan, A.-M.; Malik, S.; Nash, J.; Nikitenko, A.; Pela, J.; Pesaresi, M.; Petridis, K.; Raymond, D. M.; Richards, A.; Rose, A.; Seez, C.; Sharp, P.; Tapper, A.; Uchida, K.; Vazquez Acosta, M.; Virdee, T.; Zenz, S. C.; Cole, J. E.; Hobson, P. R.; Khan, A.; Kyberd, P.; Leggat, D.; Leslie, D.; Reid, I. D.; Symonds, P.; Teodorescu, L.; Turner, M.; Borzou, A.; Dittmann, J.; Hatakeyama, K.; Kasmi, A.; Liu, H.; Pastika, N.; Scarborough, T.; Charaf, O.; Cooper, S. I.; Henderson, C.; Rumerio, P.; Avetisyan, A.; Bose, T.; Fantasia, C.; Gastler, D.; Lawson, P.; Rankin, D.; Richardson, C.; Rohlf, J.; John, J. St.; Sulak, L.; Zou, D.; Alimena, J.; Berry, E.; Bhattacharya, S.; Cutts, D.; Demiragli, Z.; Dhingra, N.; Ferapontov, A.; Garabedian, A.; Heintz, U.; Laird, E.; Landsberg, G.; Mao, Z.; Narain, M.; Sagir, S.; Sinthuprasith, T.; Breedon, R.; Breto, G.; Calderon De La Barca Sanchez, M.; Chauhan, S.; Chertok, M.; Conway, J.; Conway, R.; Cox, P. T.; Erbacher, R.; Gardner, M.; Ko, W.; Lander, R.; Mulhearn, M.; Pellett, D.; Pilot, J.; Ricci-Tam, F.; Shalhout, S.; Smith, J.; Squires, M.; Stolp, D.; Tripathi, M.; Wilbur, S.; Yohay, R.; Cousins, R.; Everaerts, P.; Farrell, C.; Hauser, J.; Ignatenko, M.; Rakness, G.; Saltzberg, D.; Takasugi, E.; Valuev, V.; Weber, M.; Burt, K.; Clare, R.; Ellison, J.; Gary, J. W.; Hanson, G.; Heilman, J.; Ivova Rikova, M.; Jandir, P.; Kennedy, E.; Lacroix, F.; Long, O. R.; Luthra, A.; Malberti, M.; Olmedo Negrete, M.; Shrinivas, A.; Sumowidagdo, S.; Wei, H.; Wimpenny, S.; Branson, J. G.; Cerati, G. B.; Cittolin, S.; D'Agnolo, R. T.; Holzner, A.; Kelley, R.; Klein, D.; Letts, J.; Macneill, I.; Olivito, D.; Padhi, S.; Pieri, M.; Sani, M.; Sharma, V.; Simon, S.; Tadel, M.; Tu, Y.; Vartak, A.; Wasserbaech, S.; Welke, C.; Würthwein, F.; Yagil, A.; Zevi Della Porta, G.; Barge, D.; Bradmiller-Feld, J.; Campagnari, C.; Dishaw, A.; Dutta, V.; Flowers, K.; Franco Sevilla, M.; Geffert, P.; George, C.; Golf, F.; Gouskos, L.; Gran, J.; Incandela, J.; Justus, C.; Mccoll, N.; Mullin, S. D.; Richman, J.; Stuart, D.; To, W.; West, C.; Yoo, J.; Anderson, D.; Apresyan, A.; Bornheim, A.; Bunn, J.; Chen, Y.; Duarte, J.; Mott, A.; Newman, H. B.; Pena, C.; Pierini, M.; Spiropulu, M.; Vlimant, J. R.; Xie, S.; Zhu, R. Y.; Azzolini, V.; Calamba, A.; Carlson, B.; Ferguson, T.; Iiyama, Y.; Paulini, M.; Russ, J.; Sun, M.; Vogel, H.; Vorobiev, I.; Cumalat, J. P.; Ford, W. T.; Gaz, A.; Jensen, F.; Johnson, A.; Krohn, M.; Mulholland, T.; Nauenberg, U.; Smith, J. G.; Stenson, K.; Wagner, S. R.; Alexander, J.; Chatterjee, A.; Chaves, J.; Chu, J.; Dittmer, S.; Eggert, N.; Mirman, N.; Nicolas Kaufman, G.; Patterson, J. R.; Rinkevicius, A.; Ryd, A.; Skinnari, L.; Sun, W.; Tan, S. M.; Teo, W. D.; Thom, J.; Thompson, J.; Tucker, J.; Weng, Y.; Wittich, P.; Abdullin, S.; Albrow, M.; Anderson, J.; Apollinari, G.; Bauerdick, L. A. T.; Beretvas, A.; Berryhill, J.; Bhat, P. C.; Bolla, G.; Burkett, K.; Butler, J. N.; Cheung, H. W. K.; Chlebana, F.; Cihangir, S.; Elvira, V. D.; Fisk, I.; Freeman, J.; Gottschalk, E.; Gray, L.; Green, D.; Grünendahl, S.; Gutsche, O.; Hanlon, J.; Hare, D.; Harris, R. M.; Hirschauer, J.; Hooberman, B.; Hu, Z.; Jindariani, S.; Johnson, M.; Joshi, U.; Jung, A. W.; Klima, B.; Kreis, B.; Kwan, S.; Lammel, S.; Linacre, J.; Lincoln, D.; Lipton, R.; Liu, T.; Lopes De Sá, R.; Lykken, J.; Maeshima, K.; Marraffino, J. M.; Martinez Outschoorn, V. I.; Maruyama, S.; Mason, D.; McBride, P.; Merkel, P.; Mishra, K.; Mrenna, S.; Nahn, S.; Newman-Holmes, C.; O'Dell, V.; Prokofyev, O.; Sexton-Kennedy, E.; Soha, A.; Spalding, W. J.; Spiegel, L.; Taylor, L.; Tkaczyk, S.; Tran, N. V.; Uplegger, L.; Vaandering, E. W.; Vernieri, C.; Verzocchi, M.; Vidal, R.; Whitbeck, A.; Yang, F.; Yin, H.; Acosta, D.; Avery, P.; Bortignon, P.; Bourilkov, D.; Carnes, A.; Carver, M.; Curry, D.; Das, S.; Di Giovanni, G. P.; Field, R. D.; Fisher, M.; Furic, I. K.; Hugon, J.; Konigsberg, J.; Korytov, A.; Kypreos, T.; Low, J. F.; Ma, P.; Matchev, K.; Mei, H.; Milenovic, P.; Mitselmakher, G.; Muniz, L.; Rank, D.; Shchutska, L.; Snowball, M.; Sperka, D.; Wang, S. J.; Yelton, J.; Hewamanage, S.; Linn, S.; Markowitz, P.; Martinez, G.; Rodriguez, J. L.; Ackert, A.; Adams, J. R.; Adams, T.; Askew, A.; Bochenek, J.; Diamond, B.; Haas, J.; Hagopian, S.; Hagopian, V.; Johnson, K. F.; Khatiwada, A.; Prosper, H.; Veeraraghavan, V.; Weinberg, M.; Bhopatkar, V.; Hohlmann, M.; Kalakhety, H.; Mareskas-palcek, D.; Roy, T.; Yumiceva, F.; Adams, M. R.; Apanasevich, L.; Berry, D.; Betts, R. R.; Bucinskaite, I.; Cavanaugh, R.; Evdokimov, O.; Gauthier, L.; Gerber, C. E.; Hofman, D. J.; Kurt, P.; O'Brien, C.; Sandoval Gonzalez, I. D.; Silkworth, C.; Turner, P.; Varelas, N.; Wu, Z.; Zakaria, M.; Bilki, B.; Clarida, W.; Dilsiz, K.; Durgut, S.; Gandrajula, R. P.; Haytmyradov, M.; Khristenko, V.; Merlo, J.-P.; Mermerkaya, H.; Mestvirishvili, A.; Moeller, A.; Nachtman, J.; Ogul, H.; Onel, Y.; Ozok, F.; Penzo, A.; Sen, S.; Snyder, C.; Tan, P.; Tiras, E.; Wetzel, J.; Yi, K.; Anderson, I.; Barnett, B. A.; Blumenfeld, B.; Fehling, D.; Feng, L.; Gritsan, A. V.; Maksimovic, P.; Martin, C.; Nash, K.; Osherson, M.; Swartz, M.; Xiao, M.; Xin, Y.; Baringer, P.; Bean, A.; Benelli, G.; Bruner, C.; Gray, J.; Kenny, R. P.; Majumder, D.; Malek, M.; Murray, M.; Noonan, D.; Sanders, S.; Stringer, R.; Wang, Q.; Wood, J. S.; Chakaberia, I.; Ivanov, A.; Kaadze, K.; Khalil, S.; Makouski, M.; Maravin, Y.; Saini, L. K.; Skhirtladze, N.; Svintradze, I.; Lange, D.; Rebassoo, F.; Wright, D.; Anelli, C.; Baden, A.; Baron, O.; Belloni, A.; Calvert, B.; Eno, S. C.; Ferraioli, C.; Gomez, J. A.; Hadley, N. J.; Jabeen, S.; Kellogg, R. G.; Kolberg, T.; Kunkle, J.; Lu, Y.; Mignerey, A. C.; Pedro, K.; Shin, Y. H.; Skuja, A.; Tonjes, M. B.; Tonwar, S. C.; Apyan, A.; Barbieri, R.; Baty, A.; Bierwagen, K.; Brandt, S.; Busza, W.; Cali, I. A.; Di Matteo, L.; Gomez Ceballos, G.; Goncharov, M.; Gulhan, D.; Klute, M.; Kovalskyi, D.; Lai, Y. S.; Lee, Y.-J.; Levin, A.; Luckey, P. D.; Mcginn, C.; Niu, X.; Paus, C.; Ralph, D.; Roland, C.; Roland, G.; Stephans, G. S. F.; Sumorok, K.; Varma, M.; Velicanu, D.; Veverka, J.; Wang, J.; Wang, T. W.; Wyslouch, B.; Yang, M.; Zhukova, V.; Dahmes, B.; Finkel, A.; Gude, A.; Hansen, P.; Kalafut, S.; Kao, S. C.; Klapoetke, K.; Kubota, Y.; Mans, J.; Nourbakhsh, S.; Ruckstuhl, N.; Rusack, R.; Tambe, N.; Turkewitz, J.; Acosta, J. G.; Oliveros, S.; Avdeeva, E.; Bloom, K.; Bose, S.; Claes, D. R.; Dominguez, A.; Fangmeier, C.; Gonzalez Suarez, R.; Kamalieddin, R.; Keller, J.; Knowlton, D.; Kravchenko, I.; Lazo-Flores, J.; Meier, F.; Monroy, J.; Ratnikov, F.; Siado, J. E.; Snow, G. R.; Alyari, M.; Dolen, J.; George, J.; Godshalk, A.; Iashvili, I.; Kaisen, J.; Kharchilava, A.; Kumar, A.; Rappoccio, S.; Alverson, G.; Barberis, E.; Baumgartel, D.; Chasco, M.; Hortiangtham, A.; Massironi, A.; Morse, D. M.; Nash, D.; Orimoto, T.; Teixeira De Lima, R.; Trocino, D.; Wang, R.-J.; Wood, D.; Zhang, J.; Hahn, K. A.; Kubik, A.; Mucia, N.; Odell, N.; Pollack, B.; Pozdnyakov, A.; Schmitt, M.; Stoynev, S.; Sung, K.; Trovato, M.; Velasco, M.; Won, S.; Brinkerhoff, A.; Dev, N.; Hildreth, M.; Jessop, C.; Karmgard, D. J.; Kellams, N.; Lannon, K.; Lynch, S.; Marinelli, N.; Meng, F.; Mueller, C.; Musienko, Y.; Pearson, T.; Planer, M.; Ruchti, R.; Smith, G.; Valls, N.; Wayne, M.; Wolf, M.; Woodard, A.; Antonelli, L.; Brinson, J.; Bylsma, B.; Durkin, L. S.; Flowers, S.; Hart, A.; Hill, C.; Hughes, R.; Kotov, K.; Ling, T. Y.; Liu, B.; Luo, W.; Puigh, D.; Rodenburg, M.; Winer, B. L.; Wulsin, H. W.; Driga, O.; Elmer, P.; Hardenbrook, J.; Hebda, P.; Koay, S. A.; Lujan, P.; Marlow, D.; Medvedeva, T.; Mooney, M.; Olsen, J.; Palmer, C.; Piroué, P.; Quan, X.; Saka, H.; Stickland, D.; Tully, C.; Werner, J. S.; Zuranski, A.; Barnes, V. E.; Benedetti, D.; Bortoletto, D.; Gutay, L.; Jha, M. K.; Jones, M.; Jung, K.; Kress, M.; Leonardo, N.; Miller, D. H.; Neumeister, N.; Primavera, F.; Radburn-Smith, B. C.; Shi, X.; Shipsey, I.; Silvers, D.; Sun, J.; Svyatkovskiy, A.; Wang, F.; Xie, W.; Xu, L.; Zablocki, J.; Parashar, N.; Stupak, J.; Adair, A.; Akgun, B.; Chen, Z.; Ecklund, K. M.; Geurts, F. J. M.; Guilbaud, M.; Li, W.; Michlin, B.; Northup, M.; Padley, B. P.; Redjimi, R.; Roberts, J.; Rorie, J.; Tu, Z.; Zabel, J.; Betchart, B.; Bodek, A.; de Barbaro, P.; Demina, R.; Eshaq, Y.; Ferbel, T.; Galanti, M.; Garcia-Bellido, A.; Goldenzweig, P.; Han, J.; Harel, A.; Hindrichs, O.; Khukhunaishvili, A.; Petrillo, G.; Verzetti, M.; Vishnevskiy, D.; Demortier, L.; Arora, S.; Barker, A.; Chou, J. P.; Contreras-Campana, C.; Contreras-Campana, E.; Duggan, D.; Ferencek, D.; Gershtein, Y.; Gray, R.; Halkiadakis, E.; Hidas, D.; Hughes, E.; Kaplan, S.; Kunnawalkam Elayavalli, R.; Lath, A.; Panwalkar, S.; Park, M.; Salur, S.; Schnetzer, S.; Sheffield, D.; Somalwar, S.; Stone, R.; Thomas, S.; Thomassen, P.; Walker, M.; Foerster, M.; Riley, G.; Rose, K.; Spanier, S.; York, A.; Bouhali, O.; Castaneda Hernandez, A.; Dalchenko, M.; De Mattia, M.; Delgado, A.; Dildick, S.; Eusebi, R.; Flanagan, W.; Gilmore, J.; Kamon, T.; Krutelyov, V.; Montalvo, R.; Mueller, R.; Osipenkov, I.; Pakhotin, Y.; Patel, R.; Perloff, A.; Roe, J.; Rose, A.; Safonov, A.; Suarez, I.; Tatarinov, A.; Ulmer, K. A.; Akchurin, N.; Cowden, C.; Damgov, J.; Dragoiu, C.; Dudero, P. R.; Faulkner, J.; Kunori, S.; Lamichhane, K.; Lee, S. W.; Libeiro, T.; Undleeb, S.; Volobouev, I.; Appelt, E.; Delannoy, A. G.; Greene, S.; Gurrola, A.; Janjam, R.; Johns, W.; Maguire, C.; Mao, Y.; Melo, A.; Sheldon, P.; Snook, B.; Tuo, S.; Velkovska, J.; Xu, Q.; Arenton, M. W.; Boutle, S.; Cox, B.; Francis, B.; Goodell, J.; Hirosky, R.; Ledovskoy, A.; Li, H.; Lin, C.; Neu, C.; Wolfe, E.; Wood, J.; Xia, F.; Clarke, C.; Harr, R.; Karchin, P. E.; Kottachchi Kankanamge Don, C.; Lamichhane, P.; Sturdy, J.; Belknap, D. A.; Carlsmith, D.; Cepeda, M.; Christian, A.; Dasu, S.; Dodd, L.; Duric, S.; Friis, E.; Gomber, B.; Grothe, M.; Hall-Wilton, R.; Herndon, M.; Hervé, A.; Klabbers, P.; Lanaro, A.; Levine, A.; Long, K.; Loveless, R.; Mohapatra, A.; Ojalvo, I.; Perry, T.; Pierro, G. A.; Polese, G.; Ross, I.; Ruggles, T.; Sarangi, T.; Savin, A.; Smith, N.; Smith, W. H.; Taylor, D.; Woods, N.

2015-09-01

A search for pair production of neutral color-octet weak-triplet scalar particles (Θ0) is performed in processes where one Θ0 decays to a pair of b quark jets and the other to a Z boson plus a jet, with the Z boson decaying to a pair of electrons or muons. The search is performed with data collected by the CMS experiment at the CERN LHC corresponding to an integrated luminosity of 19.7 fb-1 of proton-proton collisions at √{s}=8 TeV. The number of observed events is found to be in agreement with the standard model predictions. The 95% confidence level upper limit on the product of the cross section and branching fraction is obtained as a function of the Θ0 mass. The 95% confidence level lower bounds on the Θ0 mass are found to be 623 and 426 GeV, for two different octo-triplet theoretical scenarios. These are the first direct experimental bounds on particles predicted by the octo-triplet model. [Figure not available: see fulltext.

Time-resolved EPR study on the photoexcited triplet state of the electron-donor-acceptor complex formed in the system of fac-tris[2-(4-octyl-phenyl) pyridine] iridium(III) and tetracene.

PubMed

Zhebin, Fu; Shuhei, Yoshioka; Hisao, Murai

2014-01-09

The physical properties of the phosphorescent organic light-emitting diode material fac-tris(phenylpyridine) iridium(III), Ir(ppy)3, have been reported with experimental and theoretical studies. Here, the photochemical properties of the excited triplet state of partially modified fac-tris[2-(4-octyl-phenyl) pyridine] iridium(III), Ir(C8ppy)3, were investigated using time-resolved electron paramagnetic resonance (tr-EPR) and optical methods by adding tetracene in the toluene solution. The tr-EPR observation at 77 K revealed the following two species: the excited triplet state of tetracene and another triplet species with zero field splitting parameters of |D| = 0.088 cm(-1) and |E| = 0.018 cm(-1) with characteristic spin polarization. The latter species was assigned to the electron-donor-acceptor (EDA) complex formed between Ir(C8ppy)3 and tetracene. The mechanism of formation and the properties of this EDA complex, including the information on the principal axes of (3)Ir(C8ppy)3*, are discussed.

Energy deposition studies for the high-luminosity Large Hadron Collider inner triplet magnets

DOE PAGES

Mokhov, N. V.; Rakhno, I. L.; Tropin, I. S.; ...

2015-05-06

A detailed model of the high-luminosity LHC inner triplet region with new large-aperture Nb 3Sn magnets, field maps, corrector packages, and segmented tungsten inner absorbers was built and implemented into the fluka and mars15 codes. Detailed simulations have been performed coherently with the codes on the impact of particle debris from the 14-TeV center-of-mass pp-collisions on the short- and long-term stability of the inner triplet magnets. After optimizing the absorber configuration, the peak power density averaged over the magnet inner cable width is found to be safely below the quench limit at the luminosity of 5×10 34 cm -2s -1.more » For the anticipated lifetime integrated luminosity of 3000 fb -1, the peak dose calculated for the innermost magnet insulator ranges from 20 to 35 MGy, a figure close to the commonly accepted limit. Dynamic heat loads to the triplet magnet cold mass are calculated to evaluate the cryogenic capability. fluka and mars results on energy deposition are in very good agreement.« less

Half-metallic superconducting triplet spin multivalves

NASA Astrophysics Data System (ADS)

Alidoust, Mohammad; Halterman, Klaus

2018-02-01

We study spin switching effects in finite-size superconducting multivalve structures. We examine F1F2SF3 and F1F2SF3F4 hybrids where a singlet superconductor (S) layer is sandwiched among ferromagnet (F) layers with differing thicknesses and magnetization orientations. Our results reveal a considerable number of experimentally viable spin-valve configurations that lead to on-off switching of the superconducting state. For S widths on the order of the superconducting coherence length ξ0, noncollinear magnetization orientations in adjacent F layers with multiple spin axes leads to a rich variety of triplet spin-valve effects. Motivated by recent experiments, we focus on samples where the magnetizations in the F1 and F4 layers exist in a fully spin-polarized half-metallic phase, and calculate the superconducting transition temperature, spatially and energy resolved density of states, and the spin-singlet and spin-triplet superconducting correlations. Our findings demonstrate that superconductivity in these devices can be completely switched on or off over a wide range of magnetization misalignment angles due to the generation of equal-spin and opposite-spin triplet pairings.

Quenching of cascade reaction between triplet and photochrome probes with nitroxide radicals. A novel labeling method in study of membranes and surface systems.

PubMed

Papper, V; Medvedeva, N; Fishov, I; Likhtenshtein, G I

2000-01-01

We proposed a new method for the study of molecular dynamics and fluidity of the living and model biomembranes and surface systems. The method is based on the measurements of the sensitized photoisomerization kinetics of a photochrome probe. The cascade triplet cis-trans photoisomerization of the excited stilbene derivative sensitized with the excited triplet Erythrosin B has been studied in a model liposome membrane. The photoisomerization reaction is depressed with nitroxide radicals quenching the excited triplet state of the sensitizer. The enhanced fluorescence polarization of the stilbene probe incorporated into liposome membranes indicates that the stilbene molecules are squeezed in a relatively viscous media of the phospholipids. Calibration of the "triple" cascade system is based on a previously proposed method that allows the measurement of the product of the quenching rate constant and the sensitizer's triplet lifetime, as well as the quantitative detection of the nitroxide radicals in the vicinity of the membrane surface. The experiment was conducted using the constant-illumination fluorescence technique. Sensitivity of the method using a standard commercial spectrofluorimeter is about 10(-12) mol of fluorescence molecules per sample and can be improved using an advanced fluorescence technique. The minimal local concentration of nitroxide radicals or any other quenchers being detected is about 10(-5) M. This method enables the investigation of any chemical and biological surface processes of microscopic scale when the minimal volume is about 10(-3) microL or less.

SU(2) slave-boson formulation of spin nematic states in S=(1)/(2) frustrated ferromagnets

NASA Astrophysics Data System (ADS)

Shindou, Ryuichi; Momoi, Tsutomu

2009-08-01

An SU(2) slave-boson formulation of bond-type spin nematic orders is developed in frustrated ferromagnets, where the spin nematic states are described as the resonating spin-triplet valence bond (RVB) states. The d vectors of spin-triplet pairing ansatzes play the role of the directors in the bond-type spin-quadrupolar states. The low-energy excitations around such spin-triplet RVB ansatzes generally comprise the (potentially massless) gauge bosons, massless Goldstone bosons, and spinon individual excitations. Extending the projective symmetry-group argument to the spin-triplet ansatzes, we show how to identify the number of massless gauge bosons efficiently. Applying this formulation, we next (i) enumerate possible mean-field solutions for the S=(1)/(2) ferromagnetic J1-J2 Heisenberg model on the square lattice, with ferromagnetic nearest neighbor J1 and competing antiferromagnetic next-nearest neighbor J2 and (ii) argue their stability against small gauge fluctuations. As a result, two stable spin-triplet RVB ansatzes are found in the intermediate coupling regime around J1:J2≃1:0.4 . One is the Z2 Balian-Werthamer (BW) state stabilized by the Higgs mechanism and the other is the SU(2) chiral p -wave (Anderson-Brinkman-Morel) state stabilized by the Chern-Simon mechanism. The former Z2 BW state in fact shows the same bond-type spin-quadrupolar order as found in the previous exact diagonalization study [Shannon , Phys. Rev. Lett. 96, 027213 (2006)].

Theoretical investigation of the photochemical C2-C6 cyclisation of enyne-heteroallenes.

PubMed

Spöler, Carsten; Engels, Bernd

2003-10-06

Herein we discuss computations that explain experimental results regarding a highly efficient triplet analogue of the C(2)-C(6) cyclisation of enyne-heteroallenes recently discovered by Schmittel and co-workers.1 To shed some light on the reasons for the differences found between enyne-carbodiimides, enyne-ketenimines and enyne-allenes, we have computed the reaction profiles of the C(2)-C(6) and of the C(2)-C(7) cyclisations for various model compounds, assuming that the reactions take place on the lowest-lying triplet surfaces. Our results nicely explain the differences and the unexpected high efficiency found for the enyne-carbodiimides. The differences between enyne-carbodiimides and enyne-ketenimines prove to be due to differences in the shapes of the corresponding triplet surfaces. In contrast to the enyne-carbodiimides, for which our calculations predict that a direct cyclisation to the biradical intermediates should occur after the vertical excitation, the enyne-ketenimines relax into a local minimum on the triplet surface. As a consequence, further reaction channels are opened. Our computations indicate that enyne-allene compounds do not react because the necessary excitation energy lies outside the range of the employed triplet photosensitizer. Finally, the close agreement between our results and the experimental findings indicates that the underlying reasons for the differences in the photochemical behaviour of enyne-carbodiimides, enyne-ketenimines and enyne-allenes are related to differences in the electronic structures of the parent systems, while substituent effects are less important.

Triplet–triplet energy transfer in artificial and natural photosynthetic antennas

PubMed Central

Ho, Junming; Kish, Elizabeth; Méndez-Hernández, Dalvin D.; WongCarter, Katherine; Pillai, Smitha; Kodis, Gerdenis; Niklas, Jens; Poluektov, Oleg G.; Gust, Devens; Moore, Thomas A.; Moore, Ana L.; Batista, Victor S.

2017-01-01

In photosynthetic organisms, protection against photooxidative stress due to singlet oxygen is provided by carotenoid molecules, which quench chlorophyll triplet species before they can sensitize singlet oxygen formation. In anoxygenic photosynthetic organisms, in which exposure to oxygen is low, chlorophyll-to-carotenoid triplet–triplet energy transfer (T-TET) is slow, in the tens of nanoseconds range, whereas it is ultrafast in the oxygen-rich chloroplasts of oxygen-evolving photosynthetic organisms. To better understand the structural features and resulting electronic coupling that leads to T-TET dynamics adapted to ambient oxygen activity, we have carried out experimental and theoretical studies of two isomeric carotenoporphyrin molecular dyads having different conformations and therefore different interchromophore electronic interactions. This pair of dyads reproduces the characteristics of fast and slow T-TET, including a resonance Raman-based spectroscopic marker of strong electronic coupling and fast T-TET that has been observed in photosynthesis. As identified by density functional theory (DFT) calculations, the spectroscopic marker associated with fast T-TET is due primarily to a geometrical perturbation of the carotenoid backbone in the triplet state induced by the interchromophore interaction. This is also the case for the natural systems, as demonstrated by the hybrid quantum mechanics/molecular mechanics (QM/MM) simulations of light-harvesting proteins from oxygenic (LHCII) and anoxygenic organisms (LH2). Both DFT and electron paramagnetic resonance (EPR) analyses further indicate that, upon T-TET, the triplet wave function is localized on the carotenoid in both dyads. PMID:28652359

Triplets of galaxies: Their dynamics, evolution, and the origin of chaos in them

NASA Technical Reports Server (NTRS)

Chernin, Arthur D.; Ivanov, Alexei V.

1990-01-01

Recently Karachentsev's group at The Smithsonian Astrophysical Observatory (SAO) (6-meter Telescope Observatory) published a list of 84 triple systems of galaxies with their distances, radial (line of sight) velocities, and angular sizes (Karachentseva et al., 1988). This gives a new ground for studies of the dark matter problem which fills the gap between the large cosmic scales (White, 1987; Dekel and Rees, 1987, and Einasto et al., 1977) and the scale of individual galaxies (Erickson et al., 1987). The data on the typical velocity dispersions and linear dimension of the triplets indicate that they contain considerable amounts of dark matter (see also earlier work of Karachentseva et al., 1979). Numerical simulations show that the statistical characteristics of the Karachentsev triplets can be imitated by model ensembles of triple systems with dark matter masses M sub d = (1-3 x 10(exp 12) M sub O, which is almost ten times greater than the typical mass of stellar galaxies estimated by the standard mass-to-luminosity ration (Kiseleva and Chernin, 1988). Here, the authors report that important information can be drawn from the data on the visible configurations of these systems. The statistics of configurations provide an independent evidence for dark matter in the triplets; moreover, it enables one to argue that dark matter seems to be distributed over the whole volume of the typical triplet forming its common corona rather than concentrated within individual coronae (or haloes) of the member galaxies.

Enhanced Access to the Dark Triplet States of 7Li 2 through New Singlet-Triplet A1Σ +u ˜ b3Π u Perturbation Window Levels: Perturbation-Facilitated Optical-Optical Double Resonance Study of the 2 3Σ +g State

NASA Astrophysics Data System (ADS)

Lazarov, Guenadiy; Lyyra, A. Marjatta; Li, Li

2001-01-01

Two new pairs of singlet-triplet A1Σ+u ∼ b3Πu mixed levels of 7Li2 have been observed and used here as 'window' levels in cw perturbation-facilitated optical-optical double-resonance (PFOODR) experiments. Previously, only one b3Πu vibrational level, v = 19, was known to mix with the singlet A1Σ+uv = 13 level, resulting in three perturbed A ∼ b pairs [L. Li, T. An, T.-J. Whang, A. M. Lyyra, W. C. Stwalley, R. W. Field, and R. A. Bernheim, J. Chem. Phys. 96, 3342 (1992)]. The scarcity of window levels and the resulting difficulty in accessing the dark triplet states of Li2 is caused by the weak spin-orbit interaction of Li2. The two new mixed b3Πuv = 15 and 22 levels reported here enhance access to the dark triplet state manifold through expansion of the Franck-Condon overlap factor range. Furthermore, the earlier range of accessible rotational levels, N = 5, 7, and 10, is now expanded to include N = 8 and N = 16, thereby allowing for more reliable determination of the excited triplet states rotational structure. To demonstrate the importance of the new A1Σ+u ∼ b3Πu mixed levels, we have studied the 23Σ+g state by cw PFOODR fluorescence excitation spectroscopy. New molecular constants and RKR potential curve have been determined. As previously reported [L. Li, G. Lazarov, and A. M. Lyyra, J. Mol. Spectrosc. 191, 387 (1998)], the 23Σ+g state interacts with the repulsive 13Πg state by L-uncoupling and predissociates. We show that some 23Πg levels predissociate accidentally by the 13Πg state via the 23Σ+g state through L-uncoupling.

Effect of olanzapine for breast cancer patients resistant to triplet antiemetic therapy with nausea due to anthracycline-containing adjuvant chemotherapy.

PubMed

Sato, Junya; Kashiwaba, Masahiro; Komatsu, Hideaki; Ishida, Kazushige; Nihei, Satoru; Kudo, Kenzo

2016-05-01

Triplet antiemetic therapy with neurokinin 1 receptor blocker, 5-hydroxytryptamine receptor blocker and steroids is commonly used in patients who are highly emetic after chemotherapy. However, an alternative antiemetic therapy for patients who are resistant to triplet antiemetic therapy is not established. Olanzapine is recommended in the guidelines as an optional antiemetic drug. However, the effectiveness of adding olanzapine to triplet antiemetic therapy is unknown. In this study, the effectiveness and safety of adding olanzapine to triplet antiemetic therapy with aprepitant, palonosetron and dexamethasone as highly emetic anthracycline-containing adjuvant chemotherapy for primary breast cancer patients were prospectively investigated. Forty-five patients with breast cancer who experienced >Grade 1 nausea or any vomiting after the first cycle of chemotherapy using both epirubicin and cyclophosphamide were included. Low-dose olanzapine (2.5 mg/day) was administered orally from the first day of chemotherapy for 4 days, and the number of episodes of vomiting, scale of nausea, dietary intake and somnolence were compared with the symptoms after the first cycle. As the primary endpoint, the nausea grade was significantly improved by adding olanzapine (P < 0.05). As the secondary endpoints, mean nausea scale (3.2→1.9, Day 1; 3→1.3-1, Days 2-6) and dietary intake (33.6→53.8%, Day 1; 42.0→60.7-78.1%, Days 2-6) were improved by adding olanzapine. Only four patients withdrew due to somnolence and/or dizziness. This study demonstrated the effectiveness and tolerability of adding low-dose olanzapine for patients with insufficient nausea relief with triplet antiemetic therapy consisting of palonosetron, steroid and aprepitant. Published by Oxford University Press 2016. This work is written by (a) US Government employee(s) and is in the public domain in the US.

Singlet versus Triplet Excited State Mediated Photoinduced Dehalogenation Reactions of Itraconazole in Acetonitrile and Aqueous Solutions.

PubMed

Zhu, Ruixue; Li, Ming-de; Du, Lili; Phillips, David Lee

2017-04-06

Photoinduced dehalogenation of the antifungal drug itraconazole (ITR) in acetonitrile (ACN) and ACN/water mixed solutions was investigated using femtosecond and nanosecond time-resolved transient absorption (fs-TA and ns-TA, respectively) and nanosecond time-resolved resonance Raman spectroscopy (ns-TR 3 ) experiments. An excited resonance energy transfer is found to take place from the 4-phenyl-4,5-dihydro-3H-1,2,4-triazol-3-one part of the molecule to the 1,3-dichlorobenzene part of the molecule when ITR is excited by ultraviolet light. This photoexcitation is followed by a fast carbon-halogen bond cleavage that leads to the generation of radical intermediates via either triplet and/or singlet excited states. It is found that the singlet excited state-mediated carbon-halogen cleavage is the predominant dehalogenation process in ACN solvent, whereas a triplet state-mediated carbon-halogen cleavage prefers to occur in the ACN/water mixed solutions. The singlet-to-triplet energy gap is decreased in the ACN/water mixed solvents and this helps facilitate an intersystem crossing process, and thus, the carbon-halogen bond cleavage happens mostly through an excited triplet state in the aqueous solutions examined. The ns-TA and ns-TR 3 results also provide some evidence that radical intermediates are generated through a homolytic carbon-halogen bond cleavage via predominantly the singlet excited state pathway in ACN but via mainly the triplet state pathway in the aqueous solutions. In strong acidic solutions, protonation at the oxygen and/or nitrogen atoms of the 1,2,4-triazole-3-one group appears to hinder the dehalogenation reactions. This may offer the possibility that the phototoxicity of ITR due to the generation of aryl or halogen radicals can be reduced by protonation of certain moieties in suitably designed ITR halogen-containing derivatives.

Theoretical study of triplet state properties of free-base porphin

NASA Astrophysics Data System (ADS)

Loboda, Oleksandr; Tunell, Ingvar; Minaev, Boris; Ågren, Hans

2005-06-01

This paper presents results and analysis of various properties of the triplet state of free-base porphin (FBP) as calculated by density-functional theory. The radiative lifetime of phosphorescence lines and microwave signals in optical detection of magnetic resonance (ODMR) spectra are obtained using the B3LYP hybrid density-functional and the quadratic response method. The zero-field splitting (ZFS) in the lowest triplet state, a3 B2u, of FBP is calculated as an expectation value of spin-spin coupling operator using the self-consistent field wavefunction. The second-order contribution to ZFS from the spin-orbit coupling operator is found to be almost negligible. The interpretation of the ODMR spectrum is completed by computing the hyperfine tensors of the 14N, 13C and hydrogen atoms in the lowest triplet state. The most intense phosphorescence emission corresponds to the Tz-spin-sublevel of the a3 B2u state, where the z-axis lies in the N-H direction of the FBP molecule in a qualitative agreement with ODMR data. The results indicate that the observed decay of the lowest triplet state of FBP molecule is determined by non-radiative deactivation. The calculated radiative rate constant for the Tz-spin-sublevel kz = 2.65 × 10-3 s-1 is in agreement with the value kz ≃ 2 × 10-3 s-1, estimated by van Dorp et al. [W. van Dorp, W. Schoemaker, M. Soma, J. van der Waals, Mol. Phys. 30 (1975) 1701] from kinetic analysis of microwave-induced fluorescent signals. The correct prediction of the spin quantization axis of the most active spin sublevel and of its radiative lifetime in the lowest triplet state of the FBP molecule is taken as a proof of capability of the quadratic response time-dependent density-functional theory.

Text Mining Genotype-Phenotype Relationships from Biomedical Literature for Database Curation and Precision Medicine.

PubMed

Singhal, Ayush; Simmons, Michael; Lu, Zhiyong

2016-11-01

The practice of precision medicine will ultimately require databases of genes and mutations for healthcare providers to reference in order to understand the clinical implications of each patient's genetic makeup. Although the highest quality databases require manual curation, text mining tools can facilitate the curation process, increasing accuracy, coverage, and productivity. However, to date there are no available text mining tools that offer high-accuracy performance for extracting such triplets from biomedical literature. In this paper we propose a high-performance machine learning approach to automate the extraction of disease-gene-variant triplets from biomedical literature. Our approach is unique because we identify the genes and protein products associated with each mutation from not just the local text content, but from a global context as well (from the Internet and from all literature in PubMed). Our approach also incorporates protein sequence validation and disease association using a novel text-mining-based machine learning approach. We extract disease-gene-variant triplets from all abstracts in PubMed related to a set of ten important diseases (breast cancer, prostate cancer, pancreatic cancer, lung cancer, acute myeloid leukemia, Alzheimer's disease, hemochromatosis, age-related macular degeneration (AMD), diabetes mellitus, and cystic fibrosis). We then evaluate our approach in two ways: (1) a direct comparison with the state of the art using benchmark datasets; (2) a validation study comparing the results of our approach with entries in a popular human-curated database (UniProt) for each of the previously mentioned diseases. In the benchmark comparison, our full approach achieves a 28% improvement in F1-measure (from 0.62 to 0.79) over the state-of-the-art results. For the validation study with UniProt Knowledgebase (KB), we present a thorough analysis of the results and errors. Across all diseases, our approach returned 272 triplets (disease-gene-variant) that overlapped with entries in UniProt and 5,384 triplets without overlap in UniProt. Analysis of the overlapping triplets and of a stratified sample of the non-overlapping triplets revealed accuracies of 93% and 80% for the respective categories (cumulative accuracy, 77%). We conclude that our process represents an important and broadly applicable improvement to the state of the art for curation of disease-gene-variant relationships.

Three-dimensional parabolic equation models of the acoustic coverage of the CTBT hydrophone station at Crozet

NASA Astrophysics Data System (ADS)

Zampolli, Mario; Haralabus, Georgios; Prior, Mark K.; Heaney, Kevin D.; Campbell, Richard

2014-05-01

Hydrophone stations of the Comprehensive Nuclear-Test-Ban Organisation (CTBTO) International Monitoring System (IMS), with the exception of one in Australia, comprise two triplets of submerged moored hydrophones, one North and one South of the island from which the respective system is deployed. Triplet distances vary approximately between 50 - 100 km from the island, with each triplet connected to the receiving shore equipment by fibre-optic submarine data cables. Once deployed, the systems relay underwater acoustic waveforms in the band 1 - 100 Hz in real time to Vienna via a shore based satellite link. The design life of hydroacoustic stations is at least 20 years, without need for any maintenance of the underwater system. The re-establishment of hydrophone monitoring station HA04 at Crozet (French Southern and Antarctic Territories) in the South-Western Indian Ocean is currently being investigated. In order to determine appropriate locations and depths for the installation of the hydrophones a number of constraints need to be taken into account and balanced against each other. The most important of these are (i) hydrophone depth in a region where the sound-speed profile is mostly upward refracting and the Sound Fixing and Ranging (SOFAR) channel is not well defined, (ii) a safe distance from the surface currents which occupy the first few hundred meters of the water column, (iii) seabed slopes that enable the safe deployment of the hydrophone mooring bases, (iv) avoidance of regions of high internal tide activity, (v) choice of locations to optimize basin and cross-basin scale acoustic coverage of each triplet and (vi) redundancy considerations so that one triplet can partially cover for the other one in case of necessity. A state-of-the-art three-dimensional (3-D) parabolic equation acoustic propagation model was used to model the propagation for a number of potential triplet locations. Criteria for short-listing candidate triplet locations were based on acoustic coverage towards the North and South, as well as overall acoustic coverage, taking into account different scales of source strength. An increase in the predicted area coverage compared to predictions based on 2-D modelling was observed and attributed to diffraction around sharp localized features such as islands or sea-mounts.

Soft collinear effective theory for heavy WIMP annihilation

DOE PAGES

Bauer, Martin; Cohen, Timothy; Hill, Richard J.; ...

2015-01-19

In a large class of models for Weakly Interacting Massive Particles (WIMPs), the WIMP mass M lies far above the weak scale m W . This work identifies universal Sudakov-type logarithms ~ α log 2(2 M/m W) that spoil the naive convergence of perturbation theory for annihilation processes. An effective field theory (EFT) framework is presented, allowing the systematic resummation of these logarithms. Another impact of the large separation of scales is that a long-distance wavefunction distortion from electroweak boson exchange leads to observable modifications of the cross section. Careful accounting of momentum regions in the EFT allows the rigorousmore » disentanglement of this so-called Sommerfeld enhancement from the short-distance hard annihilation process. In addition, the WIMP is described as a heavy-particle field, while the electroweak gauge bosons are treated as soft and collinear fields. Hard matching coefficients are computed at renormalization scale μ ~ 2 M , then evolved down to μ ~ m W , where electroweak symmetry breaking is incorporated and the matching onto the relevant quantum mechanical Hamiltonian is performed. The example of an SU(2) W triplet scalar dark matter candidate annihilating to line photons is used for concreteness, allowing the numerical exploration of the impact of next-to-leading order corrections and log resummation. As a result, for M ≃ 3 TeV, the resummed Sommerfeld enhanced cross section is reduced by a factor of ~ 3 with respect to the treelevel fixed order result.« less

Macro, Submicro, and Symbolic: The Many Faces of the Chemistry "Triplet"

ERIC Educational Resources Information Center

Talanquer, Vicente

2011-01-01

The idea that chemical knowledge can be represented in three main ways: macro, submicro, and symbolic (chemistry triplet) has become paradigmatic in chemistry and science education. It has served both as the base of theoretical frameworks that guide research in chemical education and as a central idea in various curriculum projects. However, this…

Tri-P-LETS: Changing the Face of High School Computer Science

ERIC Educational Resources Information Center

Sherrell, Linda; Malasri, Kriangsiri; Mills, David; Thomas, Allen; Greer, James

2012-01-01

From 2004-2007, the University of Memphis carried out the NSF-funded Tri-P-LETS (Three P Learning Environment for Teachers and Students) project to improve local high-school computer science curricula. The project reached a total of 58 classrooms in eleven high schools emphasizing problem solving skills, programming concepts as opposed to syntax,…

Vaporisation of a dicationic ionic liquid.

PubMed

Lovelock, Kevin R J; Deyko, Alexey; Corfield, Jo-Anne; Gooden, Peter N; Licence, Peter; Jones, Robert G

2009-02-02

Highest heat of vaporization yet: The dicationic ionic liquid [C(3)(C(1)Im)(2)][Tf(2)N](2) evaporates as a neutral ion triplet. These neutral ion triplets can then be ionised to form singly and doubly charged ions. The mass spectrum exhibits the dication attached to one remaining anion, and the naked dication itself (see picture).

Optimal design of FIR triplet halfband filter bank and application in image coding.

PubMed

Kha, H H; Tuan, H D; Nguyen, T Q

2011-02-01

This correspondence proposes an efficient semidefinite programming (SDP) method for the design of a class of linear phase finite impulse response triplet halfband filter banks whose filters have optimal frequency selectivity for a prescribed regularity order. The design problem is formulated as the minimization of the least square error subject to peak error constraints and regularity constraints. By using the linear matrix inequality characterization of the trigonometric semi-infinite constraints, it can then be exactly cast as a SDP problem with a small number of variables and, hence, can be solved efficiently. Several design examples of the triplet halfband filter bank are provided for illustration and comparison with previous works. Finally, the image coding performance of the filter bank is presented.

Singlet-triplet splittings from the virial theorem and single-particle excitation energies

NASA Astrophysics Data System (ADS)

Becke, Axel D.

2018-01-01

The zeroth-order (uncorrelated) singlet-triplet energy difference in single-particle excited configurations is 2Kif, where Kif is the Coulomb self-energy of the product of the transition orbitals. Here we present a non-empirical, virial-theorem argument that the correlated singlet-triplet energy difference should be half of this, namely, Kif. This incredibly simple result gives vertical HOMO-LUMO excitation energies in small-molecule benchmarks as good as the popular TD-B3LYP time-dependent approach to excited states. For linear acenes and nonlinear polycyclic aromatic hydrocarbons, the performance is significantly better than TD-B3LYP. In addition to the virial theorem, the derivation borrows intuitive pair-density concepts from density-functional theory.

Enantioselective photochemistry via Lewis acid catalyzed triplet energy transfer

PubMed Central

Blum, Travis R.; Miller, Zachary D.; Bates, Desiree M.; Guzei, Ilia A.; Yoon, Tehshik P.

2017-01-01

Relatively few catalytic systems are able to control the stereochemistry of electronically excited organic intermediates. Here we report the discovery that a chiral Lewis acid complex can catalyze triplet energy transfer from an electronically excited photosensitizer. This strategy is applied to asymmetric [2+2] photocycloadditions of 2′-hydroxychalcones using tris(bipyridyl) ruthenium(II) as a sensitizer. A variety of electrochemical, computational, and spectroscopic data rule out substrate activation via photoinduced electron transfer and instead support a mechanism in which Lewis acid coordination dramatically lowers the triplet energy of the chalcone substrate. We expect that this approach will enable chemists to more broadly apply their detailed understanding of chiral Lewis acid catalysis to stereocontrol in reactions of electronically excited states. PMID:27980203

Molecular excited states from the SCAN functional

NASA Astrophysics Data System (ADS)

Tozer, David J.; Peach, Michael J. G.

2018-06-01

The performance of the strongly constrained and appropriately normed (SCAN) meta-generalised gradient approximation exchange-correlation functional is investigated for the calculation of time-dependent density-functional theory molecular excitation energies of local, charge-transfer and Rydberg character, together with the excited ? potential energy curve in H2. The SCAN results frequently resemble those obtained using a global hybrid functional, with either a standard or increased fraction of exact orbital exchange. For local excitations, SCAN can exhibit significant triplet instability problems, resulting in imaginary triplet excitation energies for a number of cases. The Tamm-Dancoff approximation offers a simple approach to improve the situation, but the excitation energies are still significantly underestimated. Understanding the origin of these (near)-triplet instabilities may provide useful insight into future functional development.

q-triplet for Brazos River discharge: The edge of chaos?

NASA Astrophysics Data System (ADS)

Stosic, Tatijana; Stosic, Borko; Singh, Vijay P.

2018-04-01

We study the daily discharge data of Brazos River in Texas, USA, from 1900 to 2017, in terms of concepts drawn from the non-extensive statistics recently introduced by Tsallis. We find that the Brazos River discharge indeed follows non-extensive statistics regarding equilibrium, relaxation and sensitivity. Besides being the first such finding of a full-fledged q-triplet in hydrological data with possible future impact on water resources management, the fact that all three Tsallis q-triplet values are remarkably close to those of the logistic map at the onset of chaos opens up new questions towards a deeper understanding of the Brazos River dynamics, that may prove relevant for hydrological research in a more general sense.

Effect of electron spin-spin interaction on level crossings and spin flips in a spin-triplet system

NASA Astrophysics Data System (ADS)

Jia, Wei; Hu, Fang-Qi; Wu, Ning; Zhao, Qing

2017-12-01

We study level crossings and spin flips in a system consisting of a spin-1 (an electron spin triplet) coupled to a nuclear spin of arbitrary size K , in the presence of a uniform magnetic field and the electron spin-spin interaction within the triplet. Through an analytical diagonalization based on the SU (3 ) Lie algebra, we find that the electron spin-spin interaction not only removes the curious degeneracy which appears in the absence of the interaction, but also produces some level anticrossings (LACs) for strong interactions. The real-time dynamics of the system shows that periodic spin flips occur at the LACs for arbitrary K , which might provide an option for nuclear or electron spin polarization.

Design and construction of a high-energy photon polarimeter

NASA Astrophysics Data System (ADS)

Dugger, M.; Ritchie, B. G.; Sparks, N.; Moriya, K.; Tucker, R. J.; Lee, R. J.; Thorpe, B. N.; Hodges, T.; Barbosa, F. J.; Sandoval, N.; Jones, R. T.

2017-09-01

We report on the design and construction of a high-energy photon polarimeter for measuring the degree of polarization of a linearly-polarized photon beam. The photon polarimeter uses the process of pair production on an atomic electron (triplet production). The azimuthal distribution of scattered atomic electrons following triplet production yields information regarding the degree of linear polarization of the incident photon beam. The polarimeter, operated in conjunction with a pair spectrometer, uses a silicon strip detector to measure the recoil electron distribution resulting from triplet photoproduction in a beryllium target foil. The analyzing power ΣA for the device using a 75 μm beryllium converter foil is about 0.2, with a relative systematic uncertainty in ΣA of 1.5%.

The examination of berberine excited state by laser flash photolysis

NASA Astrophysics Data System (ADS)

Cheng, Lingli; Wang, Mei; Zhao, Ping; Zhu, Hui; Zhu, Rongrong; Sun, Xiaoyu; Yao, Side; Wang, Shilong

2009-07-01

The property of the excited triplet state of berberine (BBR) was investigated by using time-resolved laser flash photolysis of 355 nm in acetonitrile. The transient absorption spectra of the excited triplet BBR were obtained in acetonitrile, which have an absorption maximum at 420 nm. And the ratio of excitation to ionization of BBR in acetonitrile solvent was calculated. The self-decay and self-quenching rate constants, and the absorption coefficient of 3BBR* were investigated and the excited state quantum yield was determined. Furthermore utilizing the benzophenone (BEN) as a triplet sensitizer, and the β-carotene (Car) as an excited energy transfer acceptor, the assignment of 3BBR* was further confirmed and the related energy transfer rate constants were also determined.

Final Progress Report

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

Josef Michl

2011-10-31

In this project we have established guidelines for the design on organic chromophores suitable for producing high triplet yields via singlet fission. We have proven their utility by identifying a chromophore of a structural class that had never been examined for singlet fission before, 1,3-diphenylisobenzofuran, and demonstrating in two independent ways that a thin layer of this material produces a triplet yield of 200% within experimental error. We have also designed a second chromophore of a very different type, again of a structural class that had not been examined for singlet fission before, and found that in a thin layermore » it produces a 70% triplet yield. Finally, we have enhanced the theoretical understanding of the quantum mechanical nature of the singlet fission process.« less

Three-particle correlation functions of quasi-two-dimensional one-component and binary colloid suspensions.

PubMed

Ho, Hau My; Lin, Binhua; Rice, Stuart A

2006-11-14

We report the results of experimental determinations of the triplet correlation functions of quasi-two-dimensional one-component and binary colloid suspensions in which the colloid-colloid interaction is short ranged. The suspensions studied range in density from modestly dilute to solid. The triplet correlation function of the one-component colloid system reveals extensive ordering deep in the liquid phase. At the same density the ordering of the larger diameter component in a binary colloid system is greatly diminished by a very small amount of the smaller diameter component. The possible utilization of information contained in the triplet correlation function in the theory of melting of a quasi-two-dimensional system is briefly discussed.

Exciton Dynamics in Alternative Solar Cell Materials: Polymers, Nanocrystals, and Small Molecules

NASA Astrophysics Data System (ADS)

Pundsack, Thomas J.

To keep fossil fuel usage in 2040 even with 2010 usage, 50% of global energy will need to come from alternative sources such as solar cells. While the photovoltaic market is currently dominated by crystalline silicon, there are many low-cost solar cell materials such as conjugated polymers, semiconductor nanocrystals, and organic small molecules which could compete with fossil fuels. To create cost-competitive devices, understanding the excited state dynamics of these materials is necessary. The first section of this thesis looks at aggregation in poly(3-hexylthiophene) (P3HT) which is commonly used in organic photovoltaics. The amount of aggregation in P3HT thin films was controlled by using a mixture of regioregular and regiorandom P3HT. Even with few aggregates present, excited states were found to transfer from amorphous to aggregate domains in <50 fs which could indicate efficient long-range energy transfer. To further study P3HT aggregation, a triblock consisting of two P3HT chains with a coil polymer between them was investigated. By changing solvents, aggregation was induced in a stable and reversible manner allowing for spectroscopic studies of P3HT aggregates in solution. The polarity of the solvent was adjusted, and no change in excited state dynamics was observed implying the excited state has little charge-transfer character. Next, the conduction band density of states for copper zinc tin sulfide nanocrystals (CZTS NCs) was measured using pump-probe spectroscopy and found to be in agreement with theoretical results. The density of states shifted and dilated for smaller NCs indicative of quantum confinement. The excited state lifetime was found to be short (<20 ps) and independent of NC size which could limit the efficiency of CZTS photovoltaic devices. Finally, triplet-triplet annihilation (TTA) was studied in platinum octaethylporphyrin (PtOEP) thin films. By analyzing pump-probe spectra, the product of TTA in PtOEP thin films was assigned to a long-lived metal-centered state. To elucidate the mechanism of TTA, the annihilation dynamics were modeled using second order kinetics as well as Forster and Dexter energy transfer. Dexter energy transfer provided the best fits and the most reasonable fitting parameters.

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

NASA Astrophysics Data System (ADS)

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

2017-02-01

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

Unveiling Singlet Fission Mediating States in TIPS-pentacene and its Aza Derivatives.

PubMed

Herz, Julia; Buckup, Tiago; Paulus, Fabian; Engelhart, Jens U; Bunz, Uwe H F; Motzkus, Marcus

2015-06-25

Femtosecond pump-depletion-probe experiments were carried out in order to shed light on the ultrafast excited-state dynamics of triisopropylsilylethynyl (TIPS)-pentacene and two nitrogen-containing derivatives, namely, diaza-TIPS-pentacene and tetraaza-TIPS-pentacene. Measurements performed in the visible and near-infrared spectral range in combination with rate model simulations reveal that singlet fission proceeds via the extremely short-lived intermediate (1)TT state, which absorbs in the near-infrared spectral region only. The T1 → T3 transition probed in the visible region shows a rise time that comprises two components according to a consecutive reaction (S1 → (1)TT → T1). The incorporation of nitrogen atoms into the acene structure leads to shorter dynamics, but the overall triplet formation follows the same kinetic model. This is of particular importance, since experiments on tetraaza-TIPS-pentacene allow for investigation of the triplet state in the visible range without an overlapping singlet contribution. In addition, the pump-depletion-probe experiments show that the triplet absorption in the visible (T1 → T3) and near-infrared (T1 → T2) regions occurs from the same initial state, which was questioned in previous studies. Furthermore, an additional ultrafast transfer between the excited triplet states (T3 → T2) is identified, which is also in agreement with the rate model simulation. By applying depletion pulses, which are resonant with higher vibrational levels, we gain insight into internal vibrational energy redistribution processes within the triplet manifold. This additional information is of great relevance regarding the study of loss channels within these materials.

A Comparison Between Magnetic Field Effects in Excitonic and Exciplex Organic Light-Emitting Diodes

NASA Astrophysics Data System (ADS)

Sahin Tiras, Kevser; Wang, Yifei; Harmon, Nicholas J.; Wohlgenannt, Markus; Flatte, Michael E.

In flat-panel displays and lighting applications, organic light emitting diodes (OLEDs) have been widely used because of their efficient light emission, low-cost manufacturing and flexibility. The electrons and holes injected from the anode and cathode, respectively, form a tightly bound exciton as they meet at a molecule in organic layer. Excitons occur as spin singlets or triplets and the ratio between singlet and triplet excitons formed is 1:3 based on spin degeneracy. The internal quantum efficiency (IQE) of fluorescent-based OLEDs is limited 25% because only singlet excitons contribute the light emission. To overcome this limitation, thermally activated delayed fluorescent (TADF) materials have been introduced in the field of OLEDs. The exchange splitting between the singlet and triplet states of two-component exciplex systems is comparable to the thermal energy in TADF materials, whereas it is usually much larger in excitons. Reverse intersystem crossing occurs from triplet to singlet exciplex state, and this improves the IQE. An applied small magnetic field can change the spin dynamics of recombination in TADF blends. In this study, magnetic field effects on both excitonic and exciplex OLEDs will be presented and comparison similarities and differences will be made.

Intransitivity is infrequent and fails to promote annual plant coexistence without pairwise niche differences.

PubMed

Godoy, Oscar; Stouffer, Daniel B; Kraft, Nathan J B; Levine, Jonathan M

2017-05-01

Intransitive competition is often projected to be a widespread mechanism of species coexistence in ecological communities. However, it is unknown how much of the coexistence we observe in nature results from this mechanism when species interactions are also stabilized by pairwise niche differences. We combined field-parameterized models of competition among 18 annual plant species with tools from network theory to quantify the prevalence of intransitive competitive relationships. We then analyzed the predicted outcome of competitive interactions with and without pairwise niche differences. Intransitive competition was found for just 15-19% of the 816 possible triplets, and this mechanism was never sufficient to stabilize the coexistence of the triplet when the pair-wise niche differences between competitors were removed. Of the transitive and intransitive triplets, only four were predicted to coexist and these were more similar in multidimensional trait space defined by 11 functional traits than non-coexisting triplets. Our results argue that intransitive competition may be less frequent than recently posed, and that even when it does operate, pairwise niche differences may be key to possible coexistence. © 2017 by the Ecological Society of America.

The nature of trapping sites and recombination centres in PVK and PVK-PBD electroluminescent matrices seen by spectrally resolved thermoluminescence

NASA Astrophysics Data System (ADS)

Glowacki, Ireneusz; Szamel, Zbigniew

2010-07-01

Two electroluminescent polymer matrices poly(N-vinylcarbazole) (PVK) and PVK with 40 wt% of 2-tert-butylphenyl-5-biphenyl-1,3,4-oxadiazole (PBD) were studied using spectrally resolved thermoluminescence (SRTL) in the temperature range 15-325 K. The comparison of the SRTL results with the electroluminescence (EL) spectra has allowed identification of the localized (trapping) sites and the radiative recombination centres present in the investigated matrices. In the neat PVK films deep traps with a depth about 200 meV, related to triplet excimers dominate, while in the PVK-PBD (40 wt%) blend films the traps that are related to triplet exciplexes formed by the carbazole groups and the PBD molecules dominate. Depth of the traps in the PVK-PBD blend is somewhat lower than that in the neat PVK. An analysis of the EL spectra shows that in the PVK and in the PVK-PBD blend the dominant radiative centres are singlet excimers and singlet exciplexes, respectively. However, in the neat PVK some contributions of the triplet monomer and the triplet excimer states in the EL were also detected.

Preliminary results for a higher-precision measurement of the helium n=2 triplet P fine structure

NASA Astrophysics Data System (ADS)

Kato, K.; Skinner, T. D. G.; George, M. C.; Fitzakerley, D. W.; Vutha, A. C.; Storry, C. H.; Bezginov, N.; Valdez, T.; Hessels, E. A.

2017-04-01

Preliminary results for a higher-precision measurement of the n=2 triplet P J=1 to J=2 fine-structure interval in atomic helium are presented. A beam of metastable helium atoms is created in a liquid-nitrogen-cooled dc-discharge source, and is intensified using a 2D-MOT. These atoms are excited to the 2 triplet P state, and undergo a frequency-offset separated-oscillatory-field (FOSOF) microwave experiment. Only atoms which undergo a microwave transition, in the time-separated microwave fields are laser-excited to a Rydberg state and then Stark ionized and counted. Our new experimental design has eliminated the major systematic effects of previous experiments, and has led to a substantial improvement in the signal-to-noise ratio of the collected data. Our final improved measurement (with an expected uncertainty of less than 100 Hz) will allow for a test of 2-electron QED-theory in the helium n=2 triplet P system, and will be an important step towards obtaining a precise determination of the fine-structure constant. This research is supported by NSERC, CRC, CFI and NIST.

DNA triplet repeats mediate heterochromatin-protein-1-sensitive variegated gene silencing.

PubMed

Saveliev, Alexander; Everett, Christopher; Sharpe, Tammy; Webster, Zoë; Festenstein, Richard

2003-04-24

Gene repression is crucial to the maintenance of differentiated cell types in multicellular organisms, whereas aberrant silencing can lead to disease. The organization of DNA into chromatin and heterochromatin is implicated in gene silencing. In chromatin, DNA wraps around histones, creating nucleosomes. Further condensation of chromatin, associated with large blocks of repetitive DNA sequences, is known as heterochromatin. Position effect variegation (PEV) occurs when a gene is located abnormally close to heterochromatin, silencing the affected gene in a proportion of cells. Here we show that the relatively short triplet-repeat expansions found in myotonic dystrophy and Friedreich's ataxia confer variegation of expression on a linked transgene in mice. Silencing was correlated with a decrease in promoter accessibility and was enhanced by the classical PEV modifier heterochromatin protein 1 (HP1). Notably, triplet-repeat-associated variegation was not restricted to classical heterochromatic regions but occurred irrespective of chromosomal location. Because the phenomenon described here shares important features with PEV, the mechanisms underlying heterochromatin-mediated silencing might have a role in gene regulation at many sites throughout the mammalian genome and modulate the extent of gene silencing and hence severity in several triplet-repeat diseases.

Optical and electron paramagnetic resonance studies of the excited triplet states of UV-B absorbers: 2-ethylhexyl salicylate and homomenthyl salicylate.

PubMed

Sugiyama, Kazuto; Tsuchiya, Takumi; Kikuchi, Azusa; Yagi, Mikio

2015-09-26

The energy levels and lifetimes of the lowest excited triplet (T1) states of UV-B absorbers, 2-ethylhexyl salicylate (EHS) and homomenthyl salicylate (HMS), and their deprotonated anions (EHS(-) and HMS(-)) were determined through measurements of phosphorescence and electron paramagnetic resonance (EPR) spectra in rigid solutions at 77 K. The observed T1 energies of EHS and HMS are higher than those of butylmethoxydibenzoylmethane, the most widely used UV-A absorber, and octyl methoxycinnamate, the most widely used UV-B absorber. The T1 states of EHS, HMS, EHS(-) and HMS(-) were assigned to almost pure (3)ππ* state from the observed T1 lifetimes and zero-field splitting parameters. EHS and HMS with an intramolecular hydrogen bond show a photoinduced phosphorescence enhancement in ethanol at 77 K. The EPR signals of the T1 states of EHS and HMS also increase in intensity with UV-irradiation time (photoinduced EPR enhancement). The T1 lifetimes of EHS and HMS at room temperature were determined through triplet-triplet absorption measurements in ethanol. The quantum yields of singlet oxygen production by EHS and HMS were determined by using time-resolved near-IR phosphorescence.

A color-communication scheme for digital imagery

USGS Publications Warehouse

Acosta, Alex

1987-01-01

Color pictures generated from digital images are frequently used by geologists, foresters, range managers, and others. These color products are preferred over black and white pictures because the human eye is more sensitive to color differences than to various shades of gray. Color discrimination is a function of perception, and therefore colors in these color composites are generally described subjectively, which can lead to ambiguous color communication. Numerous color-coordinate systems are available that quantitively relate digital triplets representing amounts of red, free, and blue to the parameters of hue, saturation, and intensity perceived by the eye. Most of these systems implement a complex transformation of the primary colors to a color space that is hard to visualize, thus making it difficult to relate digital triplets to perception parameters. This paper presents a color-communcation scheme that relates colors on a color triangle to corresponding values of "hue" (H), "saturation" (S), and chromaticity coordinates (x,y,z). The scheme simplifies the relation between red, green, and blue (RGB) digital triplets and the color generated by these triplets. Some examples of the use of the color-communication scheme in digital image processing are presented.

Matrix Isolation Spectroscopy and Photochemistry of Triplet 1,3-DIMETHYLPROPYNYLIDENE (MeC3Me)

NASA Astrophysics Data System (ADS)

Knezz, Stephanie N.; Waltz, Terese A.; Haenni, Benjamin C.; Burrmann, Nicola J.; McMahon, Robert J.

2015-06-01

Acetylenic carbenes and conjugated carbon chain molecules of the HCnH family are relevant to the study of combustion and chemistry in the interstellar medium (ISM). Propynylidene (HC3H) has been thoroughly studied and its structure and photochemistry determined. Here, we produce triplet diradical 1,3-dimethylpropynylidene (MeC3Me) photochemically from a precursor diazo compound in a cryogenic matrix (N2 or Ar) at 10 K, and spectroscopic analysis is carried out. The infrared, electronic absorption, and electron paramagnetic resonance spectra were examined in light of the parent (HC3H) system to ascertain the effect of alkyl substituents on delocalized carbon chains of this type. Computational analysis, EPR, and infrared analysis indicate a triplet ground state with a quasilinear structure. Infrared experiments reveal photochemical reaction to penten-3-yne upon UV irradiation. Further experimental and computational results pertaining to the structure and photochemistry will be presented. Seburg, R. A.; Patterson, E. V.; McMahon, R. J., Structure of Triplet Propynylidene (HCCCH) as Probed by IR, UV/vis, and EPR Spectroscopy of Isotopomers. Journal of the American Chemical Society 2009, 131 (26), 9442-9455.

Recalculation of the infrared continuum spectrum of the lowest energy triplet transitions in K2

NASA Astrophysics Data System (ADS)

Ligare, Martin; Edmonds, J. Brent

1991-09-01

The observation and identification of the spectra arising from transitions between the lowest energy triplet electronic states of diatomic potassium molecules were made by Huennekens et al. [J. Chem. Phys. 80, 4794 (1984)]. In this letter we recalculate theoretical spectra for these transitions using quasistatic line broadening theory and the recently published ab initio potential energy curves of Jeung and Ross [J. Phys. B 21, 1473 (1988)]. The calculated satellite of the 3Σ+g-3Σ+u transition occurs at 1.105 μm while the satellite is experimentally observed at 1.096 μm. This improved agreement both solidifies the original identification of Huennekens et al. and indicates the accuracy of the recent potential energy curves of Jeung and Ross for the low energy triplet states.

Computational investigation of the photochemical deoxygenation of thiophene-S-oxide and selenophene-Se-oxide.

PubMed

Stoffregen, Stacey A; Lee, Stephanie Y; Dickerson, Pearl; Jenks, William S

2014-02-01

CASSCF and multireference MP2 calculations were carried out on thiophene-S-oxide (TO) and selenophene-Se-oxide (SeO), comparing the energies of the ground state to the first two electronically excited singlet and triplet states, using constrained optimizations and multiple fixed S-O or Se-O distances. For both molecules, one of the two triplet states smoothly dissociates to yield O((3)P) with little or no barrier. Single point calculations are consistent with the same phenomenon occurring for dibenzothiophene-S-oxide (DBTO). This provides an explanation for the inefficient unimolecular photochemical dissociation of O((3)P) from DBTO despite a phosphorescence energy below that of S-O dissociation, i.e., that S-O scission probably occurs from a spectroscopically unobserved triplet (T2) state.

Collisional spin-oriented Sherman function in electron-hole semiconductor plasmas: Landau damping effect

NASA Astrophysics Data System (ADS)

Lee, Myoung-Jae; Jung, Young-Dae

2018-04-01

The influence of Landau damping on the spin-oriented collisional asymmetry is investigated in electron-hole semiconductor plasmas. The analytical expressions of the spin-singlet and the spin-triplet scattering amplitudes as well as the spin-oriented asymmetry Sherman function are obtained as functions of the scattering angle, the Landau parameter, the effective Debye length, and the collision energy. It is found that the Landau damping effect enhances the spin-singlet and spin-triplet scattering amplitudes in the forward and back scattering domains, respectively. It is also found that the Sherman function increases with an increase in the Landau parameter. In addition, the spin-singlet scattering process is found to be dominant rather than the spin-triplet scattering process in the high collision energy domain.

Design and construction of a high-energy photon polarimeter

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

Dugger, M.; Ritchie, B. G.; Sparks, N.

Here, we report on the design and construction of a high-energy photon polarimeter for measuring the degree of polarization of a linearly-polarized photon beam. The photon polarimeter uses the process of pair production on an atomic electron (triplet production). The azimuthal distribution of scattered atomic electrons following triplet production yields information regarding the degree of linear polarization of the incident photon beam. Furthermore, the polarimeter, operated in conjunction with a pair spectrometer, uses a silicon strip detector to measure the recoil electron distribution resulting from triplet photoproduction in a beryllium target foil. The analyzing power Σ A for the devicemore » using a 75 μm beryllium converter foil is about 0.2, with a relative systematic uncertainty in Σ A of 1.5%.« less

Intramolecular Singlet Fission in Oligoacene Heterodimers

DOE PAGES

Sanders, Samuel N.; Kumarasamy, Elango; Pun, Andrew B.; ...

2016-02-02

In this Communication we investigate singlet fission (SF) in heterodimers comprising a pentacene unit covalently bonded to another acene as we systematically vary the singlet and triplet pair energies. We find that these energies control the SF process, where dimers undergo SF provided that the resulting triplet pair energy is similar or lower in energy than the singlet state. In these systems the singlet energy is determined by the lower energy chromophore, and the rate of SF is found to be relatively independent of the driving force. However, triplet pair recombination in these heterodimers follows the energy gap law. Themore » ability to tune the energies of these materials provides a key strategy to study and design new SF materials – an important process for third generation photovoltaics.« less

Design and construction of a high-energy photon polarimeter

DOE PAGES

Dugger, M.; Ritchie, B. G.; Sparks, N.; ...

2017-06-12

Here, we report on the design and construction of a high-energy photon polarimeter for measuring the degree of polarization of a linearly-polarized photon beam. The photon polarimeter uses the process of pair production on an atomic electron (triplet production). The azimuthal distribution of scattered atomic electrons following triplet production yields information regarding the degree of linear polarization of the incident photon beam. Furthermore, the polarimeter, operated in conjunction with a pair spectrometer, uses a silicon strip detector to measure the recoil electron distribution resulting from triplet photoproduction in a beryllium target foil. The analyzing power Σ A for the devicemore » using a 75 μm beryllium converter foil is about 0.2, with a relative systematic uncertainty in Σ A of 1.5%.« less

High-efficiency electroluminescence and amplified spontaneous emission from a thermally activated delayed fluorescent near-infrared emitter

NASA Astrophysics Data System (ADS)

Kim, Dae-Hyeon; D'Aléo, Anthony; Chen, Xian-Kai; Sandanayaka, Atula D. S.; Yao, Dandan; Zhao, Li; Komino, Takeshi; Zaborova, Elena; Canard, Gabriel; Tsuchiya, Youichi; Choi, Eunyoung; Wu, Jeong Weon; Fages, Frédéric; Brédas, Jean-Luc; Ribierre, Jean-Charles; Adachi, Chihaya

2018-02-01

Near-infrared organic light-emitting diodes and semiconductor lasers could benefit a variety of applications including night-vision displays, sensors and information-secured displays. Organic dyes can generate electroluminescence efficiently at visible wavelengths, but organic light-emitting diodes are still underperforming in the near-infrared region. Here, we report thermally activated delayed fluorescent organic light-emitting diodes that operate at near-infrared wavelengths with a maximum external quantum efficiency of nearly 10% using a boron difluoride curcuminoid derivative. As well as an effective upconversion from triplet to singlet excited states due to the non-adiabatic coupling effect, this donor-acceptor-donor compound also exhibits efficient amplified spontaneous emission. By controlling the polarity of the active medium, the maximum emission wavelength of the electroluminescence spectrum can be tuned from 700 to 780 nm. This study represents an important advance in near-infrared organic light-emitting diodes and the design of alternative molecular architectures for photonic applications based on thermally activated delayed fluorescence.

The string-junction picture of multiquark states: an update

NASA Astrophysics Data System (ADS)

Rossi, G. C.; Veneziano, G.

2016-06-01

We recall and update, both theoretically and phenomenologically, our (nearly) forty-years-old proposal of a string-junction as a necessary complement to the conventional classification of hadrons based just on their quark-antiquark constituents. In that proposal single (though in general metastable) hadronic states are associated with "irreducible" gauge-invariant operators consisting of Wilson lines (visualized as strings of color flux tubes) that may either end on a quark or an antiquark, or annihilate in triplets at a junction J or an anti-junction overline{J} . For the junction-free sector (ordinary qoverline{q} mesons and glueballs) the picture is supported by large- N (number of colors) considerations as well as by a lattice strong-coupling expansion. Both imply the famous OZI rule suppressing quark-antiquark annihilation diagrams. For hadrons with J and/or overline{J} constituents the same expansions support our proposal, including its generalization of the OZI rule to the suppression of J-overline{J} annihilation diagrams. Such a rule implies that hadrons with junctions are "mesophobic" and thus unusually narrow if they are below threshold for decaying into as many baryons as their total number of junctions (two for a tetraquark, three for a pentaquark). Experimental support for our claim, based on the observation that narrow multiquark states typically lie below (well above) the relevant baryonic (mesonic) thresholds, will be presented.

The electronically excited states of LH2 complexes from Rhodopseudomonas acidophila strain 10050 studied by time-resolved spectroscopy and dynamic Monte Carlo simulations. II. Homo-arrays of LH2 complexes reconstituted into phospholipid model membranes.

PubMed

Pflock, Tobias J; Oellerich, Silke; Krapf, Lisa; Southall, June; Cogdell, Richard J; Ullmann, G Matthias; Köhler, Jürgen

2011-07-21

We performed time-resolved spectroscopy on homoarrays of LH2 complexes from the photosynthetic purple bacterium Rhodopseudomonas acidophila. Variations of the fluorescence transients were monitored as a function of the excitation fluence and the repetition rate of the excitation. These parameters are directly related to the excitation density within the array and to the number of LH2 complexes that still carry a triplet state prior to the next excitation. Comparison of the experimental observations with results from dynamic Monte Carlo simulations for a model cluster of LH2 complexes yields qualitative agreement without the need for any free parameter and reveals the mutual relationship between energy transfer and annihilation processes.

Samatha, Matthew, and Shane: A Case Study of the Motivational Factors That Drive These Triplets To Learn.

ERIC Educational Resources Information Center

Holmes, Julie A.

This paper describes a case study which sought to determine the motivational factors that prompted a set of triplets to excel in school. The working research questions dealt with different facets of school and home, and explored whether motivation was linked to certain subjects or certain topics within various subjects or was a function of the…

Effects of Implementing a Hybrid Wet Lab and Online Module Lab Curriculum into a General Chemistry Course: Impacts on Student Performance and Engagement with the Chemistry Triplet

ERIC Educational Resources Information Center

Irby, Stefan M.; Borda, Emily J.; Haupt, Justin

2018-01-01

Here, we describe the implementation a hybrid general chemistry teaching laboratory curriculum that replaces a portion of a course's traditional "wet lab" experiences with online virtual lab modules. These modules intentionally utilize representations on all three levels of the chemistry triplet-macroscopic, submicroscopic, and symbolic.…

Effect of Tensor Range in Nuclear Two-Body Problems

DOE R&D Accomplishments Database

Feshbach, H.; Schwinger, J.; Harr, J. A.

1949-11-01

The interaction between neutron and proton in the triplet state is investigated, a wide variation in the values of both central and tensor ranges are included; the per cent D state in the deuteron and the effective triplet range have been computed; the results are applied tot he discussion of the magnetic moment of the deuteron, the photoelectric disintegration of the deuteron, and neutron-proton scattering.

Quantum chemical study of the mechanism of reaction between NH (X 3sigma-) and H2, H2O, and CO2 under combustion conditions.

PubMed

Mackie, John C; Bacskay, George B

2005-12-29

Reactions of ground-state NH (3sigma-) radicals with H2, H2O, and CO2 have been investigated quantum chemically, whereby the stationary points of the appropriate reaction potential energy surfaces, that is, reactants, products, intermediates, and transition states, have been identified at the G3//B3LYP level of theory. Reaction between NH and H2 takes place via a simple abstraction transition state, and the rate coefficient for this reaction as derived from the quantum chemical calculations, k(NH + H2) = (1.1 x 10(14)) exp(-20.9 kcal mol(-1)/RT) cm3 mol(-1) s(-1) between 1000 and 2000 K, is found to be in good agreement with experiment. For reaction between triplet NH and H2O, no stable intermediates were located on the triplet reaction surface although several stable species were found on the singlet surface. No intersystem crossing seam between triplet NH + H2O and singlet HNO + H2 (the products of lowest energy) was found; hence there is no evidence to support the existence of a low-energy pathway to these products. A rate coefficient of k(NH + H2O) = (6.1 x 10(13)) exp(-32.8 kcal mol(-1)/RT) cm3 mol(-1) s(-1) between 1000 and 2000 K for the reaction NH (3sigma-) + H2O --> NH2 (2B) + OH (2pi) was derived from the quantum chemical results. The reverse rate coefficient, calculated via the equilibrium constant, is in agreement with values used in modeling the thermal de-NO(x) process. For the reaction between triplet NH and CO2, several stable intermediates on both triplet and singlet reaction surfaces were located. Although a pathway from triplet NH + CO2 to singlet HNO + CO involving intersystem crossing in an HN-CO2 adduct was discovered, no pathway of sufficiently low activation energy was discovered to compare with that found in an earlier experiment [Rohrig, M.; Wagner, H. G. Proc. Combust. Inst. 1994, 25, 993.].

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

PubMed

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

2017-02-15

Photoinduced electron transfer between triplet state of 9,10-anthraquinone (AQ) and its two derivatives: 2-chloro-9,10-anthraquinone (CAQ) and sodium anthraquinone-2-sulfonate (AQS) and ground state aniline (AN) and its dimethyl substitutions: 2,3-dimethylaniline (2,3-DMA), 2,6-dimethylaniline (2,6-DMA), 3,5-dimethylaniline (3,5-DMA) and N,N-dimethylaniline (N,N-DMA) is studied using nanosecond laser flash photolysis at room temperature. Detection of radical bands of quinone anions and aniline cations along with their formation and/or decay kinetics are used to confirm the electron transfer (ET) process. In MeCN medium, AN quenches the triplet state of CAQ (CAQ T ) but not the triplets AQ T or AQS T . However in aqueous medium, AN quenches AQS T and forms radical ion pair. All the DMAs can react through ET with all the triplet quinones at different degrees of efficiency in MeCN medium. Noticeably, the ring substituted DMAs are less efficient in electron donation to AQ T or AQS T while the N,N-DMA shows high efficiency in donating electron to all triplet quinones in MeCN medium. Charge distribution of donor molecules, in MeCN medium is calculated using density functional theory (DFT), and shows an enhancement of electron density of the ring of N,N-DMA, making it an ideal electron donor for ET studies compared to other DMAs. This systematic selection and usage of anilines with electrochemically tunable quinones can be viewed as a working model of donor-acceptor system that can be utilized in photoinduced ET applications. Copyright © 2016 Elsevier B.V. All rights reserved.

Charge Separation and Triplet Exciton Formation Pathways in Small-Molecule Solar Cells as Studied by Time-Resolved EPR Spectroscopy

DOE PAGES

Thomson, Stuart A. J.; Niklas, Jens; Mardis, Kristy L.; ...

2017-09-13

Organic solar cells are a promising renewable energy technology, offering the advantages of mechanical flexibility and solution processability. An understanding of the electronic excited states and charge separation pathways in these systems is crucial if efficiencies are to be further improved. Here we use light induced electron paramagnetic resonance (LEPR) spectroscopy and density functional theory calculations (DFT) to study the electronic excited states, charge transfer (CT) dynamics and triplet exciton formation pathways in blends of the small molecule donors (DTS(FBTTh 2) 2, DTS(F2BTTh 2) 2, DTS(PTTh 2) 2, DTG(FBTTh 2) 2 and DTG(F2BTTh 2) 2) with the fullerene derivative PCmore » 61BM. Using high frequency EPR the g-tensor of the positive polaron on the donor molecules was determined. The experimental results are compared with DFT calculations which reveal that the spin density of the polaron is distributed over a dimer or trimer. Time-resolved EPR (TR-EPR) spectra attributed to singlet CT states were identified and the polarization patterns revealed similar charge separation dynamics in the four fluorobenzothiadiazole donors, while charge separation in the DTS(PTTh 2) 2 blend is slower. Using TR-EPR we also investigated the triplet exciton formation pathways in the blend. The polarization patterns reveal that the excitons originate from both intersystem crossing (ISC) and back electron transfer (BET) processes. The DTS(PTTh 2) 2 blend was found to contain substantially more triplet excitons formed by BET than the fluorobenzothiadiazole blends. As a result, the higher BET triplet exciton population in the DTS(PTTh 2) 2 blend is in accordance with the slower charge separation dynamics observed in this blend.« less

Quantum mechanical reaction probability of triplet ketene at the multireference second-order perturbation level of theory.

PubMed

Ogihara, Yusuke; Yamamoto, Takeshi; Kato, Shigeki

2010-09-23

Triplet ketene exhibits a steplike structure in the experimentally observed dissociation rates, but its mechanism is still unknown despite many theoretical efforts in the past decades. In this paper we revisit this problem by quantum mechanically calculating the reaction probability with multireference-based electronic structure theory. Specifically, we first construct an analytical potential energy surface of triplet state by fitting it to about 6000 ab initio energies computed at the multireference second-order Mller-Plesset perturbation (MRMP2) level. We then evaluate the cumulative reaction probability by using the transition state wave packet method together with an adiabatically constrained Hamiltonian. The result shows that the imaginary barrier frequency on the triplet surface is 328i cm-1, which is close to the CCSD(T) result (321i cm-1) but is likely too large for reproducing the experimentally observed steps. Indeed, our calculated reaction probability exhibits no signature of steps, reflecting too strong tunneling effect along the reaction coordinate. Nevertheless, it is emphasized that the flatness of the potential profile in the transition-state region (which governs the degree of tunneling) depends strongly on the level of electronic structure calculation, thus leaving some possibility that the use of more accurate theories might lead to the observed steps. We also demonstrate that the triplet potential surface differs significantly between the CASSCF and MRMP2 results, particularly in the transition-state region. This fact seems to require more attention when studying the "nonadiabatic" scenario for the steps, in which the crossing seam between S0 and T1 surfaces is assumed to play a central role.

Embryo reduction versus expectant management in triplet pregnancies.

PubMed

Antsaklis, A; Souka, A P; Daskalakis, G; Papantoniou, N; Koutra, P; Kavalakis, Y; Mesogitis, S

2004-10-01

In triplet pregnancies, to compare pregnancy outcome of expectant management with that after embryo reduction to twins. Retrospective study of 255 trichorionic triplet pregnancies, of which 185 had embryo reduction to twins (reduced group) and 70 were managed expectantly (non-reduced group). Median birth weight was higher by about 500 g and gestation prolonged by about 3 weeks in the reduced pregnancies compared with the expectantly managed pregnancies (2300 vs. 1760 g; 36 vs. 33 weeks). The rates of preterm delivery were significantly lower in the reduced group (11.17 vs. 36.76% for delivery at < or = 32 weeks and 40.58 vs. 83.82% for delivery at < or = 35 weeks, reduced vs. non-reduced group). The percentage of infants born with low birth weight was significantly higher in the expectantly managed triplets (10.98 vs. 28.44% for birth weight < or = 1500 g and 68.55 vs. 92.89% for birth weight < or = 2500 g, reduced vs. non-reduced group). Total fetal loss was significantly higher in the reduced group than in the non-reduced group (15.41 and 4.76%, respectively) and the difference was mainly due to the higher miscarriage rate in the reduced group (8.11 vs. 2.86% in the non-reduced group). With the expected rates of handicap in preterm infants, we would anticipate 0.63% of severely handicapped children due to extreme prematurity in the reduced group and 1.64% in the non-reduced group. In triplet pregnancies, embryo reduction to twins significantly reduces the risk of severe preterm delivery and very low birth weight by about one-third, at the expense of a significant increase in total fetal loss, by about one-quarter. The procedure is likely to reduce the risk of having a severely handicapped child due to extreme prematurity.

Kinetics of photoinduced electron transfer between DNA bases and triplet 3,3',4,4'-benzophenone tetracarboxylic acid in aqueous solution of different pH's: proton-coupled electron transfer?

PubMed

Nguyen, Truong X; Kattnig, Daniel; Mansha, Asim; Grampp, Günter; Yurkovskaya, Alexandra V; Lukzen, Nikita

2012-11-08

The kinetics of triplet state quenching of 3,3',4,4'-benzophenone tetracarboxylic acid (BPTC) by DNA bases adenine, adenosine, thymine, and thymidine has been investigated in aqueous solution using time-resolved laser flash photolysis. The observation of the BPTC ketyl radical anion at λ(max) = 630 nm indicates that one electron transfer is involved in the quenching reactions. The pH-dependence of the quenching rate constants is measured in detail. As a result, the chemical reactivity of the reactants is assigned. The bimolecular rate constants of the quenching reactions between triplet BPTC and adenine, adenosine, thymine, and thymidine are k(q) = 2.3 × 10(9) (4.7 < pH < 9.9), k(q) = 4.0 × 10(9) (3.5 < pH < 4.7), k(q) = 1.0 × 10(9) (4.7 < pH < 9.9), and k(q) = 4.0 × 10(8) M(-1) s(-1) (4.7 < pH < 9.8), respectively. Moreover, it reveals that in strong basic medium (pH = 12.0) a keto-enol tautomerism of thymine inhibits its reaction with triplet BPTC. Such a behavior is not possible for thymidine because of its deoxyribose group. In addition, the pH-dependence of the apparent electrochemical standard potential of thymine in aqueous solution was investigated by cyclic voltammetry. The ΔE/ΔpH ≈ -59 mV/pH result is characteristic of proton-coupled electron transfer. This behavior, together with the kinetic analysis, leads to the conclusion that the quenching reactions between triplet BPTC and thymine involve one proton-coupled electron transfer.

Kinetics of Photoinduced Electron Transfer between DNA Bases and Triplet 3,3′,4,4′-Benzophenone Tetracarboxylic Acid in Aqueous Solution of Different pH's: Proton-Coupled Electron Transfer?

PubMed Central

2012-01-01

The kinetics of triplet state quenching of 3,3′,4,4′-benzophenone tetracarboxylic acid (BPTC) by DNA bases adenine, adenosine, thymine, and thymidine has been investigated in aqueous solution using time-resolved laser flash photolysis. The observation of the BPTC ketyl radical anion at λmax = 630 nm indicates that one electron transfer is involved in the quenching reactions. The pH-dependence of the quenching rate constants is measured in detail. As a result, the chemical reactivity of the reactants is assigned. The bimolecular rate constants of the quenching reactions between triplet BPTC and adenine, adenosine, thymine, and thymidine are kq = 2.3 × 109 (4.7 < pH < 9.9), kq = 4.0 × 109 (3.5 < pH < 4.7), kq = 1.0 × 109 (4.7 < pH < 9.9), and kq = 4.0 × 108 M–1 s–1 (4.7 < pH < 9.8), respectively. Moreover, it reveals that in strong basic medium (pH = 12.0) a keto–enol tautomerism of thymine inhibits its reaction with triplet BPTC. Such a behavior is not possible for thymidine because of its deoxyribose group. In addition, the pH-dependence of the apparent electrochemical standard potential of thymine in aqueous solution was investigated by cyclic voltammetry. The ΔE/ΔpH ≈ −59 mV/pH result is characteristic of proton-coupled electron transfer. This behavior, together with the kinetic analysis, leads to the conclusion that the quenching reactions between triplet BPTC and thymine involve one proton-coupled electron transfer. PMID:23038981

Heterogeneous substitution effects in chlorocyanomethyl radical and chlorocyanocarbene.

PubMed

Khuseynov, Dmitry; Dixon, Andrew R; Goebbert, Daniel J; Sanov, Andrei

2013-10-17

We report a photoelectron-imaging investigation of the chlorocyanomethyl radical (CHClCN) and the corresponding carbene (CClCN). The results are discussed in comparison with the corresponding dichloro- and dicyano-substituted species, focusing on the divergent effects of the halogen and pseudohalogen (CN) substitutions. A cooperative (captodative) interaction of the π-donor Cl and π-acceptor cyano groups favors the increased stability of the CHClCN radical, but a competition of the two substituents is observed in the singlet-triplet splitting of the carbene. The vertical detachment energy (VDE) of CHClCN(-) is determined to be 2.39 ± 0.04 eV, with the broad photoelectron band consistent with the significant geometry change predicted by theory for the detachment transition. The adiabatic electron affinity of CHClCN, EA = 1.86 ± 0.08 eV, is estimated on the basis of the experimental VDE and the computed difference between the VDE and EA values. This result allows the calculation of the bond dissociation energy of chloroacetonitrile, DH298(H-CHClCN) = 87.0 ± 2.7 kcal/mol. Photoelectron imaging of CClCN(-) reveals two main transitions, assigned to the singlet ((1)A') and triplet ((3)A″) states of the CClCN carbene. The respective VDEs are 2.76 ± 0.05 and 3.25 ± 0.05 eV. The experimental results are in good agreement with the theoretically predicted singlet-triplet vertical energy gap at the anion geometry, but inconclusive with regard to the adiabatic singlet-triplet splitting in CClCN. Consistent with the experimental findings, ab initio calculations using the spin-flip approach in combination with the coupled-cluster theory, indicate that the (1)A' and (3)A″ states are nearly degenerate, with the singlet state lying adiabatically only ∼0.01 eV below the triplet.

Charge Separation and Triplet Exciton Formation Pathways in Small Molecule Solar Cells as Studied by Time-resolved EPR Spectroscopy.

PubMed

Thomson, Stuart A J; Niklas, Jens; Mardis, Kristy L; Mallares, Christopher; Samuel, Ifor D W; Poluektov, Oleg G

2017-10-19

Organic solar cells are a promising renewable energy technology, offering the advantages of mechanical flexibility and solution processability. An understanding of the electronic excited states and charge separation pathways in these systems is crucial if efficiencies are to be further improved. Here we use light induced electron paramagnetic resonance (LEPR) spectroscopy and density functional theory calculations (DFT) to study the electronic excited states, charge transfer (CT) dynamics and triplet exciton formation pathways in blends of the small molecule donors (DTS(FBTTh 2 ) 2 , DTS(F 2 BTTh 2 ) 2 , DTS(PTTh 2 ) 2 , DTG(FBTTh 2 ) 2 and DTG(F 2 BTTh 2 ) 2 ) with the fullerene derivative PC 61 BM. Using high frequency EPR the g-tensor of the positive polaron on the donor molecules was determined. The experimental results are compared with DFT calculations which reveal that the spin density of the polaron is distributed over a dimer or trimer. Time-resolved EPR (TR-EPR) spectra attributed to singlet CT states were identified and the polarization patterns revealed similar charge separation dynamics in the four fluorobenzothiadiazole donors, while charge separation in the DTS(PTTh 2 ) 2 blend is slower. Using TR-EPR we also investigated the triplet exciton formation pathways in the blend. The polarization patterns reveal that the excitons originate from both intersystem crossing (ISC) and back electron transfer (BET) processes. The DTS(PTTh 2 ) 2 blend was found to contain substantially more triplet excitons formed by BET than the fluorobenzothiadiazole blends. The higher BET triplet exciton population in the DTS(PTTh 2 ) 2 blend is in accordance with the slower charge separation dynamics observed in this blend.

Excited singlet molecular O2 (1Δg) is generated enzymatically from excited carbonyls in the dark

PubMed Central

Mano, Camila M.; Prado, Fernanda M.; Massari, Júlio; Ronsein, Graziella E.; Martinez, Glaucia R.; Miyamoto, Sayuri; Cadet, Jean; Sies, Helmut; Medeiros, Marisa H. G.; Bechara, Etelvino J. H.; Di Mascio, Paolo

2014-01-01

In mammalian tissues, ultraweak chemiluminescence arising from biomolecule oxidation has been attributed to the radiative deactivation of singlet molecular oxygen [O2 (1Δg)] and electronically excited triplet carbonyl products involving dioxetane intermediates. Herein, we describe evidence of the generation of O2 (1Δg) in aqueous solution via energy transfer from excited triplet acetone. This involves thermolysis of 3,3,4,4-tetramethyl-1,2-dioxetane, a chemical source, and horseradish peroxidase-catalyzed oxidation of 2-methylpropanal, as an enzymatic source. Both sources of excited carbonyls showed characteristic light emission at 1,270 nm, directly indicative of the monomolecular decay of O2 (1Δg). Indirect analysis of O2 (1Δg) by electron paramagnetic resonance using the chemical trap 2,2,6,6-tetramethylpiperidine showed the formation of 2,2,6,6-tetramethylpiperidine-1-oxyl. Using [18O]-labeled triplet, ground state molecular oxygen [18O2 (3Σg-)], chemical trapping of 18O2 (1Δg) with disodium salt of anthracene-9,10-diyldiethane-2,1-diyl disulfate yielding the corresponding double-[18O]-labeled 9,10-endoperoxide, was detected through mass spectrometry. This corroborates formation of O2 (1Δg). Altogether, photoemission and chemical trapping studies clearly demonstrate that chemically and enzymatically nascent excited carbonyl generates 18O2 (1Δg) by triplet-triplet energy transfer to ground state oxygen O2 (3Σg−), and supports the long formulated hypothesis of O2 (1Δg) involvement in physiological and pathophysiological events that might take place in tissues in the absence of light. PMID:25087485

Charge Separation and Triplet Exciton Formation Pathways in Small-Molecule Solar Cells as Studied by Time-Resolved EPR Spectroscopy

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

Thomson, Stuart A. J.; Niklas, Jens; Mardis, Kristy L.

Organic solar cells are a promising renewable energy technology, offering the advantages of mechanical flexibility and solution processability. An understanding of the electronic excited states and charge separation pathways in these systems is crucial if efficiencies are to be further improved. Here we use light induced electron paramagnetic resonance (LEPR) spectroscopy and density functional theory calculations (DFT) to study the electronic excited states, charge transfer (CT) dynamics and triplet exciton formation pathways in blends of the small molecule donors (DTS(FBTTh 2) 2, DTS(F2BTTh 2) 2, DTS(PTTh 2) 2, DTG(FBTTh 2) 2 and DTG(F2BTTh 2) 2) with the fullerene derivative PCmore » 61BM. Using high frequency EPR the g-tensor of the positive polaron on the donor molecules was determined. The experimental results are compared with DFT calculations which reveal that the spin density of the polaron is distributed over a dimer or trimer. Time-resolved EPR (TR-EPR) spectra attributed to singlet CT states were identified and the polarization patterns revealed similar charge separation dynamics in the four fluorobenzothiadiazole donors, while charge separation in the DTS(PTTh 2) 2 blend is slower. Using TR-EPR we also investigated the triplet exciton formation pathways in the blend. The polarization patterns reveal that the excitons originate from both intersystem crossing (ISC) and back electron transfer (BET) processes. The DTS(PTTh 2) 2 blend was found to contain substantially more triplet excitons formed by BET than the fluorobenzothiadiazole blends. As a result, the higher BET triplet exciton population in the DTS(PTTh 2) 2 blend is in accordance with the slower charge separation dynamics observed in this blend.« less

Singlet oxygen feedback delayed fluorescence of protoporphyrin IX in organic solutions.

PubMed

Vinklárek, Ivo S; Scholz, Marek; Dědic, Roman; Hála, Jan

2017-04-12

Delayed fluorescence (DF) of protoporphyrin IX (PpIX) has been recently proposed as a tool for monitoring of mitochondrial oxygen tension in vivo as well as for observation of the effectiveness of photodynamic therapy (PDT) [E. G. Mik, Anesth. Analg., 2013, 117, 834-346; F. Piffaretti et al., J. Biomed. Opt., 2012, 17, 115007]. However, the efficiency of the mechanism of thermal activation (E-type DF), which was considered in the papers, is limited due to a large energy gap between the first excited singlet and the first triplet state of PpIX at room or body temperatures. Moreover, the energy gap is roughly equal to other porphyrinoid photosensitizers that generate DF mostly through the Singlet Oxygen Feedback-Induced mechanism (SOFDF) under certain conditions [M. Scholz and R. Dědic, Singlet Oxygen: Applications in Biosciences and Nanosciences, 2016, vol. 2, pp. 63-81]. The mechanisms of delayed fluorescence of PpIX dissolved either in dimethylformamide (DMF) or in the mixture of DMF with ethylene glycol (EG) were investigated at atmospheric partial pressure of oxygen by means of a simultaneous time-resolved detection of 1 O 2 phosphorescence and PpIX DF which makes a direct comparison of the kinetics and lifetimes of both the luminescence channels possible. Samples of PpIX (100 μM) exhibit concave DF kinetics, which is a typical footprint of the SOFDF mechanism. The dramatic decrease in the DF intensity after adding a selective 1 O 2 quencher sodium azide (NaN 3 , 10 mM) proves that >90% of DF is indeed generated through SOFDF. Moreover, the analysis of the DF kinetics in the presence of NaN 3 implies that the second significant mechanism of DF generation is the triplet-triplet annihilation (P-type DF). The bimolecular mechanism of DF was further confirmed by the decrease of the DF intensity in the more viscous mixture DMF/EG and by the increase of the ratio of DF to the prompt fluorescence (PF) intensity with the increasing excitation intensity. These results show the significant role of the SOFDF mechanism in the DF of PpIX at high concentrations and at atmospheric partial pressure of oxygen and should be considered when developing diagnostic tools for clinical applications.

Mechanistic study of fulvic acid assisted propranolol photodegradation in aqueous solution.

PubMed

Makunina, Maria P; Pozdnyakov, Ivan P; Chen, Yong; Grivin, Vyacheslav P; Bazhin, Nikolay M; Plyusnin, Victor F

2015-01-01

Laser flash (355 nm) and stationary (365 nm) photolysis were used to study the mechanisms of propranolol photolysis in the presence of fulvic acid in aqueous solutions. The FA-assisted photodegradation of propranolol was observed using UV-A irradiation (where propranolol is stable). Direct evidence indicated that the photodegradation resulted from the static quenching of the FA triplet state by propranolol via the electron transfer mechanism. The triplet state yield (ϕT≈0.6%) and the T-T absorption coefficient (ɛT(620 nm)≈5×10(4) M(-1) cm(-1)) were estimated for the first time by modeling the yields of the FA triplet state in the presence of propranolol. Thus, fulvic acid is a promising agent for accelerating propranolol photodegradation in aqueous solutions under UV-A light irradiation. Copyright © 2014 Elsevier Ltd. All rights reserved.

Phase transition in conservative diffusive contact processes

NASA Astrophysics Data System (ADS)

Fiore, Carlos E.; de Oliveira, Mário J.

2004-10-01

We determine the phase diagrams of conservative diffusive contact processes by means of numerical simulations. These models are versions of the ordinary diffusive single-creation, pair-creation, and triplet-creation contact processes in which the particle number is conserved. The transition between the frozen and active states was determined by studying the system in the subcritical regime, and the nature of the transition, whether continuous or first order, was determined by looking at the fractal dimension of the critical cluster. For the single-creation model the transition remains continuous for any diffusion rate. For pair- and triplet-creation models, however, the transition becomes first order for high enough diffusion rate. Our results indicate that in the limit of infinite diffusion rate the jump in density equals 2/3 for the pair-creation model and 5/6 for the triplet-creation model.

High-Yield Excited Triplet States in Pentacene Self-Assembled Monolayers on Gold Nanoparticles through Singlet Exciton Fission.

PubMed

Kato, Daiki; Sakai, Hayato; Tkachenko, Nikolai V; Hasobe, Taku

2016-04-18

One of the major drawbacks of organic-dye-modified self-assembled monolayers on metal nanoparticles when employed for efficient use of light energy is the fact that singlet excited states on dye molecules can be easily deactivated by means of energy transfer to the metal surface. In this study, a series of 6,13-bis(triisopropylsilylethynyl)pentacene-alkanethiolate monolayer protected gold nanoparticles with different particle sizes and alkane chain lengths were successfully synthesized and were employed for the efficient generation of excited triplet states of the pentacene derivatives by singlet fission. Time-resolved transient absorption measurements revealed the formation of excited triplet states in high yield (172±26 %) by suppressing energy transfer to the gold surface. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Supercurrent as a probe for topological superconductivity in magnetic adatom chains

NASA Astrophysics Data System (ADS)

Mohanta, Narayan; Kampf, Arno P.; Kopp, Thilo

2018-06-01

A magnetic adatom chain, proximity coupled to a conventional superconductor with spin-orbit coupling, exhibits locally an odd-parity, spin-triplet pairing amplitude. We show that the singlet-triplet junction, thus formed, leads to a net spin accumulation in the near vicinity of the chain. The accumulated spins are polarized along the direction of the local d vector for triplet pairing and generate an enhanced persistent current flowing around the chain. The spin polarization and the "supercurrent" reverse their directions beyond a critical exchange coupling strength at which the singlet superconducting order changes its sign on the chain. The current is strongly enhanced in the topological superconducting regime where Majorana bound states appear at the chain ends. The current and the spin profile offer alternative routes to characterize the topological superconducting state in adatom chains and islands.

Selecting band combinations with thematic mapper data

NASA Technical Reports Server (NTRS)

Sheffield, C. A.

1983-01-01

A problem arises in making color composite images because there are 210 different possible color presentations of TM three-band images. A method is given for reducing that 210 to a single choice, decided by the statistics of a scene or subscene, and taking into full account any correlations that exist between different bands. Instead of using total variance as the measure for information content of the band triplets, the ellipsoid of maximum volume is selected which discourages selection of bands with high correlation. The band triplet is obtained by computing and ranking in order the determinants of each 3 x 3 principal submatrix of the original matrix M. After selection of the best triplet, the assignment of colors is made by using the actual variances (the diagonal elements of M): green (maximum variance), red (second largest variance), blue (smallest variance).

THE SEARCH FOR CELESTIAL POSITRONIUM VIA THE RECOMBINATION SPECTRUM

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

Ellis, S. C.; Bland-Hawthorn, J., E-mail: sce@physics.usyd.edu.a, E-mail: jbh@physics.usyd.edu.a

2009-12-10

Positronium is a short-lived atom consisting of a bound electron-positron pair. In the triplet state, when the spins of both particles are parallel, radiative recombination lines will be emitted prior to annihilation. The existence of celestial positronium is revealed through gamma-ray observations of its annihilation products. These observations, however, have intrinsically low angular resolution. In this paper, we examine the prospects for detecting the positronium recombination spectrum. Such observations have the potential to reveal discrete sources of e {sup +} for the first time and will allow the acuity of optical telescopes and instrumentation to be applied to observations ofmore » high-energy phenomena. We review the theory of the positronium recombination spectrum and provide formulae to calculate expected line strengths from the e {sup +} production rate and for different conditions in the interstellar medium. We estimate the positronium emission line strengths for several classes of Galactic and extragalactic sources. These are compared to current observational limits and to current and future sensitivities of optical and infrared instrumentation. We find that observations of the Psalpha line should soon be possible due to recent advances in NIR spectroscopy.« less

Cytomegalovirus infection in preterm triplets transmitted via breast milk.

PubMed

Demirel, Gamze; Celik, Istemi Han; Canpolat, Fuat Emre; Dilmen, Ugur

2014-04-01

Cytomegalovirus (CMV) may transmit perinatally or from breast milk. The risk for development of symptomatic CMV disease in very-low-birth-weight premature infants after transmission from maternal breast milk is not clear. There are scarce data in the literature about congenital CMV infection in multiple pregnancies, being mostly with twin gestations. Here we present a unique case of triplets with CMV infection transmitted via breast milk.

An ab initio mechanism for efficient population of triplet states in cytotoxic sulfur substituted DNA bases: the case of 6-thioguanine.

PubMed

Martínez-Fernández, Lara; González, Leticia; Corral, Inés

2012-02-18

The deactivation mechanism of the cytotoxic 6-thioguanine, the 6-sulfur-substituted analogue of the canonical DNA base, is unveiled by ab initio calculations. Oxygen-by-sulfur substitution leads to efficient population of triplet states-the first step for generating singlet oxygen-which is responsible for its cytotoxicity. This journal is © The Royal Society of Chemistry 2012

An Objective Measurement of the Build-Up of Auditory Streaming and of Its Modulation by Attention

ERIC Educational Resources Information Center

Thompson, Sarah K.; Carlyon, Robert P.; Cusack, Rhodri

2011-01-01

Three experiments studied auditory streaming using sequences of alternating "ABA" triplets, where "A" and "B" were 50-ms tones differing in frequency by [delta]f semitones and separated by 75-ms gaps. Experiment 1 showed that detection of a short increase in the gap between a B tone and the preceding A tone, imposed on one ABA triplet, was better…

Solid State Photochemical Generation of Triplet Phenoxy-Phenoxy Radical Pairs

DTIC Science & Technology

1990-04-01

of diphenyl oxalate . Tert-butylated bis-aryloxalat s show good radical pair stability, with triplet ESR signals surviving days at room temperature in...between the geminate phenoxyl radicals. The comparable breadth of the spectra for diphenyl carbonate and the oxalates implies a similar interaction strength...ferromagnetic coupling that may be achieved in geminate pairs generated from a diphenyl oxalate vs. a diphenyl carbonate. In addition, we see similar

Triplet Birth and Infant Development: The Impact of Intrauterine Growth and Maternal-Infant Interaction on the Infant's Emotional and Cognitive Development

ERIC Educational Resources Information Center

Eidelman, Arthur I.; Feldman, Ruth

2006-01-01

The explosion in the rate of multiple births has led to new questions about how adequately prepared parents are for the demands of raising triplets and the implications for the healthy development of the infants. The authors examined the relationship between mothering, infant social behavior, and cognitive development in a longitudinal study of 23…

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.

Does test-enhanced learning transfer for triple associates?

PubMed

Pan, Steven C; Wong, Carol M; Potter, Zachary E; Mejia, Jonathan; Rickard, Timothy C

2016-01-01

Test-enhanced learning and transfer for triple-associate word stimuli was assessed in three experiments. In each experiment, training and final-test trials involved the presentation of two words per triple associate (triplet), with the third word having to be retrieved. In agreement with the prior literature on different stimuli, training through testing with feedback yielded markedly better final-test performance than did restudy. However, in contrast to the positive transfer reported for paired associate stimuli, minimal or no positive transfer was observed, relative to a restudy control, from a trained cue combination (e.g., A, B, ?) to other cue combinations from the same triplet that required a different response (e.g., B, C, ?). That result also held when two unique cue combinations per triplet were tested during training, and for triplets with low and high average associative strengths. Supplementary analyses provided insight into the overall transfer effect: An incorrect response during training appears to yield positive transfer relative to restudy, whereas a correct response appears to yield no, or even negative, transfer. Cross-experiment analyses indicated that test-enhanced learning is not diminished when two or three cue combinations are presented during training. Thus, even though learning through testing is highly specific, testing on all possible stimulus-response combinations remains the most efficient strategy for the learning of triple associates.

Charge recombination in organic photovoltaic devices with high open-circuit voltages.

PubMed

Westenhoff, Sebastian; Howard, Ian A; Hodgkiss, Justin M; Kirov, Kiril R; Bronstein, Hugo A; Williams, Charlotte K; Greenham, Neil C; Friend, Richard H

2008-10-15

A detailed charge recombination mechanism is presented for organic photovoltaic devices with a high open-circuit voltage. In a binary blend comprised of polyfluorene copolymers, the performance-limiting process is found to be the efficient recombination of tightly bound charge pairs into neutral triplet excitons. We arrive at this conclusion using optical transient absorption (TA) spectroscopy with visible and IR probes and over seven decades of time resolution. By resolving the polarization of the TA signal, we track the movement of polaronic states generated at the heterojunction not only in time but also in space. It is found that the photogenerated charge pairs are remarkably immobile at the heterojunction during their lifetime. The charge pairs are shown to be subject to efficient intersystem crossing and terminally recombine into F8BT triplet excitons within approximately 40 ns. Long-range charge separation competes rather unfavorably with intersystem crossing--75% of all charge pairs decay into triplet excitons. Triplet exciton states are thermodynamically accessible in polymer solar cells with high open circuit voltage, and we therefore suggest this loss mechanism to be general. We discuss guidelines for the design of the next generation of organic photovoltaic materials where separating the metastable interfacial charge pairs within approximately 40 ns is paramount.

Reversible Photoisomerization among Triplet Amino Naphthylnitrene, Triplet Diimine Biradical, and Indazole: Matrix-Isolation IR Spectra of 8-Amino-1-naphthylnitrene, 1,8-Naphthalenediimine, and 1,2-Dihydrobenz[cd]indazole.

PubMed

Okamura, Takuya; Akai, Nobuyuki; Nakata, Munetaka

2017-03-02

Reaction mechanisms of nitrene, one of the most famous biradicals, have been frequently studied, and many spectral data have been obtained so far. In the present study, the experimental IR spectra of triplet 8-amino-1-naphthylnitrene ( 3 ANN), a triplet diimine biradical 1,8-dihydro-1,8-naphthalenediimine ( 3 DND), and 1,2-dihydrobenz[cd]indazole (DBI), which are produced in the UV photolysis of 1,8-diaminonaphthalene in an Ar matrix and identified by a combination method of IR spectroscopy and DFT quantum chemical calculations, are first reported. 3 ANN is found to change to DBI by hydrogen-atom migration with bond making between the two nitrogen atoms upon visible-light irradiation (λ > 580 nm) with its backward reaction caused by 350 nm irradiation. In addition, 3 ANN isomerizes to 3 DND by 700 nm irradiation, while its backward reaction occurs upon 500 nm irradiation. The wavelength dependences of these photoisomerizations are explained in terms of their electronic transition energies estimated by time-dependent DFT calculations. It is concluded that the novel reversible photoisomerization system among 3 ANN, 3 DND, and DBI is totally different from the well-known photoisomerization between phenylnitrene and a seven-membered cyclic compound.

Dynamics of singlet fission and electron injection in self-assembled acene monolayers on titanium dioxide† †Electronic supplementary information (ESI) available: Steady-state UV-VIS and PL, solution transient absorption, X-ray diffraction, decay associated spectra, and TIPS Tc COOH/Al2O3/TiO2 film kinetics. See DOI: 10.1039/c7sc04688j

PubMed Central

Pace, Natalie A.; Arias, Dylan H.; Granger, Devin B.; Christensen, Steven; Anthony, John E.

2018-01-01

We employ a combination of linear spectroscopy, electrochemistry, and transient absorption spectroscopy to characterize the interplay between electron transfer and singlet fission dynamics in polyacene-based dyes attached to nanostructured TiO2. For triisopropyl silylethynyl (TIPS)-pentacene, we find that the singlet fission time constant increases to 6.5 ps on a nanostructured TiO2 surface relative to a thin film time constant of 150 fs, and that triplets do not dissociate after they are formed. In contrast, TIPS-tetracene singlets quickly dissociate in 2 ps at the molecule/TiO2 interface, and this dissociation outcompetes the relatively slow singlet fission process. The addition of an alumina layer slows down electron injection, allowing the formation of triplets from singlet fission in 40 ps. However, the triplets do not inject electrons, which is likely due to a lack of sufficient driving force for triplet dissociation. These results point to the critical balance required between efficient singlet fission and appropriate energetics for interfacial charge transfer. PMID:29732084

Temperature dependence of regioselectivity in nucleophilic photosubstitution of 4-nitroanisole. The activation energy criterion for regioselectivity.

PubMed

Wubbels, Gene G; Danial, Hanan; Policarpio, Danielle

2010-11-19

Photosubstitution of the nitro group vs the methoxy group of triplet 4-nitroanisole by hydroxide ion in water leads to product yields of about 80% 4-methoxyphenol and 20% 4-nitrophenol. The ratio depends slightly on temperature from 3 to 73 °C. The slight temperature variation in the yield ratio is reproduced almost perfectly with a simple Arrhenius model for a mechanism involving bonding of hydroxide ion with the triplet state of 4-nitroanisole. The competing transition states have activation energies of 2.2 and 2.6 kcal/mol, respectively. Correct prediction of regioselectivity can be done for this case by quantum chemical calculation of the competing triplet transition-state energies, or those of the corresponding triplet σ-complexes. Other models for aromatic photosubstitution regioselectivity in mechanisms of the S(N)2Ar* type, such as those based on calculated electron densities, HOMO/LUMO coefficients, or energy gap sizes, are discussed and shown to be inferior to the relative activation energies model. The photoreaction in alcohol solvents, claimed by others to generate the same products as in water and to have an exceedingly large variation of the product ratio with temperature, may reflect chemical changes other than those reported.

Extending the cleavage rules for the hammerhead ribozyme: mutating adenosine15.1 to inosine15.1 changes the cleavage site specificity from N16.2U16.1H17 to N16.2C16.1H17.

PubMed Central

Ludwig, J; Blaschke, M; Sproat, B S

1998-01-01

In this paper, we show that an adenosine to inosine mutation at position 15.1 changes the substrate specificity of the hammerhead ribozyme from N16.2U16.1H17to N16.2C16.1H17(H represents A, C or U). This result extends the hammerhead cleavage triplet definition from N16.2U16.1H17to the more general N16.2Y16.1H17. Comparison of cleavage rates using I15.1ribozymes for NCH triplets and standard A15.1 ribozymes for NUH triplets under single turnover conditions shows similar or slightly enhanced levels of reactivity for the I15. 1-containing structures. The effect of I15.1 substitution was also tested in nuclease-resistant 2'- O -alkyl substituted derivatives (oligozymes), showing a similar level of activity for the NUH and NCH cleaving structures. The availability of NCH triplets that can be targeted without loss of efficiency increases the flexibility of ribozyme targeting strategies. This was demonstrated by an efficient cleavage of an HCV transcript at a previously inaccessible GCA site in codon 2. PMID:9580675

Gift from statistical learning: Visual statistical learning enhances memory for sequence elements and impairs memory for items that disrupt regularities.

PubMed

Otsuka, Sachio; Saiki, Jun

2016-02-01

Prior studies have shown that visual statistical learning (VSL) enhances familiarity (a type of memory) of sequences. How do statistical regularities influence the processing of each triplet element and inserted distractors that disrupt the regularity? Given that increased attention to triplets induced by VSL and inhibition of unattended triplets, we predicted that VSL would promote memory for each triplet constituent, and degrade memory for inserted stimuli. Across the first two experiments, we found that objects from structured sequences were more likely to be remembered than objects from random sequences, and that letters (Experiment 1) or objects (Experiment 2) inserted into structured sequences were less likely to be remembered than those inserted into random sequences. In the subsequent two experiments, we examined an alternative account for our results, whereby the difference in memory for inserted items between structured and random conditions is due to individuation of items within random sequences. Our findings replicated even when control letters (Experiment 3A) or objects (Experiment 3B) were presented before or after, rather than inserted into, random sequences. Our findings suggest that statistical learning enhances memory for each item in a regular set and impairs memory for items that disrupt the regularity. Copyright © 2015 Elsevier B.V. All rights reserved.

Exact solution of the PPP model for correlated electronic states of tetracene and substituted tetracene.

PubMed

Pati, Y Anusooya; Ramasesha, S

2014-06-12

Tetracene is an important conjugated molecule for device applications. We have used the diagrammatic valence bond method to obtain the desired states, in a Hilbert space of about 450 million singlets and 902 million triplets. We have also studied the donor/acceptor (D/A)-substituted tetracenes with D and A groups placed symmetrically about the long axis of the molecule. In these cases, by exploiting a new symmetry, which is a combination of C2 symmetry and electron-hole symmetry, we are able to obtain their low-lying states. In the case of substituted tetracene, we find that optically allowed one-photon excitation gaps reduce with increasing D/A strength, while the lowest singlet-triplet gap is only weakly affected. In all the systems we have studied, the excited singlet state, S1, is at more than twice the energy of the lowest triplet state and the second triplet is very close to the S1 state. Thus, donor-acceptor-substituted tetracene could be a good candidate in photovoltaic device application as it satisfies energy criteria for singlet fission. We have also obtained the model exact second harmonic generation (SHG) coefficients using the correction vector method, and we find that the SHG responses increase with the increase in D/A strength.

Superconductivity switch from spin-singlet to -triplet pairing in a topological superconducting junction.

PubMed

Tao, Ze; Chen, F J; Zhou, L Y; Li, Bin; Tao, Y C; Wang, J

2018-06-06

The interedge coupling is the cardinal characteristic of the narrow quantum spin Hall (QSH) insulator, and thus could bring about exotic transport phenomena. Herein, we present a theoretical investigation of the spin-resolved Andreev reflection (AR) in a QSH insulator strip touching on two neighbouring ferromagnetic insulators and one s-wave superconductor. It is demonstrated that, due to the interplay of the interedge coupling and ferromagnetic configuration, there could be not only usual local ARs leading to the spin-singlet pairing with the incident electron and Andreev-reflected hole from different spin subbands, but also novel local ARs giving rise to the spin-triplet pairing from the same spin subband. However, only the latter exists in the absence of the interedge coupling, and therefore the two pairings in turn testify the helical spin texture of the edge states. By proper tuning of the band structures of the ferromagnetic layers, under the resonance bias voltage, the usual and novel local ARs of [Formula: see text] can be all exhibited, resulting in fully spin-polarized pure spin-singlet superconductivity and pure spin-triplet superconductivity, respectively, which suggests a superconductivity switch from spin-singlet to -triplet pairing by electrical control. The results can be experimentally confirmed by the tunneling conductance and the noise power.

Superconductivity switch from spin-singlet to -triplet pairing in a topological superconducting junction

NASA Astrophysics Data System (ADS)

Tao, Ze; Chen, F. J.; Zhou, L. Y.; Li, Bin; Tao, Y. C.; Wang, J.

2018-06-01

The interedge coupling is the cardinal characteristic of the narrow quantum spin Hall (QSH) insulator, and thus could bring about exotic transport phenomena. Herein, we present a theoretical investigation of the spin-resolved Andreev reflection (AR) in a QSH insulator strip touching on two neighbouring ferromagnetic insulators and one s-wave superconductor. It is demonstrated that, due to the interplay of the interedge coupling and ferromagnetic configuration, there could be not only usual local ARs leading to the spin-singlet pairing with the incident electron and Andreev-reflected hole from different spin subbands, but also novel local ARs giving rise to the spin-triplet pairing from the same spin subband. However, only the latter exists in the absence of the interedge coupling, and therefore the two pairings in turn testify the helical spin texture of the edge states. By proper tuning of the band structures of the ferromagnetic layers, under the resonance bias voltage, the usual and novel local ARs of can be all exhibited, resulting in fully spin-polarized pure spin-singlet superconductivity and pure spin-triplet superconductivity, respectively, which suggests a superconductivity switch from spin-singlet to -triplet pairing by electrical control. The results can be experimentally confirmed by the tunneling conductance and the noise power.

Negative Ion Photoelectron Spectroscopy Confirms the Prediction that D-3h Carbontrioxide (CO 3) Has a Singlet Ground State

DOE PAGES

Hrovat, David; Hou, Gao-Lei; Chen, Bo; ...

2015-11-13

The CO 3 radical anion (CO 3 •–) has been formed by electrospraying carbonate dianion (CO 3 2–) into the gas phase. The negative ion photoelectron (NIPE) spectrum of CO 3 •– shows that, unlike trimethylenemethane [C(CH 2) 3], carbontrioxide (CO 3) has a singlet ground state. From the NIPE spectrum, the electron affinity of CO 3 was determined to be EA = 4.06 ± 0.03 eV, and the singlet-triplet energy difference was found to be ΔEST = - 17.8 ± 0.9 kcal/mol. B3LYP, CCSD(T), and CASPT2 calculations all find that the two lowest triplet states of CO 3 aremore » very close in energy, a prediction that is confirmed by the relative intensities of the bands in the NIPE spectrum of CO 3 •–. The 560 cm -1 vibrational progression, seen in the low energy region of the triplet band, enables the identification of the lowest, Jahn-Teller-distorted, triplet state as 3A 1, in which both unpaired electrons reside in σ MOs, rather than 3A 2, in which one unpaired electron occupies the b 2 σ MO, and the other occupies the b 1 π MO.« less

Study on optoelectronic properties of Spiro-CN for developing an efficient OLED

NASA Astrophysics Data System (ADS)

Mishra, Ashok Kumar

2018-05-01

There are a class of organic molecules and polymers which exhibit semiconductor behavior because of nearly free conjugate π-electrons. Hopping of these electrons in molecules forms different excited singlet and triplet states named as excitons. Some of these organic molecules can be set to emit photons by triplet-singlet excitonic transition via a process called Thermally Activated Delayed Fluorescence (TADF) which is exploited for designing the Organic Light Emitting diode (OLED.) Spiro-CN (spirobifluorene skeletons) Spiro is one of these reported noble metal-free TADF molecules which offers unique optical and electronic properties arising from the efficient transition and reverse intersystem crossing between the lowest singlet (S) and triplet (T) excited states. Its ability to harvest triplet excitons for fluorescence through facilitated reverse intersystem crossing (T→S) could directly impact their properties and performances, which is attractive for a wide variety of low-cost optoelectronic device. In the present study, the Spiro-CN compounds have been taken up for the investigation of various optoelectronic properties including the thermally activated delayed fluorescence (TADF) by using the Koopmans Method and Density Functional Theory. The present study discusses the utility of the Spiro-CN organic semiconductor as a suitable TADF material essential for developing an efficient Organic Light Emitting Diode (OLED).

Triplet state dissolved organic matter in aquatic photochemistry: reaction mechanisms, substrate scope, and photophysical properties.

PubMed

McNeill, Kristopher; Canonica, Silvio

2016-11-09

Excited triplet states of chromophoric dissolved organic matter ( 3 CDOM*) play a major role among the reactive intermediates produced upon absorption of sunlight by surface waters. After more than two decades of research on the aquatic photochemistry of 3 CDOM*, the need for improving the knowledge about the photophysical and photochemical properties of these elusive reactive species remains considerable. This critical review examines the efforts to date to characterize 3 CDOM*. Information on 3 CDOM* relies mainly on the use of probe compounds because of the difficulties associated with directly observing 3 CDOM* using transient spectroscopic methods. Singlet molecular oxygen ( 1 O 2 ), which is a product of the reaction between 3 CDOM* and dissolved oxygen, is probably the simplest indicator that can be used to estimate steady-state concentrations of 3 CDOM*. There are two major modes of reaction of 3 CDOM* with substrates, namely triplet energy transfer or oxidation (via electron transfer, proton-coupled electron transfer or related mechanisms). Organic molecules, including several environmental contaminants, that are susceptible to degradation by these two different reaction modes are reviewed. It is proposed that through the use of appropriate sets of probe compounds and model photosensitizers an improved estimation of the distribution of triplet energies and one-electron reduction potentials of 3 CDOM* can be achieved.

Rationalizing substituent effects in 1-azathioxanthone photophysics

NASA Astrophysics Data System (ADS)

Junker, Anne Kathrine R.; Just Sørensen, Thomas

2018-01-01

The influence of an electron donating substituent on the photophysical properties of 1-azathioxanthone dyes has been investigated using optical spectroscopy and theoretical models. The motivation behind the study is based on the fact that thioxanthones are efficient triplet sensitizers, and thus promising sensitizers for lanthanide centered emission. By adding an aza group to one of the phenyl ring systems, direct coordination to a lanthanide center becomes possible, which makes azathoixanthones great candidates as antenna chromophores in lanthanide(III) based dyes. Here, three 1-azathioxanthone derivatives have been synthesized targeting efficient triplet formation following absorption in the visible range of the spectrum. This is achieved by adding methoxy groups to the 1-azathioxanthone core. The derivatives were characterized using absorption, emission, and time-gated emission spectroscopy, where fluorescent quantum yields, singlet and triplet excited states lifetimes were determined. The experimentally determined photophysical properties of the three 1-azathioxanthone compounds are contrasted to those of the parent thioxanthone and is rationalized using the Strickler-Berg equation, Hückel MO theory, and Dewar’s rules in combination with computational chemistry. We find that the transition energies follow predictions, but that the overall photophysical properties are determined by the relative energies as well as the nature of the involved states in both the singlet and the triplet excited state manifolds.

Synthesis of Phosphorescent Asymmetrically π-Extended Porphyrins for Two-Photon Applications

PubMed Central

2015-01-01

Significant effort has been directed in recent years toward porphyrins with enhanced two-photon absorption (2PA). However, the properties of their triplet states, which are central to many applications, have rarely been examined in parallel. Here we report the synthesis of asymmetrically π-extended platinum(II) and palladium(II) porphyrins, whose 2PA into single-photon-absorbing states is enhanced as a result of the broken center-of-inversion symmetry and whose triplet states can be monitored by room-temperature phosphorescence. 5,15-Diaryl-syn-dibenzoporphyrins (DBPs) and syn-dinaphthoporphyrins (DNPs) were synthesized by [2 + 2] condensation of the corresponding dipyrromethanes and subsequent oxidative aromatization. Butoxycarbonyl groups on the meso-aryl rings render these porphyrins well-soluble in a range of organic solvents, while 5,15-meso-aryl substitution causes minimal nonplanar distortion of the macrocycle, ensuring high triplet emissivity. A syn-DBP bearing four alkoxycarbonyl groups in the benzo rings and possessing a large static dipole moment was also synthesized. Photophysical properties (2PA brightness and phosphorescence quantum yields and lifetimes) of the new porphyrins were measured, and their ground-state structures were determined by DFT calculations and/or X-ray analysis. The developed synthetic methods should facilitate the construction of π-extended porphyrins for applications requiring high two-photon triplet action cross sections. PMID:25157580

Dichorionic triamniotic triplet pregnancy complicated by twin anemia polycythemia sequence: the place of fetal therapy.

PubMed

Griersmith, Thérèse H; Fung, Alison M; Walker, Susan P

2014-12-01

Monochorionic twins as part of a high order multiple pregnancy can be an unintended consequence of the increasingly common practice of blastocyst transfer for couples requiring in vitro fertilisation (IVF) for infertility. Dichorionic triamniotic (DCTA) triplets is the most common presentation, and these pregnancies are particularly high risk because of the additional risks associated with monochorionicity. Surveillance for twin-to-twin transfusion syndrome, including twin anemia polycythemia sequence, may be more difficult, and any intervention to treat the monochorionic pair needs to balance the proposed benefits against the risks posed to the unaffected singleton. Counseling of families with DCTA triplets is therefore complex. Here, we report a case of DCTA triplets, where the pregnancy was complicated by threatened preterm labour, and twin anemia polycythemia sequence (TAPS) was later diagnosed at 28 weeks. The TAPS was managed with a single intraperitoneal transfusion, enabling safe prolongation of the pregnancy for over 2 weeks until recurrence of TAPS and preterm labour supervened. Postnatal TAPS was confirmed, and all three infants were later discharged home at term corrected age, and were normal at follow-up. This case highlights that in utero therapy has an important role in multiple pregnancies of mixed chorionicity, and can achieve safe prolongation of pregnancy at critical gestations.

Theoretical Study of the Photolysis Mechanisms of Methylpentaphenyldimetallanes (Ph₃MM'Ph₂Me; M, M' = Si and Ge).

PubMed

Su, Shih-Hao; Su, Ming-Der

2018-06-04

The mechanisms of the photolysis reactions are studied theoretically at the M06-2X/6-311G(d) level of theory, using the four types of group 14 molecules that have the general structure, Ph₃M⁻M'Ph₂Me (M and M' = Si and Ge), as model systems. This study provides the first theoretical evidence for the mechanisms of these photorearrangements of compounds that contain a M⁻M' single bond. The model investigations indicate that the preferred reaction route for the photolysis reactions is, as follows: reactant → Franck-Condon (FC) region → minimum (triplet) → transition state (triplet) → triplet/singlet intersystem crossing → photoproducts (both di-radicals and singlets). The theoretical findings demonstrate that the formation of radicals results from reactions of the triplet states of these reactants. This could be because both the atomic radius and the chemical properties of silicon and germanium are quite similar to each other and compared to other group 14 elements, their photolytic mechanisms are nearly the same. The results for the photolytic mechanisms that are studied in this work are consistent with the available experimental observations and allow for a number of predictions for other group 14 dimetallane analogues to be made.

Abnormal Magnetic Field Effects on Electrogenerated Chemiluminescence

NASA Astrophysics Data System (ADS)

Pan, Haiping; Shen, Yan; Wang, Hongfeng; He, Lei; Hu, Bin

2015-03-01

We report abnormal magnetic field effects on electrogenerated chemiluminescence (MFEECL) based on triplet emission from the Ru(bpy)3Cl2-TPrA electrochemical system: the appearance of MFEECL after magnetic field ceases. In early studies the normal MFEECL have been observed from electrochemical systems during the application of magnetic field. Here, the abnormal MFEECL suggest that the activated charge-transfer [Ru(bpy)33+ … TPrA•] complexes may become magnetized in magnetic field and experience a long magnetic relaxation after removing magnetic field. Our analysis indicates that the magnetic relaxation can gradually increase the density of charge-transfer complexes within reaction region due to decayed magnetic interactions, leading to a positive component in the abnormal MFEECL. On the other hand, the magnetic relaxation facilitates an inverse conversion from triplets to singlets within charge-transfer complexes. The inverse triplet --> singlet conversion reduces the density of triplet light-emitting states through charge-transfer complexes and gives rise to a negative component in the abnormal MFEECL. The combination of positive and negative components can essentially lead to a non-monotonic profile in the abnormal MFEECL after ceasing magnetic field. Nevertheless, our experimental studies may reveal un-usual magnetic behaviors with long magnetic relaxation from the activated charge-transfer [Ru(bpy)33+ … TPrA•] complexes in solution at room temperature.

Theoretical study on the photolysis mechanism of 2,3-diazabicyclo[2.2.2]oct-2-ene.

PubMed

Chen, Hui; Li, Shuhua

2005-09-28

A CASPT2/CASSCF study has been carried out to investigate the mechanism of the photolysis of 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO) under direct and triplet-sensitized irradiation. By exploring the detailed potential energy surfaces including intermediates, transition states, conical intersections, and singlet/triplet crossing points, for the first excited singlet (S(1)) and the low-lying triplet states (T(1), T(2), and T(3)), we provide satisfactory explanations of many experimental findings associated with the photophysical and photochemical processes of DBO. A key finding of this work is the existence of a significantly twisted S(1) minimum, which can satisfactorily explain the envelope of the broad emission band of DBO. It is demonstrated that the S(1) (n-pi*) intermediate can decay to the T(1) (n-pi*) state by undergoing intersystem crossing (rather inefficient) to the T(2) (pi-pi*) state followed by internal conversion to the T(1) state. The high fluorescence yield and the extraordinarily long lifetime of the singlet excited DBO are due to the presence of relatively high barriers, both for intersystem crossing and for C-N cleavage. The short lifetime of the triplet DBO is caused by fast radiationless decay to the ground state.

[C-terminal fragment of ribosomal protein S15 is located at the decoding site of the human ribosome].

PubMed

Khaĭrulina, Iu S; Molotkov, M V; Bulygin, K N; Graĭfer, D M; Ven'iaminova, A G; Karpova, G G

2008-01-01

Protein S15 is a characteristic component of the mammalian 80S ribosome that neighbors mRNA codon at the decoding site and the downstream triplets. In this study we determined S15 protein fragments located close to mRNA positions +4 to +12 with respect to the first nucleotide of the P site codon on the human ribosome. For cross-linking to ribosomal protein S15, a set of mRNA was used that contained triplet UUU/UUC at the 5'-termini and a perfluorophenyl azide-modified uridine in position 3' of this triplet. The locations of mRNA analogues on the ribosome were governed by tRNAPhe cognate to the UUU/UUC triplet targeted to the P site. Cross-linked S15 protein was isolated from the irradiated with mild UV light complexes of 80S ribosomes with tRNAPhe and mRNA analogues with subsequent cleavage with CNBr that splits polypeptide chain after methionines. Analysis of modified oligopeptides resulted from the cleavage revealed that in all cases cross-linking site was located in C-terminal fragment 111-145 of protein S15 indicating that this fragment is involved in formation of decoding site of the eukaryotic ribosome.

Control of social monogamy through aggression in a hermaphroditic shrimp

PubMed Central

2011-01-01

Introduction Sex allocation theory predicts that in small mating groups simultaneous hermaphroditism is the optimal form of gender expression. Under these conditions, male allocation is predicted to be very low and overall per-capita reproductive output maximal. This is particularly true for individuals that live in pairs, but monogamy is highly susceptible to cheating by both partners. However, certain conditions favour social monogamy in hermaphrodites. This study addresses the influence of group size on group stability and moulting cycles in singles, pairs, triplets and quartets of the socially monogamous shrimp Lysmata amboinensis, a protandric simultaneous hermaphrodite. Results The effect of group size was very strong: Exactly one individual in each triplet and exactly two individuals in each quartet were killed in aggressive interactions, resulting in group sizes of two individuals. All killed individuals had just moulted. No mortality occurred in single and pair treatments. The number of moults in the surviving shrimp increased significantly after changing from triplets and quartets to pairs. Conclusion Social monogamy in L. amboinensis is reinforced by aggressive expulsion of supernumerous individuals. We suggest that the high risk of mortality in triplets and quartets results in suppression of moulting in groups larger than two individuals and that the feeding ecology of L. amboinensis favours social monogamy. PMID:22078746

Control of social monogamy through aggression in a hermaphroditic shrimp.

PubMed

Wong, Janine Wy; Michiels, Nico K

2011-11-11

Sex allocation theory predicts that in small mating groups simultaneous hermaphroditism is the optimal form of gender expression. Under these conditions, male allocation is predicted to be very low and overall per-capita reproductive output maximal. This is particularly true for individuals that live in pairs, but monogamy is highly susceptible to cheating by both partners. However, certain conditions favour social monogamy in hermaphrodites. This study addresses the influence of group size on group stability and moulting cycles in singles, pairs, triplets and quartets of the socially monogamous shrimp Lysmata amboinensis, a protandric simultaneous hermaphrodite. The effect of group size was very strong: Exactly one individual in each triplet and exactly two individuals in each quartet were killed in aggressive interactions, resulting in group sizes of two individuals. All killed individuals had just moulted. No mortality occurred in single and pair treatments. The number of moults in the surviving shrimp increased significantly after changing from triplets and quartets to pairs. Social monogamy in L. amboinensis is reinforced by aggressive expulsion of supernumerous individuals. We suggest that the high risk of mortality in triplets and quartets results in suppression of moulting in groups larger than two individuals and that the feeding ecology of L. amboinensis favours social monogamy.

Analysis of Biophysical, Optical and Genetic Diversity of DoD Coral Reef Communities Using Advanced Fluorescence and Molecular Biology Techniques (Addendum)

DTIC Science & Technology

2011-08-01

light- harvesting antennae, the photochemistry in Photosystem II (PSII), and the photosynthetic electron transport to carbon fixation. Because these...energy transfer within the photosynthetic light- harvesting antennae is compromised under the heavy metal stress, leading to decline in the energy...photosynthetic reactions stimulates accumulation of triplet states in light- harvesting complexes that will be evident from the triplet quenching of

Deep blue exciplex organic light-emitting diodes with enhanced efficiency; P-type or E-type triplet conversion to singlet excitons?

PubMed

Jankus, Vygintas; Chiang, Chien-Jung; Dias, Fernando; Monkman, Andrew P

2013-03-13

Simple trilayer, deep blue, fluorescent exciplex organic light-emitting diodes (OLEDs) are reported. These OLEDs emit from an exciplex state formed between the highest occupied molecular orbital (HOMO) of N,N'-bis(1-naphthyl)N,N'-diphenyl-1,1'-biphenyl-4,4'-diamine (NPB) and lowest unoccupied molecular orbital (LUMO) of 1,3,5-tri(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl (TPBi) and the NPB singlet manifold, yielding 2.7% external quantum efficiency at 450 nm. It is shown that the majority of the delayed emission in electroluminescence arises from P-type triplet fusion at NPB sites not E-type reverse intersystem crossing because of the presence of the NPB triplet state acting as a deep trap. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A theoretical study of the cyclization processes of energized CCCSi and CCCP.

PubMed

Maclean, Micheal J; Eichinger, Peter C H; Wang, Tianfang; Fitzgerald, Mark; Bowie, John H

2008-12-11

Calculations at the CCSD(T)/aug-cc-pVDZ//B3LYP/6-31+G(d) level of theory have shown that cyclization of both the ground state triplet and the corresponding singlet state of CCCSi may rearrange to give cyclic isomers which upon ring opening may reform linear C(3)Si isomers in which the carbon atoms are scrambled. The cyclization processes are energetically favorable with barriers to the transition states from 13 to 16 kcal mol(-1). This should be contrasted with the analogous process of triplet CCCC to triplet rhombic C(4), which requires an excess energy of 25.8 kcal mol(-1). A similar cyclization of doublet CCCP requires 50.4 kcal mol(-1) of excess energy; this should be contrasted with the same process for CCCN, which requires 54.7 kcal mol(-1) to effect cyclization.

Spin nematics next to spin singlets

NASA Astrophysics Data System (ADS)

Yokoyama, Yuto; Hotta, Chisa

2018-05-01

We provide a route to generate nematic order in a spin-1/2 system. Unlike the well-known magnon-binding mechanism, our spin nematics requires neither the frustration effect nor spin polarization in a high field or in the vicinity of a ferromagnet, but instead appears next to the spin singlet phase. We start from a state consisting of a quantum spin-1/2 singlet dimer placed on each site of a triangular lattice, and show that interdimer ring exchange interactions efficiently dope the SU(2) triplets that itinerate and interact, easily driving a stable singlet state to either Bose-Einstein condensates or a triplet crystal, some hosting a spin nematic order. A variety of roles the ring exchange serves includes the generation of a bilinear-biquadratic interaction between nearby triplets, which is responsible for the emergent nematic order separated from the singlet phase by a first-order transition.