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Sample records for photoexcited triplet states

  1. Motional spin relaxation in photoexcited triplet states

    International Nuclear Information System (INIS)

    Harryvan, D.; Faassen, E. van

    1997-01-01

    Transient EPR experiments were performed on photoexcited spin triplet states of the luminescent dye EOSIN-Y in diluted (order of 1 nMol) frozen propane-1-ol solutions at various temperatures. Photoexcitation was achieved by irradiation with intense, short laser pulses. The details of the spin relaxation, in particular the dependence on time, magnetic field and microwave field strength are all reproduced by a model which computes the total magnetization in a population of photoexcited triplet states undergoing random reorientational motion. Using this model, we estimated the motional correlation times to be around a microsecond. This timescale is two orders of magnitude slower than the phase memory time of the triplets. (author)

  2. Spin filtering neutrons with a proton target dynamically polarized using photo-excited triplet states

    International Nuclear Information System (INIS)

    Haag, M.; Brandt, B. van den; Eichhorn, T.R.; Hautle, P.; Wenckebach, W.Th.

    2012-01-01

    In a test of principle a neutron spin filter has been built, which is based on dynamic nuclear polarization (DNP) using photo-excited triplet states. This DNP method has advantages over classical concepts as the requirements for cryogenic equipment and magnets are much relaxed: the spin filter is operated in a field of 0.3 T at a temperature of about 100 K and has performed reliably over periods of several weeks. The neutron beam was also used to analyze the polarization of the target employed as a spin filter. We obtained an independent measurement of the proton spin polarization of ∼0.13 in good agreement with the value determined with NMR. Moreover, the neutron beam was used to measure the proton spin polarization as a function of position in the naphthalene sample. The polarization was found to be homogeneous, even at low laser power, in contradiction to existing models describing the photo-excitation process.

  3. Effects of optical pumping in the photo-excitation of organic triplet states

    International Nuclear Information System (INIS)

    Lin, Tien-Sung; Yang, Tran-Chin; Sloop, David J.

    2013-01-01

    Highlights: • High electron spin polarization (ESP) was observed in pentacene triplets at room temperature. • The high ESP is transfer to the surrounding nuclear spin by optical pumping in zero-field (ZF). • The ZF transition frequencies and their line width depend on the laser pumping rate. • The spin–lattice relaxation times of the nuclear system are evaluated. - Abstract: Upon the application of laser and microwave pulses, non-zero magnetic moment of a photo-excited triplet state of organic molecules is generated in zero-field (ZF). The time evolution of the transient magnetic moments can be measured by free induction decay (FID) in ZF. The observed ZF spectra become broadened and ZF transition shifted to lower frequencies when the repetition rate of laser excitation is increased, which are attributed to the optical pumping of nuclear polarization (ONP) effect and the associated nuclear spin lattice relaxation processes. The observed ONP effect is discussed in terms of the local field effect and spin diffusion processes in optical pumping

  4. Effects of optical pumping in the photo-excitation of organic triplet states

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Tien-Sung, E-mail: lin@wustl.edu; Yang, Tran-Chin; Sloop, David J.

    2013-08-30

    Highlights: • High electron spin polarization (ESP) was observed in pentacene triplets at room temperature. • The high ESP is transfer to the surrounding nuclear spin by optical pumping in zero-field (ZF). • The ZF transition frequencies and their line width depend on the laser pumping rate. • The spin–lattice relaxation times of the nuclear system are evaluated. - Abstract: Upon the application of laser and microwave pulses, non-zero magnetic moment of a photo-excited triplet state of organic molecules is generated in zero-field (ZF). The time evolution of the transient magnetic moments can be measured by free induction decay (FID) in ZF. The observed ZF spectra become broadened and ZF transition shifted to lower frequencies when the repetition rate of laser excitation is increased, which are attributed to the optical pumping of nuclear polarization (ONP) effect and the associated nuclear spin lattice relaxation processes. The observed ONP effect is discussed in terms of the local field effect and spin diffusion processes in optical pumping.

  5. Photoexcited singlet and triplet states of a UV absorber ethylhexyl methoxycrylene.

    Science.gov (United States)

    Kikuchi, Azusa; Hata, Yuki; Kumasaka, Ryo; Nanbu, Yuichi; Yagi, Mikio

    2013-01-01

    The excited states of UV absorber, ethylhexyl methoxycrylene (EHMCR) have been studied through measurements of UV absorption, fluorescence, phosphorescence and electron paramagnetic resonance (EPR) spectra in ethanol. The energy levels of the lowest excited singlet (S1) and triplet (T1) states of EHMCR were determined. The energy levels of the S1 and T1 states of EHMCR are much lower than those of photolabile 4-tert-butyl-4'-methoxydibenzoylmethane. The energy levels of the S1 and T1 states of EHMCR are lower than those of octyl methoxycinnamate. The weak phosphorescence and EPR B(min) signals were observed and the lifetime was estimated to be 93 ms. These facts suggest that the significant proportion of the S1 molecules undergoes intersystem crossing to the T1 state, and the deactivation process from the T1 state is predominantly radiationless. The photostability of EHMCR arises from the (3)ππ* character in the T1 state. The zero-field splitting (ZFS) parameter in the T1 state is D** = 0.113 cm(-1). © 2012 The Authors Photochemistry and Photobiology © 2012 The American Society of Photobiology.

  6. Proton polarization above 70% by DNP using photo-excited triplet states, a first step towards a broadband neutron spin filter

    International Nuclear Information System (INIS)

    Eichhorn, T.R.; Niketic, N.; Brandt, B. van den; Filges, U.; Panzner, T.; Rantsiou, E.; Wenckebach, W.Th.; Hautle, P.

    2014-01-01

    The use of polarized protons as neutron spin filter is an attractive alternative to the well established neutron polarization techniques, as the large, spin-dependent neutron scattering cross-section for protons is useful up to the sub-MeV region. Employing optically excited triplet states for the dynamic nuclear polarization (DNP) of the protons relieves the stringent requirements of classical DNP schemes, i.e low temperatures and strong magnetic fields, making technically simpler systems with open geometries possible. Using triplet DNP a record polarization of 71% has been achieved in a pentacene doped naphthalene single crystal at a field of 0.36 T using a simple helium flow cryostat for cooling. Furthermore, by placing the polarized crystal in a neutron optics focus and de-focus scheme, the actual sample cross-section could be increased by a factor 35 corresponding to an effective spin filter cross-section of 18×18mm 2

  7. Proton polarization above 70% by DNP using photo-excited triplet states, a first step towards a broadband neutron spin filter

    Energy Technology Data Exchange (ETDEWEB)

    Eichhorn, T.R. [Laboratory for Developments and Methods (LDM), Paul Scherrer Institute, CH-5232 Villigen PSI (Switzerland); Laboratory of Functional and Metabolic Imaging, École Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne (Switzerland); Niketic, N.; Brandt, B. van den; Filges, U.; Panzner, T.; Rantsiou, E.; Wenckebach, W.Th. [Laboratory for Developments and Methods (LDM), Paul Scherrer Institute, CH-5232 Villigen PSI (Switzerland); Hautle, P., E-mail: patrick.hautle@psi.ch [Laboratory for Developments and Methods (LDM), Paul Scherrer Institute, CH-5232 Villigen PSI (Switzerland)

    2014-08-01

    The use of polarized protons as neutron spin filter is an attractive alternative to the well established neutron polarization techniques, as the large, spin-dependent neutron scattering cross-section for protons is useful up to the sub-MeV region. Employing optically excited triplet states for the dynamic nuclear polarization (DNP) of the protons relieves the stringent requirements of classical DNP schemes, i.e low temperatures and strong magnetic fields, making technically simpler systems with open geometries possible. Using triplet DNP a record polarization of 71% has been achieved in a pentacene doped naphthalene single crystal at a field of 0.36 T using a simple helium flow cryostat for cooling. Furthermore, by placing the polarized crystal in a neutron optics focus and de-focus scheme, the actual sample cross-section could be increased by a factor 35 corresponding to an effective spin filter cross-section of 18×18mm{sup 2}.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  10. Probing Microenvironment in Ionic Liquids by Time-Resolved EPR of Photoexcited Triplets.

    Science.gov (United States)

    Ivanov, M Yu; Veber, S L; Prikhod'ko, S A; Adonin, N Yu; Bagryanskaya, E G; Fedin, M V

    2015-10-22

    Unusual physicochemical properties of ionic liquids (ILs) open vistas for a variety of new applications. Herewith, we investigate the influence of microviscosity and nanostructuring of ILs on spin dynamics of the dissolved photoexcited molecules. We use two most common ILs [Bmim]PF6 and [Bmim]BF4 (with its close analogue [C10mim]BF4) as solvents and photoexcited Zn tetraphenylporphyrin (ZnTPP) as a probe. Time-resolved electron paramagnetic resonance (TR EPR) is employed to investigate spectra and kinetics of spin-polarized triplet ZnTPP in the temperature range 100-270 K. TR EPR data clearly indicate the presence of two microenvironments of ZnTPP in frozen ILs at 100-200 K, being manifested in different spectral shapes and different spin relaxation rates. For one of these microenvironments TR EPR data is quite similar to those obtained in common frozen organic solvents (toluene, glycerol, N-methyl-2-pyrrolidone). However, the second one favors the remarkably slow relaxation of spin polarization, being much longer than in the case of common solvents. Additional experiments using continuous wave EPR and stable nitroxide as a probe confirmed the formation of heterogeneities upon freezing of ILs and complemented TR EPR results. Thus, TR EPR of photoexcited triplets can be effectively used for probing heterogeneities and nanostructuring in frozen ILs. In addition, the increase of polarization lifetime in frozen ILs is an interesting finding that might allow investigation of short-lived intermediates inaccessible otherwise.

  11. Spin coherence in phosphorescent triplet states

    International Nuclear Information System (INIS)

    Hof, C.A. van 't

    1977-01-01

    The electron spin echo is studied on the dephasing mechanism in the photo-excited triplet state of quinoline in a durene host. First, a comparative investigation of the merits of the different spin echo techniques is presented. It turns out that the rotary echo generally yields a longer phase memory time than the two-pulse echo, whereas in the Carr-Purcell experiment, the dephasing can even be largely suppressed. Secondly, it is shown that the dephasing mechanism is determined by the nuclear spins of the guest molecules as well as those in the host material. A theoretical basis for interpreting the effect of vibronic relaxation on the decay rate of the rotary echo, as observed in parabenzoquinone, is given. Similar experiments in aniline reveal also that in this molecule, two close-lying triplet states exist, which is attributed to an inversion vibration analogous to the well-known example in ammonia

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

    Science.gov (United States)

    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

  13. Triplet State Resonance Raman Spectroscopy

    DEFF Research Database (Denmark)

    Wilbrandt, Robert Walter; Jensen, N. H.; Pagsberg, Palle Bjørn

    1978-01-01

    Makes the first report on the resonance Raman spectrum of a molecule in its triplet state generated by pulse radiolysis. A solution of 0.01 mol dm-3 of p-terphenyl in benzene was studied......Makes the first report on the resonance Raman spectrum of a molecule in its triplet state generated by pulse radiolysis. A solution of 0.01 mol dm-3 of p-terphenyl in benzene was studied...

  14. Spin-lattice relaxation in phosphorescent triplet state molecules

    International Nuclear Information System (INIS)

    Verbeek, P.J.F.

    1979-01-01

    The present thesis contains the results of a study of spin-lattice relaxation (SLR) in the photo-excited triplet state of aromatic molecules, dissolved in a molecular host crystal. It appears that SLR in phosphorescent triplet state molecules often is related to the presence of so-called (pseudo) localized phonons in the molecular mixed crystals. These local phonons can be thought to correspond with vibrations (librations) of the guest molecule in the force field of the surrounding host molecules. Since the intermolecular forces are relatively weak, the frequencies corresponding with these vibrations are relatively low and usually are of the order of 10-30 cm -1 . (Auth.)

  15. Triplet states in lead isotopes

    International Nuclear Information System (INIS)

    Naz, Tabassum; Ahmad, Shakeb; Abusara, H.

    2017-01-01

    Axial and triaxial calculations within RHB have been done to study the shape coexistence phenomena in the lead isotopes. Triplet states have been found in the 184-190 Pb which are in accordance with the experimental and other theoretical observations. The energy difference (in MeV) between the first two excited states also gives the evidence for the same

  16. Theory of Primary Photoexcitations in Donor-Acceptor Copolymers

    OpenAIRE

    Aryanpour, Karan; Dutta, Tirthankar; Huynh, Uyen N. V.; Vardeny, Zeev Valy; Mazumdar, Sumit

    2015-01-01

    We present a generic theory of primary photoexcitations in low band gap donor-acceptor conjugated copolymers. Because of the combined effects of strong electron correlations and broken symmetry, there is considerable mixing between a charge-transfer exciton and an energetically proximate triplet-triplet state with an overall spin singlet. The triplet-triplet state, optically forbidden in homopolymers, is allowed in donor-acceptor copolymers. For an intermediate difference in electron affiniti...

  17. Psoralen phototherapy and the possible involvement of triplet excited states

    International Nuclear Information System (INIS)

    Bensasson, R.V.; Salet, E.J.; Land, E.J.

    1979-01-01

    Psoralens are important drugs used in the phototherapy of psoriasis and vitiligo. It has been predicted that the triplet excited state of psoralen is photoactive. The authors have employed pulse radiolysis and laser flash photolysis to determine the quantum yields of formation of the triplet states of psoralens and related molecules including 4'5' dihydropsoralen, a model for 4'5' psoralenpyrimidine mono-adducts. The triplet spectra were used to follow the reactions of the triplets with thymine and tryptophan. Such reactions may take place via a charge transfer mechanism. For 8-methoxy psoralen, in addition to triplet formation, photoionization was detected using high laser intensities. Although significant yields of psoralen triplets are formed, and some such triplets react with thymine, it is too early yet to say definitely whether or not the therapeutic action of psoralens is mediated via such triplet states. (Auth.)

  18. The triplet excited state of bilirubin

    International Nuclear Information System (INIS)

    Land, E.J.

    1976-01-01

    Pulse radiolysis of benzene solutions of 40 μM bilirubin alone or with 0.1 M biphenyl has yielded evidence for the formation of the triplet excited state of bilirubin. Measurements were made of a number of properties, including the absorption spectrum (lambdasub(max)500nm), lifetime 9μs), extinction coefficient (8800 M -1 cm -1 ), energy level (approximately 150 kJ mol -1 ) and the rate of quenching by oxygen (rate constant, 8.2 x 10 8 M -1 s -1 ). An upper limit of 0.1 has also been obtained for the singlet to triplet crossover efficiency of bilirubin following excitation by 353 nm radiation. Consideration is given to the relevance of these data to the mechanism of bilirubin photo-destruction, both in vivo and in vitro. (U.K.)

  19. Charge Carrier Generation Followed by Triplet State Formation, Annihilation, and Carrier Recreation in PBDTTT-C:PC 60 BM Photovoltaic Blends

    KAUST Repository

    Gehrig, Dominik W.

    2015-05-22

    Triplet state formation after photoexcitation of low-bandgap polymer:fullerene blends has recently been demonstrated, however, the precise mechanism and its impact on solar cell performance is still under debate. Here, we study exciton dissociation, charge carrier generation and triplet state formation in low-bandgap polymer PBDTTT-C:PC60BM bulk heterojunction photovoltaic blends by a combination of fs-µs broadband Vis-NIR transient absorption (TA) pump-probe spectroscopy and multivariate curve resolution (MCR) data analysis. We found sub-ps exciton dissociation and charge generation followed by sub-ns triplet state creation. The carrier dynamics and triplet state dynamics exhibited a very pronounced intensity dependence indicating non-geminate recombination of free carriers is the origin of triplet formation in these blends. Triplets were found to be the dominant state present on the nanosecond timescale. Surprisingly, the carrier population increased again on the ns-µs timescale. We attribute this to triplet-triplet annihilation and the formation of higher energy excited states that subsequently underwent charge transfer. This unique dip and recovery of the charge population is a clear indication that triplets are formed by non-geminate recombination, as such a kinetic is incompatible with a monomolecular triplet state formation process.

  20. Charge Carrier Generation Followed by Triplet State Formation, Annihilation, and Carrier Recreation in PBDTTT-C:PC 60 BM Photovoltaic Blends

    KAUST Repository

    Gehrig, Dominik W.; Howard, Ian A.; Laquai, Fré dé ric

    2015-01-01

    Triplet state formation after photoexcitation of low-bandgap polymer:fullerene blends has recently been demonstrated, however, the precise mechanism and its impact on solar cell performance is still under debate. Here, we study exciton dissociation, charge carrier generation and triplet state formation in low-bandgap polymer PBDTTT-C:PC60BM bulk heterojunction photovoltaic blends by a combination of fs-µs broadband Vis-NIR transient absorption (TA) pump-probe spectroscopy and multivariate curve resolution (MCR) data analysis. We found sub-ps exciton dissociation and charge generation followed by sub-ns triplet state creation. The carrier dynamics and triplet state dynamics exhibited a very pronounced intensity dependence indicating non-geminate recombination of free carriers is the origin of triplet formation in these blends. Triplets were found to be the dominant state present on the nanosecond timescale. Surprisingly, the carrier population increased again on the ns-µs timescale. We attribute this to triplet-triplet annihilation and the formation of higher energy excited states that subsequently underwent charge transfer. This unique dip and recovery of the charge population is a clear indication that triplets are formed by non-geminate recombination, as such a kinetic is incompatible with a monomolecular triplet state formation process.

  1. Theory of Primary Photoexcitations in Donor-Acceptor Copolymers.

    Science.gov (United States)

    Aryanpour, Karan; Dutta, Tirthankar; Huynh, Uyen N V; Vardeny, Zeev Valy; Mazumdar, Sumit

    2015-12-31

    We present a generic theory of primary photoexcitations in low band gap donor-acceptor conjugated copolymers. Because of the combined effects of strong electron correlations and broken symmetry, there is considerable mixing between a charge-transfer exciton and an energetically proximate triplet-triplet state with an overall spin singlet. The triplet-triplet state, optically forbidden in homopolymers, is allowed in donor-acceptor copolymers. For an intermediate difference in electron affinities of the donor and the acceptor, the triplet-triplet state can have a stronger oscillator strength than the charge-transfer exciton. We discuss the possibility of intramolecular singlet fission from the triplet-triplet state, and how such fission can be detected experimentally.

  2. Electron paramagnetic resonance detection of carotenoid triplet states

    International Nuclear Information System (INIS)

    Frank, H.A.; Bolt, J.D.; deCosta, S.M.; Sauer, K.

    1980-01-01

    Triplet states of carotenoids have been detected by X-band electron paramagnetic resonance (EPR) and are reported here for the first time. The systems in which carotenoid triplets are observed include cells of photosynthetic bacteria, isolated bacteriochlorophyll-protein complexes, and detergent micelles which contain β-carotene. It is well known that if electron transfer is blocked following the initial acceptor in the bacterial photochemical reaction center, back reaction of the primary radical pair produces a bacteriochlorophyll dimer triplet. Previous optical studies have shown that in reaction centers containing carotenoids the bacteriochlorophyll dimer triplet sensitizes the carotenoid triplet. We have observed this carotenoid triplet state by EPR in reaction centers of Rhodopseudomonas sphaeroides, strain 2.4.1 (wild type), which contain the carotenoid spheroidene. The zero-field splitting parameters of the triplet spectrum are /D/ = 0.0290 +- 0.0005 cm -1 and /E/ = 0.0044 +-0.0006 cm -1 , in contrast with the parameters of the bacteriochlorophyll dimer triplet, which are /D/ = 0.0189 +- 0.0004 cm -1 and /E/ = 0.0032 +- 0.004 cm -1 . Bacteriochlorophyll in a light harvesting protein complex from Rps. sphaeroides, wild type, also sensitizes carotenoid triplet formation. In whole cells the EPR spectra vary with temperature between 100 and 10 K. Carotenoid triplets also have been observed by EPR in whole cells of Rps. sphaeroides and cells of Rhodospirillum rubrum which contain the carotenoid spirilloxanthin. Attempts to observe the triplet state EPR spectrum of β-carotene in numerous organic solvents failed. However, in nonionic detergent micelles and in phospholipid bilayer vesicles β-carotene gives a triplet state spectrum with /D/ = 0.0333 +- 0.0010 cm -1 and /E/ = 0.0037 +- 0.0010 cm -1 . 6 figures, 1 table

  3. Singlet versus Triplet Excited State Mediated Photoinduced Dehalogenation Reactions of Itraconazole in Acetonitrile and Aqueous Solutions.

    Science.gov (United States)

    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.

  4. Electron transfer and energy transfer reactions in photoexcited a-nonathiophene/C60 films and solutions

    NARCIS (Netherlands)

    Janssen, R.A.J.; Moses, D.; Sariciftci, N.S.; Heeger, A.J.

    1994-01-01

    Photoexcitation of a nonathiophene in film or solution across the p-p* energy gap produces a metastable triplet state. In the presence of C60, on the other hand, an ultra fast electron transfer from the photoexcited nonathiophene onto C60 is observed in films, whereas in solution C60 is involved in

  5. Triplet exciton dynamics

    International Nuclear Information System (INIS)

    Strien, A.J. van.

    1981-01-01

    Results are presented of electron spin echo experiments combined with laser flash excitation on triplet states of aromatic molecules. Some of the theoretical and experimental aspects of the photoexcited triplet state are discussed in detail and the electron spin echo spectrometers and laser systems are described. All the experiments described in this thesis were performed at liquid helium temperatures. An account is given of the ESE experiments performed on the photoexcited, non-radiative, triplet state of pentacene in napthalene. This is an example of the ESE technique being used to ascertain the zero-field splitting parameters, the populating and depopulating rates, and the orientation of the pentacene molecules in the naphthalene host. A combination of high resolution laser flash excitation and electron-spin echoes in zero-magnetic field allowed the author to observe directly k(vector)→k(vector)' exciton scattering processes in the one-dimensional triplet excitons in tetrachlorobenzene for the first time. Additional experimental data about exciton scattering is provided and a study of the orientational dependence of the spin-lattice relaxation of the triplet excitons in an external magnetic field is described. (Auth.)

  6. Energy transfer from an alkene triplet state during pulse radiolysis

    International Nuclear Information System (INIS)

    Barwise, A.J.G.; Gorman, A.A.; Rodgers, M.A.J.

    1976-01-01

    Pulse radiolysis of a benzene solution of norbornene containing low concentrations of anthracene results in delayed formation of anthracene triplet: this is the result of diffusion-controlled energy transfer from the alkene triplet state which has a natural lifetime in benzene of 250 ns. The use of various hydrocarbon acceptors has indicated that Esub(T)=20 000+-500 cm -1 for the relaxed T 1 state of the alkene, at least 5000 cm -1 below that of the spectroscopic state. (Auth.)

  7. Triplet State Resonance Raman Spectrum of all-trans-diphenylbutadiene

    DEFF Research Database (Denmark)

    Wilbrandt, Robert Walter; Grossman, W.E.L.; Killough, P.M

    1984-01-01

    The resonance Raman spectrum of all-trans-diphenylbutadiene (DPB) in its ground state and the resonance Raman spectrum (RRS) of DPB in its short-lived electronically excited triplet state are reported. Transient spectra were obtained by a pump-probe technique using two pulsed lasers...

  8. Triplet exciton formation in organic photovoltaics

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Xudong; Westenhoff, Sebastian; Howard, Ian; Ford, Thomas; Friend, Richard; Hodgkiss, Justin; Greenham, Neil [Cavendish Laboratory, University of Cambridge (United Kingdom)

    2009-07-01

    We have recently found that the formation of triplet excitons can be an important loss mechanism in organic photovoltaics, particularly in donor-acceptor blends designed to have high open-circuit voltages. This can occur when the intrachain triplet state lies lower in energy than the charge-transfer state formed at the heterojunction. We find that in a blend based on the polyfluorene derivatives F8BT and PFB, triplet excitons are formed after photoexcitation with much higher efficiency than in the component polymers. We use transient absorption spectroscopy to study the dynamics of charges and triplet excitons on timescales from picoseconds to microseconds. This allows us to determine a characteristic time of {proportional_to} 40 ns for intersystem crossing in the charge-separated state, and to estimate that as many as 75% of photoexcitations lead to the formation of triplet states. To avoid losses to triplet excitons in photovoltaic devices, it is necessary to separate charge pairs before intersystem crossing can occur. We also present photophysical measurements of saturation and relaxation of the triplet excited state absorption used to quantify triplet populations.

  9. Triplet states at an O vacancy in alpha-quartz

    DEFF Research Database (Denmark)

    Lægsgaard, Jesper

    2002-01-01

    The energy landscape of an alpha-quartz O vacancy in the lowest triplet state is investigated. Four local minima are identified and geometries, total energies, and electron paramagnetic resonance (EPR) parameters are obtained. On the basis of calculated values for the magnetic dipole interaction...

  10. Low-lying Photoexcited States of a One-Dimensional Ionic Extended Hubbard Model

    Science.gov (United States)

    Yokoi, Kota; Maeshima, Nobuya; Hino, Ken-ichi

    2017-10-01

    We investigate the properties of low-lying photoexcited states of a one-dimensional (1D) ionic extended Hubbard model at half-filling. Numerical analysis by using the full and Lanczos diagonalization methods shows that, in the ionic phase, there exist low-lying photoexcited states below the charge transfer gap. As a result of comparison with numerical data for the 1D antiferromagnetic (AF) Heisenberg model, it was found that, for a small alternating potential Δ, these low-lying photoexcited states are spin excitations, which is consistent with a previous analytical study [Katsura et al., link ext-link-type="uri" xlink:href="https://doi.org/10.1103/PhysRevLett.103.177402" xlink:type="simple">Phys. Rev. Lett. 103, 177402 (2009)link>]. As Δ increases, the spectral intensity of the 1D ionic extended Hubbard model rapidly deviates from that of the 1D AF Heisenberg model and it is clarified that this deviation is due to the neutral-ionic domain wall, an elementary excitation near the neutral-ionic transition point.

  11. Dynamics of Photoexcited State of Semiconductor Quantum Dots

    Science.gov (United States)

    Trivedi, Dhara J.

    In this thesis, non-adiabatic molecular dynamics (NAMD) of excited states in semiconductor quantum dots are investigated. Nanoscale systems provide important opportunities for theory and computation for research because the experimental tools often provide an incomplete picture of the structure and/or function of nanomaterials, and theory can often fill in missing features crucial in understanding what is being measured. The simulation of NAMD is an indispensable tool for understanding complex ultrafast photoinduced processes such as charge and energy transfer, thermal relaxation, and charge recombination. Based on the state-of-the-art ab initio approaches in both the energy and time domains, the thesis presents a comprehensive discussion of the dynamical processes in quantum dots, ranging from the initial photon absorption to the final emission. We investigate the energy relaxation and transfer rates in pure and surface passivated quantum dots of different sizes. The study establishes the fundamental mechanisms of the electron and hole relaxation processes with and without hole traps. We develop and implement more accurate and efficient methods for NAMD. These methods are advantageous over the traditional ones when one encounters classically forbidden transitions. We also explore the effect of decoherence and non-adiabatic couplings on the dynamics. The results indicate significant influence on the accuracy and related computational cost of the simulated dynamics.

  12. Observation of the long-lived triplet excited state of perylenebisimide (PBI) in C^N cyclometalated Ir(III) complexes and application in photocatalytic oxidation.

    Science.gov (United States)

    Sun, Jifu; Zhong, Fangfang; Zhao, Jianzhang

    2013-07-14

    Perylenebisimide (PBI) was used to prepare C^N cyclometalated Ir(III) complexes that show strong absorption of visible light and it is the first time the long-lived triplet excited state of PBI chromophore was observed in a transition metal complex (τT = 22.3 μs). Previously, the lifetime of the triplet state of PBI in transition metal complexes was usually shorter than 1.0 μs. Long-lived triplet excited states are useful for applications in photocatalysis or other photophysical processes concerning triplet-triplet-energy-transfer. PBI and amino-PBI were used for preparation of cyclometalated Ir(III) complexes (Ir-2 and Ir-3), in which the PBI chromophore was connected to the coordination center via C≡C π-conjugation bond. The new complexes show strong absorption in visible region (ε = 34,200 M(-1) cm(-1) at 541 nm for Ir-2, and ε = 19,000 at 669 nm for Ir-3), compared to the model complex Ir(ppy)(bpy)[PF6] Ir-1 (ε PBI-localized long-lived (3)IL states were populated for Ir-2 and Ir-3 upon photoexcitation. The complexes were used as triplet photosensitizers for (1)O2-mediated photooxidation of 1,5-dihydronaphthalene to produce juglone, an important intermediate for preparation of anti-cancer compounds. (1)O2 quantum yields (Φ(Δ)) up to 91% were observed for the new Ir(III) complexes and the overall photosensitizing ability is much higher than the conventional Ir(III) complex Ir-1, which shows the typical weak visible light absorption in visible region. Our results are useful for preparation of transition metal complexes that show strong absorption of visible light and long-lived triplet excited state and for the application of these complexes in photocatalysis.

  13. Room temperature triplet state spectroscopy of organic semiconductors.

    Science.gov (United States)

    Reineke, Sebastian; Baldo, Marc A

    2014-01-21

    Organic light-emitting devices and solar cells are devices that create, manipulate, and convert excited states in organic semiconductors. It is crucial to characterize these excited states, or excitons, to optimize device performance in applications like displays and solar energy harvesting. This is complicated if the excited state is a triplet because the electronic transition is 'dark' with a vanishing oscillator strength. As a consequence, triplet state spectroscopy must usually be performed at cryogenic temperatures to reduce competition from non-radiative rates. Here, we control non-radiative rates by engineering a solid-state host matrix containing the target molecule, allowing the observation of phosphorescence at room temperature and alleviating constraints of cryogenic experiments. We test these techniques on a wide range of materials with functionalities spanning multi-exciton generation (singlet exciton fission), organic light emitting device host materials, and thermally activated delayed fluorescence type emitters. Control of non-radiative modes in the matrix surrounding a target molecule may also have broader applications in light-emitting and photovoltaic devices.

  14. Identification of quenchers of photoexcited States as novel agents for skin photoprotection.

    Science.gov (United States)

    Wondrak, Georg T; Jacobson, Myron K; Jacobson, Elaine L

    2005-02-01

    Photooxidative stress is a key mechanism in UVA-induced skin photodamage. Photoexcited states of endogenous UVA chromophores such as porphyrins, melanin precursors, and cross-link-fluorophores of skin collagen exert skin photodamage by direct reaction with substrate molecules (type I photosensitization) or molecular oxygen (type II), leading to formation of reactive oxygen species. Based on our previous research on the role of photoexcited states of endogenous skin chromophores as sensitizers of photooxidative stress, we describe here the identification of a novel class of chemopreventive agents for topical skin photoprotection: quenchers of photoexcited states (QPES). QPES compounds antagonize the harmful excited state chemistry of endogenous sensitizers by physical quenching, facilitating the harmless return of the sensitizer excited state to the electronic ground state by energy dissipation. To identify QPES compounds suitable for development, we designed a primary screening assay based on QPES suppression of photosensitized plasmid cleavage using conditions that exclude antioxidants. This screen is followed with a screen to test for nonsacrificial quenching of dye-sensitized singlet oxygen ((1)O(2)) formation by electron paramagnetic resonance detection of 2,2,6,6-tetramethyl-piperidine-1-oxyl, a stable free radical indicative of (1)O(2) formation. These initial screens identified a pyrrolidine pharmacophore with pronounced QPES activity, and l-proline and other noncytotoxic proline derivatives containing this pharmacophore were then screened for efficacy in cellular models of sensitized photodamage. These compounds showed QPES protection against dye-sensitized and psoralen-UVA-induced apoptosis and suppression of proliferation in cultured human skin keratinocytes and fibroblasts. Furthermore, QPES photoprotection of reconstructed full thickness human skin exposed to solar simulated light has been demonstrated.

  15. Pentacene appended to a TEMPO stable free radical: the effect of magnetic exchange coupling on photoexcited pentacene.

    Science.gov (United States)

    Chernick, Erin T; Casillas, Rubén; Zirzlmeier, Johannes; Gardner, Daniel M; Gruber, Marco; Kropp, Henning; Meyer, Karsten; Wasielewski, Michael R; Guldi, Dirk M; Tykwinski, Rik R

    2015-01-21

    Understanding the fundamental spin dynamics of photoexcited pentacene derivatives is important in order to maximize their potential for optoelectronic applications. Herein, we report on the synthesis of two pentacene derivatives that are functionalized with the [(2,2,6,6-tetramethylpiperidin-1-yl)oxy] (TEMPO) stable free radical. The presence of TEMPO does not quench the pentacene singlet excited state, but does quench the photoexcited triplet excited state as a function of TEMPO-to-pentacene distance. Time-resolved electron paramagnetic resonance experiments confirm that triplet quenching is accompanied by electron spin polarization transfer from the pentacene excited state to the TEMPO doublet state in the weak coupling regime.

  16. Photoexcited riboflavin induces oxidative damage to human serum albumin

    Science.gov (United States)

    Hirakawa, Kazutaka; Yoshioka, Takuto

    2015-08-01

    Photoexcited riboflavin induced damage of human serum albumin (HSA), a water soluble protein, resulting in the diminishment of fluorescence from the tryptophan residue. Because riboflavin hardly photosensitized singlet oxygen generation and sodium azide, a singlet oxygen quencher, did not inhibit protein damage, electron transfer-mediated oxidation of HSA was speculated. Fluorescence lifetime of riboflavin was not affected by HSA, suggesting that the excited triplet state of riboflavin is responsible for protein damage through electron transfer. In addition, the preventive effect of xanthone derivatives, triplet quenchers, on photosensitized protein damage could be evaluated using this photosensitized reaction system of riboflavin and HSA.

  17. Transient transition from free carrier metallic state to exciton insulating state in GaAs by ultrafast photoexcitation

    Science.gov (United States)

    Nie, X. C.; Song, Hai-Ying; Zhang, Xiu; Gu, Peng; Liu, Shi-Bing; Li, Fan; Meng, Jian-Qiao; Duan, Yu-Xia; Liu, H. Y.

    2018-03-01

    We present systematic studies of the transient dynamics of GaAs by ultrafast time-resolved reflectivity. In photoexcited non-equilibrium states, we found a sign reverse in reflectivity change ΔR/R, from positive around room temperature to negative at cryogenic temperatures. The former corresponds to a free carrier metallic state, while the latter is attributed to an exciton insulating state, in which the transient electronic properties is mostly dominated by excitons, resulting in a transient metal–insulator transition (MIT). Two transition temperatures (T 1 and T 2) are well identified by analyzing the intensity change of the transient reflectivity. We found that photoexcited MIT starts emerging at T 1 as high as ∼ 230 K, in terms of a dip feature at 0.4 ps, and becomes stabilized below T 2 that is up to ∼ 180 K, associated with a negative constant after 40 ps. Our results address a phase diagram that provides a framework for the inducing of MIT through temperature and photoexcitation, and may shed light on the understanding of light-semiconductor interaction and exciton physics.

  18. Dynamics of excited-state intramolecular proton transfer reactions in piroxicam. Role of triplet states

    Science.gov (United States)

    Cho, Dae Won; Kim, Yong Hee; Yoon, Minjoong; Jeoung, Sae Chae; Kim, Dongho

    1994-08-01

    The picosecond time-resolved fluorescence and transient absorption behavior of piroxicam at room temperature are reported. The keto tautomer in the excited singlet state ( 1K*) formed via the fast intramolecular proton transfer (≈ 20 ps) is observed. The short-lived (7.5 ns) triplet state of keto tauomer ( 3K*) is generated from 1K * in toluene whereas it is hardly observed in ethanol. Consequently, rapid reverse proton transfer takes place from 3K * to the enol triplet state ( 3E *.

  19. Wavelength dependence of the efficiency of singlet oxygen generation upon photoexcitation of photosensitizers

    Directory of Open Access Journals (Sweden)

    Starukhin A.

    2017-01-01

    Full Text Available The dependence of the efficiency of singlet oxygen (1Δg generation upon excitation of photosensitizer at different wavelength was observed for several derivatives of palladium porphyrin in carbon tetrachloride. The efficiency of singlet oxygen generation upon excitation in a blue region of the spectrum (Soret band exceeds by several times the efficiency at excitation in the red spectral region (Q band. The effect of enhancement of singlet oxygen generation upon CW photoexcitation to Soret band of photosensitizer may be explained by influence of high laying triplet states of a donor molecule on the triplet-triplet energy transfer.

  20. Classical and quantum 'EPR'-spin correlations in the triplet state

    International Nuclear Information System (INIS)

    Barut, A.O.; Bozic, M.

    1987-01-01

    Quantum correlations and joint probabilities in the triplet state as well as the correlations of components of two correlated classical spin vectors, are evaluated. Correlations in the states with |S tot z |=1 are different from correlations in the state with S tot z =0 which may serve to distinguish different states of the triplet. As in the singlet case, we can reproduce quantum correlations by correlated classical spin vectors which also provide a precision of the notion of ''parallel spins''. Triplet state correlations could in principle be measured, for example, in the decay reaction J/ψ → e + e - for which there is a sufficiently large branching ratio. (author). 12 refs

  1. Interplay between singlet and triplet excited states in a conformationally locked donor–acceptor dyad

    KAUST Repository

    Filatov, Mikhail A.

    2015-10-13

    The synthesis and photophysical characterization of a palladium(II) porphyrin – anthracene dyad bridged via short and conformationally rigid bicyclo[2.2.2]octadiene spacer were achieved. A spectroscopic investigation of the prepared molecule in solution has been undertaken to study electronic energy transfer in excited singlet and triplet states between the anthracene and porphyrin units. By using steady-state and time-resolved photoluminescence spectroscopy it was shown that excitation of the singlet excited state of the anthracene leads to energy transfer to the lower-lying singlet state of porphyrin. Alternatively, excitation of the porphyrin followed by intersystem crossing to the triplet state leads to very fast energy transfer to the triplet state of anthracene. The rate of this energy transfer has been determined by transient absorption spectroscopy. Comparative studies of the dynamics of triplet excited states of the dyad and reference palladium octaethylporphyrin (PdOEP) have been performed.

  2. Interplay between singlet and triplet excited states in a conformationally locked donor–acceptor dyad

    KAUST Repository

    Filatov, Mikhail A.; Etzold, Fabian; Gehrig, Dominik; Laquai, Fré dé ric; Busko, Dmitri; Landfester, Katharina; Baluschev, Stanislav

    2015-01-01

    The synthesis and photophysical characterization of a palladium(II) porphyrin – anthracene dyad bridged via short and conformationally rigid bicyclo[2.2.2]octadiene spacer were achieved. A spectroscopic investigation of the prepared molecule in solution has been undertaken to study electronic energy transfer in excited singlet and triplet states between the anthracene and porphyrin units. By using steady-state and time-resolved photoluminescence spectroscopy it was shown that excitation of the singlet excited state of the anthracene leads to energy transfer to the lower-lying singlet state of porphyrin. Alternatively, excitation of the porphyrin followed by intersystem crossing to the triplet state leads to very fast energy transfer to the triplet state of anthracene. The rate of this energy transfer has been determined by transient absorption spectroscopy. Comparative studies of the dynamics of triplet excited states of the dyad and reference palladium octaethylporphyrin (PdOEP) have been performed.

  3. Triplet Excited States as a Source of Relevant (Bio)Chemical Information

    OpenAIRE

    Jiménez Molero, María Consuelo; Miranda Alonso, Miguel Ángel

    2014-01-01

    The properties of triplet excited states are markedly medium-dependent, which turns this species into valuable tools for investigating the microenvironments existing in protein binding pockets. Monitoring of the triplet excited state behavior of drugs within transport proteins (serum albumins and alpha(1)-acid glycoproteins) by laser flash photolysis constitutes a valuable source of information on the strength of interaction, conformational freedom and protection from oxygen or other external...

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

    KAUST Repository

    Pace, Natalie A.

    2017-11-30

    The conjugated polymer poly(benzothiophene dioxide) (PBTDO1) has recently been shown to exhibit efficient intramolecular singlet fission in solution. In this paper, 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 carefully engineer the solid-state microstructure of these “singlet fission polymers” in order to produce the long-lived triplets needed to realize efficient photovoltaic devices.

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

    KAUST Repository

    Pace, Natalie A.; Zhang, Weimin; Arias, Dylan H.; McCulloch, Iain; Rumbles, Garry; Johnson, Justin C.

    2017-01-01

    The conjugated polymer poly(benzothiophene dioxide) (PBTDO1) has recently been shown to exhibit efficient intramolecular singlet fission in solution. In this paper, 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 carefully engineer the solid-state microstructure of these “singlet fission polymers” in order to produce the long-lived triplets needed to realize efficient photovoltaic devices.

  6. On the Josephson effect between superconductors in singlet and triplet spin-pairing states

    International Nuclear Information System (INIS)

    Pals, J.A.; Haeringen, W. van

    1977-01-01

    An expression is derived for the Josephson current between two weakly coupled superconductors of which one or both have pairs in a spin-triplet state. It is shown that there can be no Josephson effect up to second order in the transition matrix elements between a superconductor with spin-triplet pairs and one with spin-singlet pairs if the coupling between the two superconductors can be described with a spin-conserving tunnel hamiltonian. This is shown to offer a possibility to investigate experimentally whether a particular superconductor has spin-triplet pairs by coupling it weakly to a well-known spin-singlet pairing superconductor. (Auth.)

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

    Science.gov (United States)

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

    2016-10-01

    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.

  8. Triplet states of carotenoids from photosynthetic bacteria studied by nanosecond ultraviolet and electron pulse irradiation

    International Nuclear Information System (INIS)

    Bensasson, R.; Land, E.J.; Maudinas, B.

    1976-01-01

    Absorptions of the triplet excited states of five carotenoids (15,15'-cis phytoene, all-trans phytoene, zeta-carotene, spheroidene and spirillox-anthin), extracted from the photosynthetic bacteria Rhodopseudomonas spheroides and Rhodospirillum rubrum, have been detected in solution using pulse radiolysis and laser flash photolysis. Triplet lifetimes, extinction coefficients, lowest energy levels and quantum efficiencies of formation have been determined. Comparison of the carotenoid triplet energy levels with that of O 2 ('Δsub(g)) suggests that spirilloxanthin, spheroidene and possibly also zeta-carotene, would be expected to protect against photodynamic action caused by O 2 ('Δsub(g)), but not cis or trans phytoene. The S → T intersystem crossing efficiencies of all five polyenes were found to be low, being a few per cent or less. In their protective role these triplet states can only therefore be effectively reached via energy transfer from another triplet, except in the case of O 2 (Δsub(g)). The low crossover efficiencies also mean that light absorbed in such carotenoids in their possible role as accessory pigments would not be wasted in crossing over to the triplet state. (author)

  9. Photo-excited states in germanium at liquid-helium temperatures

    International Nuclear Information System (INIS)

    Culbertson, J.C.

    1982-12-01

    A wide variety of experimental work dealing with the basic properties of photoexcited states in Ge at liquid helium temperatures is presented. The primary emphasis is on the electron-hole liquid (EHL) and the free exciton (FE). The EHL is composed of two interpenetrating Fermi liquids, one of electrons and one of holes, each with its own Fermi level. The FE dealt with here is a mobile, loosely bound state of an electron and a hole. We report the first absolute measurement of the density dependence of the enhancement factor g/sub eh/(0) for the EHL in Ge. This factor g/sub eh/(0) is a measure of the electron-hole spatial correlation function, and provides a valuable and sensitive test for the predictions of various many-body-theory approximations. An EHL droplet - FE gas system confined to a strain induced potential well was used. The measurement approach relied on only a few simple and verifiable assumptions. A byproduct of this work was the measurement as a function of stress of: the electron and hole Fermi levels E/sub F//sup e/ and E/sub F//sup h/, the EHL density n/sub l/, the condensation energy phi of a FE relative to the EHL, and the binding energy of a FE (E/sub x/) relative to free carriers (FC). The decay of a FE-FC system confined to a strain induced potential well is studied. The first direct measurement of the FE diffusivity D/sub x/ is reported. The evolution in time of spatial profiles of FE luminescence were measured. From these FE density profiles, D/sub x/(4.2K) approx. = to 300 cm 2 s - 1 , the surface recombination velocity S approx. = 3000 cm s - 1 , and the FE lifetime tau/sub x/ = 27 μs with surface effects excluded were determined

  10. Ultra-fast relaxation, decoherence, and localization of photoexcited states in π-conjugated polymers

    Science.gov (United States)

    Mannouch, Jonathan R.; Barford, William; Al-Assam, Sarah

    2018-01-01

    The exciton relaxation dynamics of photoexcited electronic states in poly(p-phenylenevinylene) are theoretically investigated within a coarse-grained model, in which both the exciton and nuclear degrees of freedom are treated quantum mechanically. The Frenkel-Holstein Hamiltonian is used to describe the strong exciton-phonon coupling present in the system, while external damping of the internal nuclear degrees of freedom is accounted for by a Lindblad master equation. Numerically, the dynamics are computed using the time evolving block decimation and quantum jump trajectory techniques. The values of the model parameters physically relevant to polymer systems naturally lead to a separation of time scales, with the ultra-fast dynamics corresponding to energy transfer from the exciton to the internal phonon modes (i.e., the C-C bond oscillations), while the longer time dynamics correspond to damping of these phonon modes by the external dissipation. Associated with these time scales, we investigate the following processes that are indicative of the system relaxing onto the emissive chromophores of the polymer: (1) Exciton-polaron formation occurs on an ultra-fast time scale, with the associated exciton-phonon correlations present within half a vibrational time period of the C-C bond oscillations. (2) Exciton decoherence is driven by the decay in the vibrational overlaps associated with exciton-polaron formation, occurring on the same time scale. (3) Exciton density localization is driven by the external dissipation, arising from "wavefunction collapse" occurring as a result of the system-environment interactions. Finally, we show how fluorescence anisotropy measurements can be used to investigate the exciton decoherence process during the relaxation dynamics.

  11. Triplet State Formation in Photovoltaic Blends of DPP-Type Copolymers and PC71BM

    KAUST Repository

    Ochsmann, Julian R.

    2015-04-29

    The exciton dynamics in pristine films of two structurally related low-bandgap diketopyrrolopyrrole (DPP)-based donor–acceptor copolymers and the photophysical processes in bulk heterojunction solar cells using DPP copolymer:PC71BM blends are investigated by broadband transient absorption (TA) pump-probe experiments covering the vis–near-infrared spectral and fs–μs dynamic range. The experiments reveal surprisingly short exciton lifetimes in the pristine poly­mer films in conjunction with fast triplet state formation. An in-depth analysis of the TA data by multivariate curve resolution analysis shows that in blends with fullerene as acceptor ultrafast exciton dissociation creates charge carriers, which then rapidly recombine on the sub-ns timescale. Furthermore, at the carrier densities created by pulsed laser excitation the charge carrier recombination leads to a substantial population of the polymer triplet state. In fact, virtually quantitative formation of triplet states is observed on the sub-ns timescale. However, the quantitative triplet formation on the sub-ns timescale is not in line with the power conversion efficiencies of devices indicating that triplet state formation is an intensity-dependent process in these blends and is reduced under solar illumination conditions, as free charge carriers can be extracted from the photoactive layer in devices.

  12. Triplet excited States as a source of relevant (bio)chemical information.

    Science.gov (United States)

    Jiménez, M Consuelo; Miranda, Miguel A

    2014-01-01

    The properties of triplet excited states are markedly medium-dependent, which turns this species into valuable tools for investigating the microenvironments existing in protein binding pockets. Monitoring of the triplet excited state behavior of drugs within transport proteins (serum albumins and α1-acid glycoproteins) by laser flash photolysis constitutes a valuable source of information on the strength of interaction, conformational freedom and protection from oxygen or other external quenchers. With proteins, formation of spatially confined triplet excited states is favored over competitive processes affording ionic species. Remarkably, under aerobic atmosphere, the triplet decay of drug@protein complexes is dramatically longer than in bulk solution. This offers a convenient dynamic range for assignment of different triplet populations or for stereochemical discrimination. In this review, selected examples of the application of the laser flash photolysis technique are described, including drug distribution between the bulk solution and the protein cavities, or between two types of proteins, detection of drug-drug interactions inside proteins, and enzyme-like activity processes mediated by proteins. Finally, protein encapsulation can also modify the photoreactivity of the guest. This is illustrated by presenting an example of retarded photooxidation.

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

    Science.gov (United States)

    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

  14. Triplet excited state properties in variable gap π-conjugated donor–acceptor–donor chromophores

    KAUST Repository

    Cekli, Seda; Winkel, Russell W.; Alarousu, Erkki; Mohammed, Omar F.; Schanze, Kirk S.

    2016-01-01

    A series of variable band-gap donor–acceptor–donor (DAD) chromophores capped with platinum(II) acetylide units has been synthesized and fully characterized by electrochemical and photophysical methods, with particular emphasis placed on probing triplet excited state properties. A counter-intuitive trend of increasing fluorescence quantum efficiency and lifetime with decreasing excited state energy (optical gap) is observed across the series of DAD chromophores. Careful study of the excited state dynamics, including triplet yields (as inferred from singlet oxygen sensitization), reveals that the underlying origin of the unusual trend in the fluorescence parameters is that the singlet–triplet intersystem crossing rate and yield decrease with decreasing optical gap. It is concluded that the rate of intersystem crossing decreases as the LUMO is increasingly localized on the acceptor unit in the DAD chromophore, and this result is interpreted as arising because the extent of spin–orbit coupling induced by the platinum heavy metal centers decreases as the LUMO is more localized on the acceptor. In addition to the trend in intersystem crossing, the results show that the triplet decay rates follow the Energy Gap Law correlation over a 1.8 eV range of triplet energy and 1000-fold range of triplet decay rates. Finally, femtosecond transient absorption studies for the DAD chromophores reveals a strong absorption in the near-infrared region which is attributed to the singlet excited state. This spectral band appears to be general for DAD chromophores, and may be a signature of the charge transfer (CT) singlet excited state.

  15. Triplet excited state properties in variable gap π-conjugated donor–acceptor–donor chromophores

    KAUST Repository

    Cekli, Seda

    2016-02-12

    A series of variable band-gap donor–acceptor–donor (DAD) chromophores capped with platinum(II) acetylide units has been synthesized and fully characterized by electrochemical and photophysical methods, with particular emphasis placed on probing triplet excited state properties. A counter-intuitive trend of increasing fluorescence quantum efficiency and lifetime with decreasing excited state energy (optical gap) is observed across the series of DAD chromophores. Careful study of the excited state dynamics, including triplet yields (as inferred from singlet oxygen sensitization), reveals that the underlying origin of the unusual trend in the fluorescence parameters is that the singlet–triplet intersystem crossing rate and yield decrease with decreasing optical gap. It is concluded that the rate of intersystem crossing decreases as the LUMO is increasingly localized on the acceptor unit in the DAD chromophore, and this result is interpreted as arising because the extent of spin–orbit coupling induced by the platinum heavy metal centers decreases as the LUMO is more localized on the acceptor. In addition to the trend in intersystem crossing, the results show that the triplet decay rates follow the Energy Gap Law correlation over a 1.8 eV range of triplet energy and 1000-fold range of triplet decay rates. Finally, femtosecond transient absorption studies for the DAD chromophores reveals a strong absorption in the near-infrared region which is attributed to the singlet excited state. This spectral band appears to be general for DAD chromophores, and may be a signature of the charge transfer (CT) singlet excited state.

  16. Solid state photon upconversion utilizing thermally activated delayed fluorescence molecules as triplet sensitizer

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Tony C.; Congreve, Daniel N.; Baldo, Marc A., E-mail: baldo@mit.edu [Department of Electrical Engineering and Computer Science, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 (United States)

    2015-07-20

    The ability to upconvert light is useful for a range of applications, from biological imaging to solar cells. But modern technologies have struggled to upconvert incoherent incident light at low intensities. Here, we report solid state photon upconversion employing triplet-triplet exciton annihilation in an organic semiconductor, sensitized by a thermally activated-delayed fluorescence (TADF) dye. Compared to conventional phosphorescent sensitizers, the TADF dye maximizes the wavelength shift in upconversion due to its small singlet-triplet splitting. The efficiency of energy transfer from the TADF dye is 9.1%, and the conversion yield of sensitizer exciton pairs to singlet excitons in the annihilator is 1.1%. Our results demonstrate upconversion in solid state geometries and with non-heavy metal-based sensitizer materials.

  17. Magnetically Bistable Nitrenes: Matrix Isolation of Furoylnitrenes in Both Singlet and Triplet States and Triplet 3-Furylnitrene.

    Science.gov (United States)

    Feng, Ruijuan; Lu, Yan; Deng, Guohai; Xu, Jian; Wu, Zhuang; Li, Hongmin; Liu, Qian; Kadowaki, Norito; Abe, Manabu; Zeng, Xiaoqing

    2018-01-10

    Two simple acylnitrenes, 2-furoylnitrene (2) and 3-furoylnitrene (6), were generated through 266 nm laser photolysis of the corresponding azides. Both are magnetically bistable in cryogenic matrices, as evidenced by the direct observation of the closed-shell singlet state with IR spectroscopy in solid Ne, Ar, Kr, Xe, and N 2 matrices (3-40 K) and the triplet state in toluene (10 K) with EPR spectroscopy ( 3 2: |D/hc| = 1.48 cm -1 and |E/hc| = 0.029 cm -1 ; 3 6: |D/hc| = 1.39 cm -1 and |E/hc|c = 0.039 cm -1 ). Subsequent visible-light and UV laser irradiations led to the formation of furyl isocyanates (3 and 7) and ring-opening product 3-cyanoacrolein (9-E and 9-Z), respectively, in which the elusive 3-furylnitrene ( 3 8) was also identified by IR and EPR spectroscopy (|D/hc| = 1.12 cm -1 and |E/hc| = 0.005 cm -1 ).

  18. Triplet superconductors as the basis for solid-state quantum computing

    International Nuclear Information System (INIS)

    Gulian, A M; Wood, K S

    2003-01-01

    We propose triplet superconductors, such as ruthenates, as prospective materials for qubit construction. The vectorial nature of the order parameter in triplet superconductors makes it conceptually easy to estimate the performance of the qubits. The Cooper condensate of pairs in triplet superconductors has all the attributes of Bose-Einstein condensates and should facilitate long decoherence times for these qubits, relative to other vectorial schemes for qubits, such as small ferromagnets. There are other benefits, which the superconducting state provides for requirements such as entanglement between qubits via the proximity effect, etc. We consider these benefits in detail, although our consideration is only preliminary and further experimental and theoretical research will undoubtedly introduce correctives

  19. ESR spectra of organic molecules in triplet state; studies on the structure, internal interaction and the influence of environment

    International Nuclear Information System (INIS)

    Kemp, T.

    1980-01-01

    The origins, features and interpretation of triplet state e.s.r. spectra are described. Examples chosen for discussion include carbenes, nitrenes and excited polyacenes. Newly discovered triplet-state substituted aryl cations are described, the D - parameters of which give information as to mechanism of π-stabilization of these unusual species. (author)

  20. A Theoretical Study of the Photodissociation Mechanism of Cyanoacetylene in Its Lowest Singlet and Triplet Excited States

    Science.gov (United States)

    Luo, Cheng; Du, Wei-Na; Duan, Xue-Mei; Li, Ze-Sheng

    2008-11-01

    Cyanoacetylene (H5-C4 ≡ C3-C2 ≡ N1) is a minor constituent of the atmosphere of Titan, and its photochemistry plays an important role in the formation of the haze surrounding the satellite. In this paper, the complete active space self-consistent field (CASSCF) and multiconfigurational second-order perturbation (CASPT2) approaches are employed to investigate the photochemical processes for cyanoacetylene in its first singlet and triplet excited states with the cc-pVTZ basis set. Fissions of the C4-H5 and C2-C3 bonds in S1 yield H(2S) + CCCN(A2Π) and HCC(A2Π) + CN(X2Σ+), respectively. In T1, the corresponding dissociation products are H(2S) + CCCN(X2Σ+) and HCC(X2Σ) + CN(X2Σ+). At the CASPT2(14,13)//CASSCF(14,13) + ZPE level, the barriers for the adiabatic dissociation of the C4-H5 and C2-C3 bonds are 6.11 and 6.94 eV in S1 and 5.71 and 6.39 eV in T1, respectively, taking the energy of S0 minimum as reference. Based on the calculated potential energy surfaces, the existence of a metastable excited molecule is anticipated upon 260-230 nm photoexcitation, which provides a probable approach for cyanoacetylene to polymerize. The internal conversion (IC) process through vibronic interaction followed by C4-H5 fission in the ground state is found to account for the observed diffuse character in the UV absorption spectrum below 240 nm.

  1. Triplet state photochemistry and the three-state crossing of acetophenone within time-dependent density-functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Huix-Rotllant, Miquel, E-mail: miquel.huix@gmail.com; Ferré, Nicolas, E-mail: nicolas.ferre@univ-amu.fr [Institut de Chimie Radicalaire (UMR-7273), Aix-Marseille Université, CNRS, 13397 Marseille Cedex 20 (France)

    2014-04-07

    Even though time-dependent density-functional theory (TDDFT) works generally well for describing excited states energies and properties in the Franck-Condon region, it can dramatically fail in predicting photochemistry, notably when electronic state crossings occur. Here, we assess the ability of TDDFT to describe the photochemistry of an important class of triplet sensitizers, namely, aromatic ketones. We take acetophenone as a test molecule, for which accurate ab initio results exist in the literature. Triplet acetophenone is generated thanks to an exotic three-state crossing involving one singlet and two triplets states (i.e., a simultaneous intersystem crossing and triplet conical intersection), thus being a stringent test for approximate TDDFT. We show that most exchange-correlation functionals can only give a semi-qualitative picture of the overall photochemistry, in which the three-state crossing is rather represented as a triplet conical intersection separated from the intersystem crossing. The best result overall is given by the double hybrid functional mPW2PLYP, which is even able to reproduce quantitatively the three-state crossing region. We rationalize this results by noting that double hybrid functionals include a larger portion of double excitation character to the excited states.

  2. High-frequency two-electron photoionization cross section of triplet states

    International Nuclear Information System (INIS)

    Krivec, R.; Amusia, M.Ya.; Mandelzweig, V.B.

    2003-01-01

    Using high precision wave functions describing the triplet ground and excited 3 S states of the He atom and heliumlike ions, the cross sections of single- and double-electron photoionization are calculated. The dependence of the ratio R of the double and single ionization cross sections on the nuclear charge Z and the principal quantum number of excitation n is studied. The results obtained are compared to those for previously studied singlet states

  3. Singlet and triplet states of trions in Zinc Selenide-based quantum wells probed by magnetic fields to 50 Tesla

    International Nuclear Information System (INIS)

    Astakhov, G.V.; Yakovlev, D.R.; Crooker, Scott A.; Barrick, Todd; Dzyubenko, A.B.; Sander, Thomas; Kochereshko, V.P.; Ossau, W.; Faschinger, W.; Waag, A.

    2002-01-01

    Singlet and triplet states of positively (X + ) and negatively (X - ) charged excitons in ZnSe-based quantum wells have been studied by means of photoluminescence in pulsed magnetic fields up to 50 T. The binding energy of the X - singlet state shows a monotonic increase with magnetic field with a tendency to saturation, while that of the X + slightly decreases. The triplet X + and X - states, being unbound at zero magnetic field, noticeably increase their binding energy in high magnetic fields. The experimental evidence for the interaction between the triplet and singlet states of lTions leading to their anticrossing in magnetic fields has been found.

  4. Triplet excited electronic state switching induced by hydrogen bonding: A transient absorption spectroscopy and time-dependent DFT study

    Energy Technology Data Exchange (ETDEWEB)

    Ravi Kumar, Venkatraman; Ariese, Freek; Umapathy, Siva, E-mail: umapathy@ipc.iisc.ernet.in [Inorganic and Physical Chemistry Department, Indian Institute of Science, Bangalore 560012 (India)

    2016-03-21

    The solvent plays a decisive role in the photochemistry and photophysics of aromatic ketones. Xanthone (XT) is one such aromatic ketone and its triplet-triplet (T-T) absorption spectra show intriguing solvatochromic behavior. Also, the reactivity of XT towards H-atom abstraction shows an unprecedented decrease in protic solvents relative to aprotic solvents. Therefore, a comprehensive solvatochromic analysis of the triplet-triplet absorption spectra of XT was carried out in conjunction with time dependent density functional theory using the ad hoc explicit solvent model approach. A detailed solvatochromic analysis of the T-T absorption bands of XT suggests that the hydrogen bonding interactions are different in the corresponding triplet excited states. Furthermore, the contributions of non-specific and hydrogen bonding interactions towards differential solvation of the triplet states in protic solvents were found to be of equal magnitude. The frontier molecular orbital and electron density difference analysis of the T{sub 1} and T{sub 2} states of XT indicates that the charge redistribution in these states leads to intermolecular hydrogen bond strengthening and weakening, respectively, relative to the S{sub 0} state. This is further supported by the vertical excitation energy calculations of the XT-methanol supra-molecular complex. The intermolecular hydrogen bonding potential energy curves obtained for this complex in the S{sub 0}, T{sub 1}, and T{sub 2} states support the model. In summary, we propose that the different hydrogen bonding mechanisms exhibited by the two lowest triplet excited states of XT result in a decreasing role of the nπ{sup ∗} triplet state, and are thus responsible for its reduced reactivity towards H-atom abstraction in protic solvents.

  5. Communication: Orbital instabilities and triplet states from time-dependent density functional theory and long-range corrected functionals

    Science.gov (United States)

    Sears, John S.; Koerzdoerfer, Thomas; Zhang, Cai-Rong; Brédas, Jean-Luc

    2011-10-01

    Long-range corrected hybrids represent an increasingly popular class of functionals for density functional theory (DFT) that have proven to be very successful for a wide range of chemical applications. In this Communication, we examine the performance of these functionals for time-dependent (TD)DFT descriptions of triplet excited states. Our results reveal that the triplet energies are particularly sensitive to the range-separation parameter; this sensitivity can be traced back to triplet instabilities in the ground state coming from the large effective amounts of Hartree-Fock exchange included in these functionals. As such, the use of standard long-range corrected functionals for the description of triplet states at the TDDFT level is not recommended.

  6. Theoretical radiative properties between states of the triplet manifold of NH radical

    International Nuclear Information System (INIS)

    Owono Owono, L.C.; Jaidane, N.; Ben Lakhdar, Z.

    2007-12-01

    Ab initio transition dipole moments between states of the triplet manifold of NH radical are presented. This enables the computation of various radiative characteristics such as Einstein coefficients, radiative lifetimes and oscillator strengths. These properties concern valence and Rydberg states as well for which spectroscopic parameters are rather scarce and sometimes inexistent. Our results show good agreement with available experimental data in comparison to other theoretical numbers reported in the literature. This helps to build confidence on the quantities for which data were not found for comparative purposes. It is expected that the present study may enhance further astrophysical and laboratory investigations. (author)

  7. Electron transfer reactions induced by the triplet state of thiacarbocyanine dimers

    International Nuclear Information System (INIS)

    Chibisov, Alexander K.; Slavnova, Tatyana D.; Goerner, Helmut

    2004-01-01

    The photoinduced electron transfer between either cationic 5,5 ' -dichloro-3,3 ' ,9-triethylthiacarbocyanine (1) or a structurally similar anionic dye (2) and appropriate donors, e.g. ascorbic acid, and acceptors, e.g. methyl viologen, was studied by ns-laser photolysis. In aqueous solution the dyes in the ground state are present as an equilibrated mixture of dimers and monomers, whereas the triplet state is mainly populated from dimers. The triplet states of both dimers and monomers are quenched by electron donors or acceptors and the rate constant for quenching is generally 2-4 times higher for dimers than for monomers. The kinetics of triplet decay and radical formation and decay as a result of primary and secondary electron transfer were analyzed. While the one-electron reduced dimer decays due to back reactions, the one-electron oxidized dimer rapidly dissociates into the monomer and the monomeric dye radical. For the dimeric dye/donor/acceptor systems the primary photoinduced electron transfer occurs either from the donor or to the acceptor yielding the dimeric dye radicals. The one-electron reduced dimer can be efficiently oxidized by acceptors, e.g. the rate constant for reaction of the dimeric dye radical of 1 with methyl viologen (photoreductive pathway of sensitization) is 1.6x10 9 M -1 s -1 . The photooxidative pathway of sensitization is more complicated; after dissociation of the dimeric dye radical, the monomeric dye radical is reduced in a secondary electron transfer from ascorbic acid, e.g. with a rate constant of 1x10 9 M -1 s -1 for 2, yielding the monomer. On increasing the donor concentration the photooxidative pathway of sensitization is switched to a photoreductive one

  8. Ultrafast Charge and Triplet State Formation in Diketopyrrolopyrrole Low Band Gap Polymer/Fullerene Blends: Influence of Nanoscale Morphology of Organic Photovoltaic Materials on Charge Recombination to the Triplet State

    Directory of Open Access Journals (Sweden)

    René M. Williams

    2017-01-01

    Full Text Available Femtosecond transient absorption spectroscopy of thin films of two types of morphologies of diketopyrrolopyrrole low band gap polymer/fullerene-adduct blends is presented and indicates triplet state formation by charge recombination, an important loss channel in organic photovoltaic materials. At low laser fluence (approaching solar intensity charge formation characterized by a 1350 nm band (in ~250 fs dominates in the two PDPP-PCBM blends with different nanoscale morphologies and these charges recombine to form a local polymer-based triplet state on the sub-ns timescale (in ~300 and ~900 ps indicated by an 1100 nm absorption band. The rate of triplet state formation is influenced by the morphology. The slower rate of charge recombination to the triplet state (in ~900 ps belongs to a morphology that results in a higher power conversion efficiency in the corresponding device. Nanoscale morphology not only influences interfacial area and conduction of holes and electrons but also influences the mechanism of intersystem crossing (ISC. We present a model that correlates morphology to the exchange integral and fast and slow mechanisms for ISC (SOCT-ISC and H-HFI-ISC. For the pristine polymer, a flat and unstructured singlet-singlet absorption spectrum (between 900 and 1400 nm and a very minor triplet state formation (5% are observed at low laser fluence.

  9. Singlet and triplet states of trions in ZuSe-based quantum wells probed by magnetic fields to 50 Tesla

    Energy Technology Data Exchange (ETDEWEB)

    Astakhov, G. V.; Yakovlev, D. R.; Crooker, S. A. (Scott A.); Barrick, T. (Todd); Dzyubenko, A. B.; Sander, Thomas; Kochereshko, V. P.; Ossau, W.; Faschinger, W.; Waag, A.

    2002-01-01

    Singlet and triplet states of positively (X{sup +}) and negatively (X{sup -}) charged excitons in ZnSe-based quantum wells have been studied by means of photoluminescence in pulsed magnetic fields up to 50 T. The binding energy of the X{sup -} singlet state shows a monotonic increase with magnetic field with a tendency to saturation, while that of the X{sup +} slightly decreases. The triplet X{sup +} and X{sup -} states, being unbound at zero magnetic field, noticeably increase their binding energy in high magnetic fields. The experimental evidence for the interaction between the triplet and singlet states of lTions leading to their anticrossing in magnetic fields has been found.

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

    Science.gov (United States)

    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.

  11. Triplet state and semiquinone free radical of 5-methoxyquinizarin : a laser flash photolysis and pulse radiolysis study

    International Nuclear Information System (INIS)

    Pal, H.; Patil, D.K.; Mukherjee, T.; Mittal, J.P.

    1992-01-01

    The triplet(T) state properties like T-T absorption spectra, quantum yield, energy level and decay kinetics of 5-methoxyquinizarin (5-methoxy-1, 4-dihydroxy-9, 10-anthraquinone; MQZ) have been investigated in cyclohexane, acetonitrile and isopropyl alcohol using nanosecond laser flash photolysis technique. In isopropylalcohol, a neutral semiquinone radical is also formed which has been characterised by comparing the long lived transient spectra with the MQZ-semiquinone spectra obtained by pulse radiolysis of MQZ in the same solvent. A relatively small amount of a long lived transient formed in cyclohexane and acetonitrile, along with the triplet state of MQZ, could not be characterised unambiguously, but has been attributed to the semiquinone radical of MQZ, produced by the reaction of the excited states of the quinone with the solvent. The quantum yield of the semiquinone radical in isopropyl alcohol is considerably higher than the triplet quantum yield, showing that both the excited singlet and the triplet states of the quinone probably react with the solvent molecules to form the semiquinone radical. The photophysical properties of the triplet and the semiquinone radical of MQZ have been compared with those of simple 1,4-disubstituted anthraquinones. (author). 23 refs., 5 figs., 1 tab

  12. Constraining nuclear photon strength functions by the decay properties of photo-excited states

    Science.gov (United States)

    Isaak, J.; Savran, D.; Krtička, M.; Ahmed, M. W.; Beller, J.; Fiori, E.; Glorius, J.; Kelley, J. H.; Löher, B.; Pietralla, N.; Romig, C.; Rusev, G.; Scheck, M.; Schnorrenberger, L.; Silva, J.; Sonnabend, K.; Tonchev, A. P.; Tornow, W.; Weller, H. R.; Zweidinger, M.

    2013-12-01

    A new approach for constraining the low-energy part of the electric dipole Photon Strength Function (E1-PSF) is presented. Experiments at the Darmstadt High-Intensity Photon Setup and the High Intensity γ→-Ray Source have been performed to investigate the decay properties of 130Te between 5.50 and 8.15 MeV excitation energy. In particular, the average γ-ray branching ratio to the ground state and the population intensity of low-lying excited states have been studied. A comparison to the statistical model shows that the latter is sensitive to the low-energy behavior of the E1-PSF, while the average ground state branching ratio cannot be described by the statistical model in the energy range between 5.5 and 6.5 MeV.

  13. Local CC2 response method for triplet states based on Laplace transform: excitation energies and first-order properties.

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  15. EPR evidence for thermally excited triplet states in exinite, vitrinite and inertinite separated from bituminous coal

    Energy Technology Data Exchange (ETDEWEB)

    Slowik, G.P.; Wojtowicz, W.; Wieckowski, A.B. [University of Zielona Gora, Zielona Gora (Poland). Inst. of Physics

    2005-07-01

    In this work we have made an electron spin resonance (EPR) study of macerals obtained from the lithotype clarain separated from Polish medium-rank coal (85.6 wt.% C). For three macerals (exinite, vitrinite, and inertinite), the temperature dependence of intensity of EPR spectra in the temperature range of 100-373 K was investigated. The experimentally obtained EPR spectra of macerals were fitted by curves of the derivatives of the Gaussian and Lorentzian functions. The best fitting was obtained, when the experimental EPR spectra were assumed to be a superposition of three lines, for exinite and vitrinite - a broad Gaussian (G), a broad Lorentzian (L1) and a narrow Lorentzian (L3) line, but for inertinite of two lines - a narrow Lorentzian (L2) and a narrow Lorentzian (L3) line. The computer-assisted fitting has shown that each individual component line has similar values of resonance field, but different linewidths and amplitudes. The temperature dependence of line intensity I of the broad Gaussian (G) and narrow Lorentzian (L2 and L3) lines fulfils the Curie law in the form I = C/T or IT = C, whereas the broad Lorentzian (L1) line does not fulfil the Curie law. In the last case the temperature dependence of the Lorentzian (L1) component was fitted by the relation I = C/T + B/(T(3 + exp(J/kT))) or IT C + B/(3 + exp(J/kT))), valid for thermally excited triplet states (S = 1). For exinite and vitrinite the curves presenting the temperature dependence of the product IT versus temperature T were resolved into two curves, one for paramagnetic centres in the doublet state (S = ), and the other for paramagnetic centres in the thermally excited triplet state (S = 1).

  16. Di-Neutral Pion Production in the Triplet P Wave States of Charmonium

    Energy Technology Data Exchange (ETDEWEB)

    Vidnovic, Theodore, III [Minnesota U.

    2002-12-01

    Fermilab experiment E835 has used proton-antiproton annihilations to perform a search for charmonium in the $\\pi^0 \\pi^0$ final state in the triplet P-wave region (3340-3570 MeV). States with even total angular momentum and positive Parity and C-parity have access to the $\\pi^0 \\pi^0$ final state. An enhancement in the $p\\bar{p} \\to \\pi^0 \\pi^0$ cross section was observed at the $X_{c0}$ resonance. The enhancement was found to be a factor of 20 larger than the expected resonant cross section and was attributed to interference between the $X_{c0}$ and the large non-resonant continuum. The general helicity structure of the $\\pi^0 \\pi^0$ differential cross section was studied and the product of the branching fractions, $Br(p\\bar{p}\\to X_{c0}$ ) x Br($X_{c0} \\to \\pi^0 \\pi^0$ ) = (5.09 ± 0.81(stat) ± 0.25 (sys) x $10^{-7}$ was measured.

  17. Control of triplet state generation in heavy atom-free BODIPY-anthracene dyads by media polarity and structural factors

    KAUST Repository

    Filatov, Mikhail A.; Karuthedath, Safakath; Polestshuk, Pavel M; Callaghan, Susan; Flanagan, Keith; Telitchko, Maxime; Wiesner, Thomas; Laquai, Fré dé ric; Senge, Mathias O

    2018-01-01

    A family of heavy atom-free BODIPY-anthracene dyads (BADs) exhibiting triplet excited state formation from charge-transfer states is reported. Four types of BODIPY scaffolds, different in the alkyl substitution pattern, and four anthracene derivatives have been used to access BADs. The fluorescence and intersystem crossing (ISC) in these dyads depend on donor-acceptor couplings and can be accurately controlled by the substitution or media polarity. Under conditions that do not allow charge transfer (CT), the dyads exhibit fluorescence with high quantum yields. Formation of charge-transfer states triggers ISC and the formation of long-lived triplet excited states in the dyads. The excited state properties were studied by steady-state techniques and ultrafast pump-probe spectroscopy to determine the parameters of the observed processes. Structural information for various BADs was derived from single crystal X-ray structure determinations alongside DFT molecular geometry optimization, revealing the effects of mutual orientation of subunits on the photophysical properties. The calculations showed that alkyl substituents on the BODIPY destabilize CT states in the dyads, thus controlling the charge transfer between the subunits. The effect of the dyad structure on the ISC efficiency was considered at M06-2X level of theory and a correlation between mutual orientation of the subunits and the energy gap between singlet and triplet CT states was studied using multireference CASSCF method.

  18. Control of triplet state generation in heavy atom-free BODIPY-anthracene dyads by media polarity and structural factors

    KAUST Repository

    Filatov, Mikhail A.

    2018-02-12

    A family of heavy atom-free BODIPY-anthracene dyads (BADs) exhibiting triplet excited state formation from charge-transfer states is reported. Four types of BODIPY scaffolds, different in the alkyl substitution pattern, and four anthracene derivatives have been used to access BADs. The fluorescence and intersystem crossing (ISC) in these dyads depend on donor-acceptor couplings and can be accurately controlled by the substitution or media polarity. Under conditions that do not allow charge transfer (CT), the dyads exhibit fluorescence with high quantum yields. Formation of charge-transfer states triggers ISC and the formation of long-lived triplet excited states in the dyads. The excited state properties were studied by steady-state techniques and ultrafast pump-probe spectroscopy to determine the parameters of the observed processes. Structural information for various BADs was derived from single crystal X-ray structure determinations alongside DFT molecular geometry optimization, revealing the effects of mutual orientation of subunits on the photophysical properties. The calculations showed that alkyl substituents on the BODIPY destabilize CT states in the dyads, thus controlling the charge transfer between the subunits. The effect of the dyad structure on the ISC efficiency was considered at M06-2X level of theory and a correlation between mutual orientation of the subunits and the energy gap between singlet and triplet CT states was studied using multireference CASSCF method.

  19. Triphenylene columnar liquid crystals: spectroscopic study of triplets states and charge carriers

    International Nuclear Information System (INIS)

    Bondkowski, Jens

    2000-01-01

    This research thesis reports the study of three oxygenated derivatives of triphenylene (two monomers, a symmetric one and an asymmetric one, and a tetramer) by using different experimental techniques: absorption spectroscopy and fluorescence spectroscopy in stationary regime, and time-resolved fluorescence spectroscopy (also said single photon counting). Moreover, the author adapted an existing experiment of transient absorption spectroscopy time-resolved at the microsecond level to obtain spectra of thin layers under electric field. A cyclic voltammetry experiment and a spectro-electrochemistry experiment have also been performed. The report first presents the studied materials, the characterisation of singlet states, and the study of the effect molecular symmetry decreasing have on molecular transitions. Then, the author reports the study of cationic species of the triphenylene derivatives. The next chapters address the characterisation of derivative triplet states, and the study of energy transfer within the meso phase of one of these derivatives. The last chapters address charge carriers of columnar liquid crystals, and the molecular nature of these charge carriers

  20. Effect of Temperature and Pressure on Correlation Energy in a Triplet State of a Two Electron Spherical Quantum Dot

    Directory of Open Access Journals (Sweden)

    A. Rejo Jeice

    2013-09-01

    Full Text Available The combined effect of hydrostatic pressure and temperature on correlation energy in a triplet state of two electron spherical quantum dot with square well potential is computed. The result is presented taking GaAs dot as an example. Our result shows the correlation energies are inegative in the triplet state contrast to the singlet state ii it increases with increase in pressure  iiifurther decreases due to the application  of temperature iv it approaches zero as dot size approaches infinity and v it contribute 10% decrement in total confined energy to the narrow dots. All the calculations have been carried out with finite models and the results are compared with existing literature.

  1. High-Yield Excited Triplet States in Pentacene Self-Assembled Monolayers on Gold Nanoparticles through Singlet Exciton Fission.

    Science.gov (United States)

    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.

  2. Spin-rotation symmetry breaking and triplet superconducting state in doped topological insulator CuxBi2Se3

    Science.gov (United States)

    Zheng, Guo-Qing

    Spontaneous symmetry breaking is an important concept for understanding physics ranging from the elementary particles to states of matter. For example, the superconducting state breaks global gauge symmetry, and unconventional superconductors can break additional symmetries. In particular, spin rotational symmetry is expected to be broken in spin-triplet superconductors. However, experimental evidence for such symmetry breaking has not been obtained so far in any candidate compounds. We report 77Se nuclear magnetic resonance measurements which showed that spin rotation symmetry is spontaneously broken in the hexagonal plane of the electron-doped topological insulator Cu0.3Bi2Se3 below the superconducting transition temperature Tc =3.4 K. Our results not only establish spin-triplet (odd parity) superconductivity in this compound, but also serve to lay a foundation for the research of topological superconductivity (Ref.). We will also report the doping mechanism and superconductivity in Sn1-xInxTe.

  3. Dye-Sensitized Molecular Charge Transfer Complexes: Magnetic and Conduction Properties in the Photoexcited States of Ni(dmit2 Salts Containing Photosensitive Dyes

    Directory of Open Access Journals (Sweden)

    Ryoma Yamamoto

    2017-05-01

    Full Text Available Photosensitive dyes often induce charge transfer (CT between adjacent chemical species and themselves under irradiation of appropriate wavelengths. Because of the reversibility and selectivity of such CT, it is considered to be interesting to utilize such dyes as optically controllable trigger components for conduction and magnetism in the photoexcited states of organic materials. Based on this idea, such a type of new salts, i.e., γ- and δ-DiCC[Ni(dmit2] in addition to DiCC2[Ni(dmit2]3 have been prepared, characterized and their physical and structural properties have been examined both under dark and irradiated conditions (dmit2− = 1,3-dithiole-2-thione-4,5-dithiolate, DiCC+ = 3,3′-Dihexyloxacarbocyanine monocation. Among them, under UV (254–450 nm irradiation, δ-DiCC[Ni(dmit2] exhibited photoconductivity being six times as high as its dark conductivity at room temperature. The electron spin resonance (ESR spectra have demonstrated that there are photoexcited spins on both DiCC and [Ni(dmit2] species as a result of the CT transition between them, serving as localized spins (DiCC and carriers ([Ni(dmit2], respectively. The results obtained in this work have indicated that the strategy mentioned above is effective in developing organic photoresponsive semiconductors with paramagnetism.

  4. An isotope dependent study of acetone in its lowest excited triplet state

    International Nuclear Information System (INIS)

    Gehrtz, M.; Brauchle, C.; Voitlaender, J.

    1984-01-01

    The lowest excited triplet state T 1 of acetone-h 6 and acetone-d 6 was investigated with a pulsed dye laser equipped ODMR spectrometer. Acetone is found to be bent in T 1 and the out-of-plane distortion angle is estimated to be approx.= 38 0 . The observed zero-field splitting (ZFS) is surprisingly small. Both the spin-spin and the spin-orbit (SO) contribution to the ZFS are evaluated. The SO tensor contribution is calculated from a correlation between the deuterium effects on the ZFS parameters and the population rates. The sub-level selective kinetics of the acetone T 1 is largely determined by the mixing of the x- and z-level characteristics owing to magnetic axis rotation caused by the excited state out-of-plane distortion. Considerable deuterium effects are observed on the kinetic data and on the microwave transition frequencies. In all cases the spin-specific isotope effects (due to the promoting modes) and the global effects (due to the Franck-Condon factors) are specified. For the population rates and the SO contribution to ZFS, the inverse global isotope effects (deuterium factor > 1) was found for the first time. Based on the isotope dependence of the rates, the mechanisms of (vibrationally induced) SO coupling in acetone are discussed. It is concluded that non-adiabatic contributions have to be taken into account for the smallest population rate only, but that otherwise the adiabatic SO coupling mechanisms by far dominates in the acetone photophysics. (author)

  5. The Kinetics of Joined Action of Triplet-Triplet Annihilation and First-Order Decay of Molecules in T1 State in the Case of Nondominant First-Order Process: The Kinetic Model in the Case of Spatially Periodic Excitation

    Directory of Open Access Journals (Sweden)

    Paweł Borowicz

    2013-01-01

    Full Text Available In this paper the model developed for estimation of the diffusion coefficient of the molecules in the triplet state is presented. The model is based on the intuitive modification of the Smoluchowski equation for the time-dependent rate parameter. Since the sample is irradiated with the spatially periodic pattern nonexponential effects can be expected in the areas of the constructive interference of the exciting laser beams. This nonexponential effects introduce changes in the observed kinetics of the diffusion-controlled triplet-triplet annihilation. Due to irradiation with so-called long excitation pulse these non-exponential effects are very weak, so they can be described with introducing very simple correction to the kinetic model described in the first paper of this series. The values of diffusion coefficient of anthracene are used to calculate the annihilation radius from the data for spatially homogeneous excitation.

  6. A fluorescence detected magnetic resonance investigation of the carotenoid triplet states associated with Photosystem II of isolated spinach thylakoid membranes

    CERN Document Server

    Santabarbara, S; Carbonera, D; Heathcote, P

    2005-01-01

    The carotenoid triplet populations associated with the fluorescence emission chlorophyll forms of Photosystem II have been investigated in isolated spinach thylakoid membranes by means of fluorescence detected magnetic resonance in zero field (FDMR). The spectra collected in the 680-690 nm emission range, have been fitted by a global analysis procedure. At least five different carotenoid triplet states coupled to the terminal emitting chlorophyll forms of PS II, peaking at 682 nm, 687 nm and 692 nm, have been characterised. The triplets associated with the outer antenna emission forms, at 682 nm, have zero field splitting parameters D = 0.0385 cm/sup -1/, E = 0.00367 cm/sup -1/; D = 0.0404 cm/sup -1/, E = 0.00379 cm/sup -1/ and D = 0.0386 cm/sup -1/, E = 0.00406 cm/sup -1/ which are very similar to those previously reported for the xanthophylls of the isolated LHC II complex. Therefore the FDMR spectra recorded in this work provide insights into the organisation of the LHC II complex in the unperturbed enviro...

  7. Laser induced transient absorptions of the excited triplet state of 9,10-anthraquinone-2-sulfonate. A further study by 248 nm laser photolysis

    International Nuclear Information System (INIS)

    Ma Jianhua; Lin Weizheng; Wang Wenfen; Yao Side; Lin Nianyun

    1999-01-01

    Transient absorption spectrum of triplet state of 9,10-anthraquinone-2-sulfonate (AQS) in aqueous solution has been investigated using 248 nm (KrF) laser photolysis. A whole transient absorption spectrum with absorption maxim at 380 nm and 580 nm has been assigned to triple AQS from detailed kinetic analysis of decay of 380 nm and 580 nm signals, which is the neat characteristic absorption of triplet AQS reported for the first time. In addition, the difference in feature of the spectrum of triplet AQS in H 2 O and that in CH 3 CN was eliminated by further study using 248 nm laser pulses

  8. Computational Prediction of Excited-State Carbon Tunneling in the Two Steps of Triplet Zimmerman Di-π-Methane Rearrangement.

    Science.gov (United States)

    Li, Xin; Liao, Tao; Chung, Lung Wa

    2017-11-22

    The photoinduced Zimmerman di-π-methane (DPM) rearrangement of polycyclic molecules to form synthetically useful cyclopropane derivatives was found experimentally to proceed in a triplet excited state. We have applied state-of-the-art quantum mechanical methods, including M06-2X, DLPNO-CCSD(T) and variational transition-state theory with multidimensional tunneling corrections, to an investigation of the reaction rates of the two steps in the triplet DPM rearrangement of dibenzobarrelene, benzobarrelene and barrelene. This study predicts a high probability of carbon tunneling in regions around the two consecutive transition states at 200-300 K, and an enhancement in the rates by 104-276/35-67% with carbon tunneling at 200/300 K. The Arrhenius plots of the rate constants were found to be curved at low temperatures. Moreover, the computed 12 C/ 13 C kinetic isotope effects were affected significantly by carbon tunneling and temperature. Our predictions of electronically excited-state carbon tunneling and two consecutive carbon tunneling are unprecedented. Heavy-atom tunneling in some photoinduced reactions with reactive intermediates and narrow barriers can be potentially observed at relatively low temperature in experiments.

  9. Concentration-modulated absorption spectroscopy and the triplet state: Photoinduced absorption/bleaching in erythrosin B, rose bengal and eosin y

    Science.gov (United States)

    Jones, W. Jeremy; Grofcsik, Andras; Kubinyi, Miklos; Thomas, Daniel

    2006-07-01

    The pump and probe method concentration-modulated absorption spectroscopy has been applied for studying the triplet characteristics of dyes erythrosin B, rose bengal and eosin y in ethanol solutions. Using the 514.5 and 488 nm lines of an argon ion laser for pump and probe beams, respectively, photoinduced bleaching for erythrosin B and eosin y and photoinduced absorption for rose bengal have been observed. The theory developed for describing the interactions of dye molecules of strong triplet forming ability with continuous wave pump and probe beams of Gaussian beam profiles has been tested by analysing the probe power gain or loss at different positions along the optical path of the focused collinear beams. From the gain-modulation frequency curves triplet absorption cross sections and the lifetimes of the triplet states have been determined.

  10. Modeling non-adiabatic photoexcited reaction dynamics in condensed phases

    International Nuclear Information System (INIS)

    Coker, D.F.

    2003-01-01

    Reactions of photoexcited molecules, ions, and radicals in condensed phase environments involve non-adiabatic dynamics over coupled electronic surfaces. We focus on how local environmental symmetries can effect non-adiabatic coupling between excited electronic states and thus influence, in a possibly controllable way, the outcome of photo-excited reactions. Semi-classical and mixed quantum-classical non-adiabatic molecular dynamics methods, together with semi-empirical excited state potentials are used to probe the dynamical mixing of electronic states in different environments from molecular clusters, to simple liquids and solids, and photo-excited reactions in complex reaction environments such as zeolites

  11. Sensitive triplet exciton detection in polyfluorene using Pd-coordinated porphyrin

    NARCIS (Netherlands)

    Mikhnenko, O.V.; Blom, P.W.M.; Loi, M.A.

    2011-01-01

    We developed a sensitive spectroscopic method to probe triplet concentration in thin films of polyfluorene (PF) at room temperature. The energy of photoexcited triplet excitons is transferred to the guest metal-organic complex, meso-tetratolylporphyrin-Pd (PdTPP), and detected as phosphorescent

  12. Excitation of triplet states of hypericin in water mediated by hydrotropic cromolyn sodium salt

    Science.gov (United States)

    Keša, Peter; Jancura, Daniel; Kudláčová, Júlia; Valušová, Eva; Antalík, Marián

    2018-03-01

    Hypericin (Hyp) is a hydrophobic pigment found in plants of the genus Hypericum which exhibits low levels of solubility in water. This work shows that the solubility of Hyp can be significantly increased through the addition of cromolyn disodium salt (DSCG). Performed studies using UV-VIS absorption and fluorescence spectroscopies demonstrate that Hyp remains in a predominantly biologically photodynamic active monomeric form in the presence of DSCG at concentrations ranging from 4.6 × 10- 3 to 1.2 × 10- 1 mol·L- 1. The low association constant between Hyp and DSCG (Ka = 71.7 ± 2 M- 1), and the polarity value of 0.3 determined for Hyp in a DSCG-water solution, lead to a suggestion that the monomerization of Hyp in aqueous solution can be explained as a result of the hydrotropic effect of DSCG. This hydrotropic effect is most likely a result of interactions between two relative rigid aromatic rings of DSCG and a delocalized charge on the surface of the Hyp molecule. The triplet-triplet (T-T) electronic transition observed in is Hyp in the presence of DSCG suggests a possible production of reactive oxygen species once Hyp is irradiated with visible light in a DSCG aqueous solution.

  13. 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.

    Science.gov (United States)

    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

  14. A study of the low-lying singlet and triplet electronic states of chlorophyll A and B

    Directory of Open Access Journals (Sweden)

    Etinski Mihajlo

    2013-01-01

    Full Text Available Chlorophylls have been extensively investigated both experimentally and theoretically owing to the fact that they are essential for photosynthesis. We have studied two forms of chlorophyll, chlorophyll a and chlorophyll b, by means of density functional theory. Optimization of S0, S1 and T1 states was performed with the B3-LYP functional. The computed fluorescence lifetimes show good agreement with the available experimental data. The electronic adiabatic energies of S1 and T1 states are 2.09/2.12 and 1.19/1.29 eV for chlorophyll a and chlorophyll b respectively. We discussed the implications of this results on the triplet formation. Also, the calculated vertical ionization potentials shows good agreement with the experimental results. [Projekat Ministarstva nauke Reoublike Srbije, br. 172040

  15. Room temperature phosphorimetric determination of cyanide based on triplet state energy transfer

    International Nuclear Information System (INIS)

    Fernandez-Argueelles, Maria Teresa; Costa-Fernandez, Jose M.; Pereiro, Rosario; Sanz-Medel, Alfredo

    2003-01-01

    The determination of cyanide ions in water samples by room temperature phosphorescence (RTP) detection is described. The method is based on the measurement of the RTP emission of α-bromonaphthalene (BrN). The principle of the RTP cyanide determination involves the energy transfer (ET) from the BrN phosphor molecule insensitive to the presence of cyanide (acting as a donor) to a cyanide-sensitive dye (acceptor). The RTP emission spectrum of BrN overlaps significantly with the absorption spectrum of the complex formed between copper and Cadion 2B, giving rise to a non-radiative ET from the phosphor molecules to the metal complex. The sensing of cyanide ions is based on the displacement by cyanide of the copper ions from its complex with Cadion 2B (the free chelating molecule presents a low absorbance in the region of maximum emission of the BrN phosphor). An increase in the concentration of cyanide causes a decrease on the concentration of the Cadion 2B-copper complex (acceptor) with the subsequent decrease of the absorbance in the overlapping region with the RTP spectra, resulting in higher RTP emission signals measured. Both, RTP intensities and triplet lifetimes of the BrN increased with the increase of the cyanide concentration. The calibration graphs were linear up to a concentration of 500 mg l -1 cyanide and a precision of ±2 and ±0.5% for five replicates of 50 μg l -1 of cyanide has been obtained when measuring intensities and triplet lifetimes values, respectively. A detection limit of 3 μg l -1 of cyanide was achieved under optimal reaction conditions and pH 11. The use of phosphorescence measurements (low background noise signals) resulted in an important improvement on the sensitivity of the cyanide detection higher than eight times as compared to the molecular absorption spectrophotometric method for cyanide detection based on the use of Cadion 2B-copper as cyanide-indicator. Interference studies were performed with cations and anions present in

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

    Science.gov (United States)

    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.

  17. Probabilistic Controlled Teleportation of a Triplet W State with Combined Channel of Non-Maximally Entangled Einstein–Podolsky–Rosen and Greenberger–Horne–Zeilinger States

    International Nuclear Information System (INIS)

    Jian, Dong; Jian-Fu, Teng

    2009-01-01

    A scheme for probabilistic controlled teleportation of a triplet W state using combined non-maximally entangled channel of two Einstein–Podolsky–Rosen (EPR) states and one Greenberger–Horne–Zeilinger (GHZ) state is proposed. In this scheme, an (m + 2)-qubit GHZ state serves not only as the control parameter but also as the quantum channel. The m control qubits are shared by m supervisors. With the aid of local operations and individual measurements, including Bell-state measurement, Von Neumann measurement, and mutual classical communication etc., Bob can faithfully reconstruct the original state by performing relevant unitary transformations. The total probability of successful teleportation is only dependent on channel coefficients of EPR states and GHZ, independent of the number of supervisor m. This protocol can also be extended to probabilistic controlled teleportation of an arbitrary N-qubit state using combined non-maximally entangled channel of N – 1 EPR states and one (m + 2)-qubit GHZ. (general)

  18. Can Baird's and Clar's Rules Combined Explain Triplet State Energies of Polycyclic Conjugated Hydrocarbons with Fused 4nπ- and (4n + 2)π-Rings?

    Science.gov (United States)

    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.

  19. Generation of fluorescence quenchers from the triplet states of chlorophylls in the major light-harvesting complex II from green plants

    NARCIS (Netherlands)

    Barzda, V.; Vengris, M.; Valkunas, L.; van Amerongen, H.; van Grondelle, R.

    2000-01-01

    Laser flash-induced changes of the fluorescence yield were studied in aggregates of light-harvesting complex II (LHCII) on a time scale ranging from microseconds to seconds. Carotenoid (Car) and chlorophyll (Chl) triplet states, decaying with lifetimes of several microseconds and hundreds of

  20. Improved film morphology reduces charge carrier recombination into the triplet excited state in a small bandgap polymer-fullerene photovoltaic cell

    NARCIS (Netherlands)

    Di Nuzzo, D.; Aguirre de Miguel, A.; Shahid, M.; Gevaerts, Veronique; Meskers, S.C.J.; Janssen, R.A.J.

    2010-01-01

    The use of diiodooctane as processing additive for construction of PCPDTBT:PCBM solar cells results in a profound change in photophysical behavior of this blend. In the improved morphology obtained with the additive, recombination of charge carriers to the lowest triplet excited state is suppressed.

  1. Local Versus Long-Range Diffusion Effects of Photoexcited States on Radiative Recombination in Organic-Inorganic Lead Halide Perovskites.

    Science.gov (United States)

    Vrućinić, Milan; Matthiesen, Clemens; Sadhanala, Aditya; Divitini, Giorgio; Cacovich, Stefania; Dutton, Sian E; Ducati, Caterina; Atatüre, Mete; Snaith, Henry; Friend, Richard H; Sirringhaus, Henning; Deschler, Felix

    2015-09-01

    Radiative recombination in thin films of the archetypical, high-performing perovskites CH 3 NH 3 PbBr 3 and CH 3 NH 3 PbI 3 shows localized regions of increased emission with dimensions ≈500 nm. Maps of the spectral emission line shape show narrower emission lines in high emission regions, which can be attributed to increased order. Excited states do not diffuse out of high emission regions before they decay, but are decoupled from nearby regions, either by slow diffusion rates or energetic barriers.

  2. Photodegradation mechanism of sulfonamides with excited triplet state dissolved organic matter: A case of sulfadiazine with 4-carboxybenzophenone as a proxy

    International Nuclear Information System (INIS)

    Li, Yingjie; Wei, Xiaoxuan; Chen, Jingwen; Xie, Hongbin; Zhang, Ya-nan

    2015-01-01

    Highlights: • Excited triplet state of dissolved organic matter ( 3 DOM * ) is largely responsible for the enhanced photodegradation of sulfadiazine. • Electron followed by proton transfer is a major mechanism for the reactions of sulfadiazine with 3 DOM * proxies. • Two reaction sites (amino- or sulfonyl-N) and sulfadiazine radicals were identified in the reactions of sulfadiazine with 3 DOM * proxies. - Abstract: Excited triplet states of dissolved organic matter ( 3 DOM*) are important players for photodegradation sulfonamide antibiotics (SAs) in sunlit natural waters. However, the triplet-mediated reaction mechanism was poorly understood. In this study, we investigated the reaction adopting sulfadiazine as a representative SA and 4-carboxybenzophenone (CBBP)as a proxy of DOM. Results showed that the excited triplet state of CBBP ( 3 CBBP*) is responsible for the photodegradation of sulfadiazine. The reaction of 3 CBBP* with substructure model compounds verified there are two reaction sites (amino-or sulfonyl-N atoms) of sulfadiazine. Density functional theory calculations were performed, which unveiled that electrons transfer from the N reaction sites to the carbonyl oxygen atom of 3 CBBP* moiety, followed by proton transfers, leading to the formation of sulfadiazine radicals. Laser flash photolysis experiments were performed to confirm the mechanism. Thus, this study identified that the photodegradation mechanism of SAs initiated by 3 DOM*, which is important for understanding the photochemical fate, predicting the photoproducts, and assessing the ecological risks of SAs in the aquatic environment

  3. High orbital angular momentum states in H2 and D2. III. Singlet--triplet splittings, energy levels, and ionization potentials

    International Nuclear Information System (INIS)

    Jungen, C.; Dabrowski, I.; Herzberg, G.; Vervloet, M.

    1990-01-01

    The 5g--4 f Rydberg groups of H 2 and D 2 first studied in paper I have been obtained with a tenfold increase in resolution which made it possible to resolve the singlet from the triplet components. As a result we can now establish separately precise values for the energy levels in the triplet and singlet systems. For this purpose we have remeasured a number of transitions between the lower energy levels for which at present only old measurements are available. In particular we obtain accurate values for the energies of the lowest (stable) triplet state a 3 Σ + g relative to the singlet ground state, as well as of the ionization potential. The values obtained for the former are more accurate than obtained from singlet--triplet anticrossings while the latter are of similar accuracy as those reported recently by McCormack et al. [Phys. Rev. A 39, 2260 (1989)] and fit well within this accuracy with the most recent ab initio values

  4. Radio frequency measurements of tunnel couplings and singlet–triplet spin states in Si:P quantum dots

    Science.gov (United States)

    House, M. G.; Kobayashi, T.; Weber, B.; Hile, S. J.; Watson, T. F.; van der Heijden, J.; Rogge, S.; Simmons, M. Y.

    2015-01-01

    Spin states of the electrons and nuclei of phosphorus donors in silicon are strong candidates for quantum information processing applications given their excellent coherence times. Designing a scalable donor-based quantum computer will require both knowledge of the relationship between device geometry and electron tunnel couplings, and a spin readout strategy that uses minimal physical space in the device. Here we use radio frequency reflectometry to measure singlet–triplet states of a few-donor Si:P double quantum dot and demonstrate that the exchange energy can be tuned by at least two orders of magnitude, from 20 μeV to 8 meV. We measure dot–lead tunnel rates by analysis of the reflected signal and show that they change from 100 MHz to 22 GHz as the number of electrons on a quantum dot is increased from 1 to 4. These techniques present an approach for characterizing, operating and engineering scalable qubit devices based on donors in silicon. PMID:26548556

  5. Quantum confinement-tunable intersystem crossing and the triplet state lifetime of cationic porphyrin–CdTe quantum dot nano-assemblies

    KAUST Repository

    Ahmed, Ghada H.

    2015-03-27

    Here, we report a ground-state interaction between the positively charged cationic porphyrin and the negatively charged carboxylate groups of the thiol ligands on the surface of CdTe quantum dots (QDs), leading to the formation of a stable nanoassembly between the two components. Our time-resolved data clearly demonstrate that we can dramatically tune the intersystem crossing (ISC) and the triplet state lifetime of porphyrin by changing the size of the QDs in the nanoassembly.

  6. Quantum confinement-tunable intersystem crossing and the triplet state lifetime of cationic porphyrin–CdTe quantum dot nano-assemblies

    KAUST Repository

    Ahmed, Ghada H.; Aly, Shawkat Mohammede; Usman, Anwar; Eita, Mohamed Samir; Melnikov, Vasily; Mohammed, Omar F.

    2015-01-01

    Here, we report a ground-state interaction between the positively charged cationic porphyrin and the negatively charged carboxylate groups of the thiol ligands on the surface of CdTe quantum dots (QDs), leading to the formation of a stable nanoassembly between the two components. Our time-resolved data clearly demonstrate that we can dramatically tune the intersystem crossing (ISC) and the triplet state lifetime of porphyrin by changing the size of the QDs in the nanoassembly.

  7. Generation of Triplet Excited States via Photoinduced Electron Transfer in meso-anthra-BODIPY: Fluorogenic Response toward Singlet Oxygen in Solution and in Vitro

    KAUST Repository

    Filatov, Mikhail A.; Karuthedath, Safakath; Polestshuk, Pavel M.; Savoie, Huguette; Flanagan, Keith J.; Sy, Cindy; Sitte, Elisabeth; Telitchko, Maxime; Laquai, Fré dé ric; Boyle, Ross W.; Senge, Mathias O.

    2017-01-01

    Heavy atom-free BODIPY-anthracene dyads (BADs) generate locally excited triplet states by way of photoinduced electron transfer (PeT), followed by recombination of the resulting charge-separated states (CSS). Subsequent quenching of the triplet states by molecular oxygen produces singlet oxygen (1O2), which reacts with the anthracene moiety yielding highly fluorescent species. The steric demand of the alkyl substituents in the BODIPY subunit defines the site of 1O2 addition. Novel bis- and tetraepoxides and bicyclic acetal products, arising from rearrangements of anthracene endoperoxides were isolated and characterized. 1O2 generation by BADs in living cells enables visualization of the dyads distribution, promising new imaging applications.

  8. Generation of Triplet Excited States via Photoinduced Electron Transfer in meso-anthra-BODIPY: Fluorogenic Response toward Singlet Oxygen in Solution and in Vitro

    KAUST Repository

    Filatov, Mikhail A.

    2017-04-14

    Heavy atom-free BODIPY-anthracene dyads (BADs) generate locally excited triplet states by way of photoinduced electron transfer (PeT), followed by recombination of the resulting charge-separated states (CSS). Subsequent quenching of the triplet states by molecular oxygen produces singlet oxygen (1O2), which reacts with the anthracene moiety yielding highly fluorescent species. The steric demand of the alkyl substituents in the BODIPY subunit defines the site of 1O2 addition. Novel bis- and tetraepoxides and bicyclic acetal products, arising from rearrangements of anthracene endoperoxides were isolated and characterized. 1O2 generation by BADs in living cells enables visualization of the dyads distribution, promising new imaging applications.

  9. Proton polarization in photo-excited aromatic molecule at room temperature enhanced by intense optical source and temperature control

    Energy Technology Data Exchange (ETDEWEB)

    Sakaguchi, S., E-mail: sakaguchi@phys.kyushu-u.ac.jp [Department of Physics, Kyushu University, Fukuoka 812-8581 (Japan); Uesaka, T. [RIKEN Nishina Center, Saitama 351-0198 (Japan); Kawahara, T. [Department of Physics, Toho University, Chiba 274-8510 (Japan); Ogawa, T. [RIKEN Advanced Science Institute, Saitama 351-0198 (Japan); Tang, L. [Center for Nuclear Study, University of Tokyo, Tokyo 113-0001 (Japan); Teranishi, T. [Department of Physics, Kyushu University, Fukuoka 812-8581 (Japan); Urata, Y.; Wada, S. [RIKEN Advanced Science Institute, Saitama 351-0198 (Japan); Wakui, T. [Cyclotron and Radioisotope Center (CYRIC), Tohoku University, Miyagi 980-8578 (Japan)

    2013-12-15

    Highlights: • Proton polarization in p-terphenyl at room-temperature is enhanced by a factor of 3. • Intense laser and temperature control are critically important for high polarization. • Optimization of time structure of laser pulse is effective for further improvement. -- Abstract: Proton polarization at room temperature, produced in a p-terphenyl crystal by using electron population difference in a photo-excited triplet state of pentacene, was enhanced by utilizing an intense laser with an average power of 1.5 W. It was shown that keeping the sample temperature below 300 K is critically important to prevent the rise of the spin–lattice relaxation rate caused by the laser heating. It is also reported that the magnitude of proton polarization strongly depends on the time structure of the laser pulse such as its width and the time interval between them.

  10. Investigation of the generation of singlet oxygen in ensembles of photoexcited silicon nanocrystals by electron paramagnetic resonance spectroscopy

    International Nuclear Information System (INIS)

    Konstantinova, E. A.; Demin, V. A.; Timoshenko, V. Yu.

    2008-01-01

    The generation of singlet oxygen is investigated and its concentration upon photoexcitation of silicon nanocrystals in porous silicon layers is determined using electron paramagnetic resonance spectroscopy. The relaxation times of spin centers, i.e., silicon dangling bonds, in vacuum and in an oxygen atmosphere in the dark and under illumination of the samples are measured for the first time. It is revealed that the spin-lattice relaxation in porous silicon is retarded as compared to that in a single-crystal substrate. From analyzing experimental data, a microscopic model is proposed for interaction of oxygen molecules in the triplet state and spin centers at the surface of silicon nanocrystals. The results obtained have demonstrated that porous silicon holds promise for the use as a photosensitizer of molecular oxygen in biomedical applications

  11. Optical and electron paramagnetic resonance studies of the excited triplet states of UV-B absorbers: 2-ethylhexyl salicylate and homomenthyl salicylate.

    Science.gov (United States)

    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.

  12. Interfacial charge recombination via the triplet state? Mimicry of photoprotection in the photosynthetic process with a dye-sensitized TiO 2 solar cell reaction

    Science.gov (United States)

    Weng, Yu-Xiang; Li, Long; Liu, Yin; Wang, Li; Yang, Guo-Zhen; Sheng, Jian-Qun

    2002-04-01

    Evidence for the photoinduced charge recombination to the excited-triplet state has been observed in chemical solar cell reaction consisting of dye-sensitized TiO 2 colloidal ethanol solution, which mimicks the photoprotection function in the photosynthetic units. The dye is all -trans-retinoic acid, a structural analog of β-carotenoid. Two channels of charge recombination, i.e., through triplet and ground states were observed by nano-second flash photolysis. The possibility of applying the function of photoprotection to the synthetic solar cell is discussed, which provides a potential entry of molecular engineering of the dye to improve the long term stability of the synthetic solar cell.

  13. Properties of the triplet metastable states of the alkaline-earth-metal atoms

    International Nuclear Information System (INIS)

    Mitroy, J.; Bromley, M.W.J.

    2004-01-01

    The static and dynamic properties of the alkaline-earth-metal atoms in their metastable state are computed in a configuration interaction approach with a semiempirical model potential for the core. Among the properties determined are the scalar and tensor polarizabilities, the quadrupole moment, some of the oscillator strengths, and the dispersion coefficients of the van der Waals interaction. A simple method for including the effect of the core on the dispersion parameters is described

  14. Toward enabling large-scale open-shell equation-of-motion coupled cluster calculations: triplet states of β-carotene

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Hanshi; Bhaskaran-Nair, Kiran; Apra, Edoardo; Govind, Niranjan; Kowalski, Karol

    2014-10-02

    In this paper we discuss the application of novel parallel implementation of the coupled cluster (CC) and equation-of-motion coupled cluster methods (EOMCC) in calculations of excitation energies of triplet states in beta-carotene. Calculated excitation energies are compared with experimental data, where available. We also provide a detailed description of the new parallel algorithms for iterative CC and EOMCC models involving single and doubles excitations.

  15. Overview of helium-like structure measurements: A focus on the N = 2 triplet states

    International Nuclear Information System (INIS)

    Berry, H.G.; Dunford, R.W.

    1992-01-01

    We present a comprehensive analysis of existing measurements of the 1s2s 3 S 1 - 1s2p 3 P 0,1,2 transition energies in heliumlike ions for nuclear charges Z=2 to Z=92. We find agreement with the standard unified calculations of |Drake except for the transitions from the 1s2p 3 P o state. We find a deviation equal to 2.3x(Z/10) 4 cm -1 for the most precise existing measurements

  16. Photoswitching of triplet-triplet annihilation upconversion with photo-generated radical from hexaphenylbiimidazole

    Energy Technology Data Exchange (ETDEWEB)

    Mahmood, Zafar [State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116024 (China); Toffoletti, Antonio [Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Via Marzolo, 1, 35131 Padova (Italy); Zhao, Jianzhang, E-mail: zhaojzh@dlut.edu.cn [State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116024 (China); Barbon, Antonio, E-mail: antonio.barbon@unipd.it [Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Via Marzolo, 1, 35131 Padova (Italy)

    2017-03-15

    Photoirradiation generated radical from hexaphenyl-biimidazole (HPBI) was used for reversible switching of triplet-triplet annihilation (TTA) upconversion, based on quenching of the photosensitizer triplet state by radical-triplet pair mechanism. Upon 365 nm irradiation, the TTA upconversion in a system composed by a boron-dipyrromethene (BODIPY) derivative and perylene, was completely switched off due to quenching of triplet state of photosensitizer by photogenerated radical from HPBI. The upconversion was recovered after leaving the samples in darkness, due to regeneration of HPBI Dimer. The photophysical process involved in the photochromism and photoswitching of TTA upconversion were studied with steady-state UV–vis absorption spectroscopy, nanosecond transient absorption spectroscopy and EPR spectroscopy. - Graphical abstract: Radical-switched TTA upconversion was achieved with reversible quenching of the triplet state by photo-generated stable organic radical from photochromic hexaphenylbiimidazole.

  17. Aqueous benzene-diols react with an organic triplet excited state and hydroxyl radical to form secondary organic aerosol.

    Science.gov (United States)

    Smith, Jeremy D; Kinney, Haley; Anastasio, Cort

    2015-04-21

    Chemical processing in atmospheric aqueous phases, such as cloud and fog drops, can play a significant role in the production and evolution of secondary organic aerosol (SOA). In this work we examine aqueous SOA production via the oxidation of benzene-diols (dihydroxy-benzenes) by the triplet excited state of 3,4-dimethoxybenzaldehyde, (3)DMB*, and by hydroxyl radical, ˙OH. Reactions of the three benzene-diols (catechol (CAT), resorcinol (RES) and hydroquinone (HQ)) with (3)DMB* or ˙OH proceed rapidly, with rate constants near diffusion-controlled values. The two oxidants exhibit different behaviors with pH, with rate constants for (3)DMB* increasing as pH decreases from pH 5 to 2, while rate constants with ˙OH decrease in more acidic solutions. Mass yields of SOA were near 100% for all three benzene-diols with both oxidants. We also examined the reactivity of atmospherically relevant mixtures of phenols and benzene-diols in the presence of (3)DMB*. We find that the kinetics of phenol and benzene-diol loss, and the production of SOA mass, in mixtures are generally consistent with rate constants determined in experiments containing a single phenol or benzene-diol. Combining our aqueous kinetic and SOA mass yield data with previously published gas-phase data, we estimate a total SOA production rate from benzene-diol oxidation in a foggy area with significant wood combustion to be nearly 0.6 μg mair(-3) h(-1), with approximately half from the aqueous oxidation of resorcinol and hydroquinone, and half from the gas-phase oxidation of catechol.

  18. Density functional theory calculations of the lowest energy quintet and triplet states of model hemes: role of functional, basis set, and zero-point energy corrections.

    Science.gov (United States)

    Khvostichenko, Daria; Choi, Andrew; Boulatov, Roman

    2008-04-24

    We investigated the effect of several computational variables, including the choice of the basis set, application of symmetry constraints, and zero-point energy (ZPE) corrections, on the structural parameters and predicted ground electronic state of model 5-coordinate hemes (iron(II) porphines axially coordinated by a single imidazole or 2-methylimidazole). We studied the performance of B3LYP and B3PW91 with eight Pople-style basis sets (up to 6-311+G*) and B97-1, OLYP, and TPSS functionals with 6-31G and 6-31G* basis sets. Only hybrid functionals B3LYP, B3PW91, and B97-1 reproduced the quintet ground state of the model hemes. With a given functional, the choice of the basis set caused up to 2.7 kcal/mol variation of the quintet-triplet electronic energy gap (DeltaEel), in several cases, resulting in the inversion of the sign of DeltaEel. Single-point energy calculations with triple-zeta basis sets of the Pople (up to 6-311G++(2d,2p)), Ahlrichs (TZVP and TZVPP), and Dunning (cc-pVTZ) families showed the same trend. The zero-point energy of the quintet state was approximately 1 kcal/mol lower than that of the triplet, and accounting for ZPE corrections was crucial for establishing the ground state if the electronic energy of the triplet state was approximately 1 kcal/mol less than that of the quintet. Within a given model chemistry, effects of symmetry constraints and of a "tense" structure of the iron porphine fragment coordinated to 2-methylimidazole on DeltaEel were limited to 0.3 kcal/mol. For both model hemes the best agreement with crystallographic structural data was achieved with small 6-31G and 6-31G* basis sets. Deviation of the computed frequency of the Fe-Im stretching mode from the experimental value with the basis set decreased in the order: nonaugmented basis sets, basis sets with polarization functions, and basis sets with polarization and diffuse functions. Contraction of Pople-style basis sets (double-zeta or triple-zeta) affected the results

  19. Sub-ns triplet state formation by non-geminate recombination in PSBTBT:PC 70 BM and PCPDTBT:PC 60 BM organic solar cells

    KAUST Repository

    Etzold, Fabian

    2015-03-02

    The solid-state morphology and photo-generated charge carrier dynamics in low-bandgap polymer:fullerene bulk heterojunction photovoltaic blends using the donor–acceptor type copolymers PCPDTBT or its silicon-substituted analogue PSBTBT as donors are compared by two-dimensional (2D) solid-state nuclear magnetic resonance (NMR) and femto-to microsecond broadband Vis-NIR transient absorption (TA) pump–probe spectroscopy. The 2D solid-state NMR experiments demonstrate that the film morphology of PCPDTBT:PC60BM blends processed with additives such as octanedithiol (ODT) are similar to those of PSBTBT:PC60BM blends in terms of crystallinity, phase segregation, and interfacial contacts. The TA experiments and analysis of the TA data by multivariate curve resolution (MCR) reveal that after exciton dissociation and free charge formation, fast sub-nanosecond non-geminate recombination occurs which leads to a substantial population of the polymer\\'s triplet state. The extent to which triplet states are formed depends on the initial concentration of free charges, which itself is controlled by the microstructure of the blend, especially in case of PCPDTBT:PC60BM. Interestingly, PSBTBT:PC70BM blends show a higher charge generation efficiency, but less triplet state formation at similar free charge carrier concentrations. This indicates that the solid-state morphology and interfacial structures of PSBTBT:PC70BM blends reduces non-geminate recombination, leading to superior device performance compared to optimized PCPDTBT:PC60BM blends.

  20. Sub-ns triplet state formation by non-geminate recombination in PSBTBT:PC 70 BM and PCPDTBT:PC 60 BM organic solar cells

    KAUST Repository

    Etzold, Fabian; Howard, Ian A.; Forler, Nina; Melnyk, Anton; Andrienko, Denis; Hansen, Michael Ryan; Laquai, Fré dé ric

    2015-01-01

    The solid-state morphology and photo-generated charge carrier dynamics in low-bandgap polymer:fullerene bulk heterojunction photovoltaic blends using the donor–acceptor type copolymers PCPDTBT or its silicon-substituted analogue PSBTBT as donors are compared by two-dimensional (2D) solid-state nuclear magnetic resonance (NMR) and femto-to microsecond broadband Vis-NIR transient absorption (TA) pump–probe spectroscopy. The 2D solid-state NMR experiments demonstrate that the film morphology of PCPDTBT:PC60BM blends processed with additives such as octanedithiol (ODT) are similar to those of PSBTBT:PC60BM blends in terms of crystallinity, phase segregation, and interfacial contacts. The TA experiments and analysis of the TA data by multivariate curve resolution (MCR) reveal that after exciton dissociation and free charge formation, fast sub-nanosecond non-geminate recombination occurs which leads to a substantial population of the polymer's triplet state. The extent to which triplet states are formed depends on the initial concentration of free charges, which itself is controlled by the microstructure of the blend, especially in case of PCPDTBT:PC60BM. Interestingly, PSBTBT:PC70BM blends show a higher charge generation efficiency, but less triplet state formation at similar free charge carrier concentrations. This indicates that the solid-state morphology and interfacial structures of PSBTBT:PC70BM blends reduces non-geminate recombination, leading to superior device performance compared to optimized PCPDTBT:PC60BM blends.

  1. Phasic Triplet Markov Chains.

    Science.gov (United States)

    El Yazid Boudaren, Mohamed; Monfrini, Emmanuel; Pieczynski, Wojciech; Aïssani, Amar

    2014-11-01

    Hidden Markov chains have been shown to be inadequate for data modeling under some complex conditions. In this work, we address the problem of statistical modeling of phenomena involving two heterogeneous system states. Such phenomena may arise in biology or communications, among other fields. Namely, we consider that a sequence of meaningful words is to be searched within a whole observation that also contains arbitrary one-by-one symbols. Moreover, a word may be interrupted at some site to be carried on later. Applying plain hidden Markov chains to such data, while ignoring their specificity, yields unsatisfactory results. The Phasic triplet Markov chain, proposed in this paper, overcomes this difficulty by means of an auxiliary underlying process in accordance with the triplet Markov chains theory. Related Bayesian restoration techniques and parameters estimation procedures according to the new model are then described. Finally, to assess the performance of the proposed model against the conventional hidden Markov chain model, experiments are conducted on synthetic and real data.

  2. Threshold law for the triplet state for electron-impact ionization in the Temkin-Poet model

    International Nuclear Information System (INIS)

    Ihra, W.; Mota-Furtado, F.; OMahony, P.F.; Macek, J.H.

    1997-01-01

    We derive the analytical threshold behavior for the triplet cross section for electron-impact ionization in the Temkin-Poet model. The analytical results indicate that the most recent numerical calculations may fail to reproduce the correct threshold behavior in an energy regime below about E=0.1 a.u. We also present an analytical expression for the energy distribution of the two electrons near threshold. copyright 1997 The American Physical Society

  3. Detailed Characterization of a Nanosecond-Lived Excited State: X-ray and Theoretical Investigation of the Quintet State in Photoexcited [Fe(terpy)(2)](2+)

    DEFF Research Database (Denmark)

    Vanko, Gyoergy; Bordage, Amelie; Pápai, Mátyás Imre

    2015-01-01

    Theoretical predictions show that depending on the populations of the Fe 3d(xy), 3d(xz), and 3d(yz) orbitals two possible quintet states can exist for the high-spin state of the photoswitchable model system [Fe(terpy)(2)](2+). The differences in the structure and molecular properties of these B-5...

  4. Theory of triplet-triplet annihilation in optically detected magnetic resonance

    Science.gov (United States)

    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.

  5. Detailed Characterization of a Nanosecond-Lived Excited State: X-ray and Theoretical Investigation of the Quintet State in Photoexcited [Fe(terpy) 2 ] 2+

    International Nuclear Information System (INIS)

    Vanko, Gyorgy; Bordage, Amelie; Papai, Matyas; Haldrup, Kristoffer; March, Anne Marie; Galler, Andreas; Assefa, Tadesse; Cabaret, Delphine; Juhin, Amelie; Driel, Tim B. van; Gallo, Erik; Rovezzi, Mauro; Nemeth, Zoltan; Rozsalyi, Emese; Rozgonyi, Tamas; Uhlig, Jens; Gawelda, Wojciech

    2015-01-01

    Theoretical predictions show that depending on the populations of the Fe 3d xy , 3d xz , and 3d yz orbitals two possible quintet states can exist for the high-spin state of the photoswitchable model system [Fe(terpy) 2 ] 2+ . The differences in the structure and molecular properties of these 5B2 and 5E quintets are very small and pose a substantial challenge for experiments to resolve them. Yet for a better understanding of the physics of this system, which can lead to the design of novel molecules with enhanced photoswitching performance, it is vital to determine which high-spin state is reached in the transitions that follow the light excitation. The quintet state can be prepared with a short laser pulse and can be studied with cutting-edge time-resolved X-ray techniques. Here we report on the application of an extended set of X-ray spectroscopy and scattering techniques applied to investigate the quintet state of [Fe(terpy) 2 ] 2+ 80 ps after light excitation. High-quality X-ray absorption, nonresonant emission, and resonant emission spectra as well as X-ray diffuse scattering data clearly reflect the formation of the high-spin state of the [Fe(terpy) 2 ] 2+ molecule; moreover, extended X-ray absorption fine structure spectroscopy resolves the Fe-ligand bond-length variations with unprecedented bond-length accuracy in time-resolved experiments. With ab initio calculations we determine why, in contrast to most related systems, one configurational mode is insufficient for the description of the low-spin (LS)-high-spin (HS) transition. We identify the electronic structure origin of the differences between the two possible quintet modes, and finally, we unambiguously identify the formed quintet state as 5E, in agreement with our theoretical expectations

  6. Singlet oxygen produced by quasi-continuous photo-excitation of hypericin in dimethyl-sulfoxide

    Energy Technology Data Exchange (ETDEWEB)

    Varchola, J.; Želonková, K. [Department of Biophysics, Faculty of Science, P. J. Šafárik University, Jesenná 5, 041 54 Košice (Slovakia); Chorvat Jr, D. [International Laser Centre, Ilkovicova 3, 841 05 Bratislava (Slovakia); Jancura, D. [Department of Biophysics, Faculty of Science, P. J. Šafárik University, Jesenná 5, 041 54 Košice (Slovakia); Center for Interdisciplinary Biosciences, Faculty of Science, P. J. Šafárik University, Jesenná 5, 041 54 Košice (Slovakia); Miskovsky, P. [Department of Biophysics, Faculty of Science, P. J. Šafárik University, Jesenná 5, 041 54 Košice (Slovakia); International Laser Centre, Ilkovicova 3, 841 05 Bratislava (Slovakia); Center for Interdisciplinary Biosciences, Faculty of Science, P. J. Šafárik University, Jesenná 5, 041 54 Košice (Slovakia); and others

    2016-09-15

    Singlet oxygen (O{sub 2}({sup 1}Δ{sub g})) production by photo-excited hypericin (Hyp) dissolved in dimethyl-sulfoxide (DMSO) was studied by means of time-resolved phosphorescence measurements. In order to minimize photo-bleaching, the samples were excited in quasi-continuous mode using long-pulse (35 μs) laser excitation. The measured lifetime of singlet oxygen is τ{sub Δ}=5.5±0.3 μs. This result helps to resolve the discrepancy existing in the literature concerning singlet oxygen lifetime in DMSO. The obtained quantum yield of singlet oxygen photosensitized by Hyp in air-saturated DMSO is Φ{sub Δ}=0.4±0.03. The rate constant for Hyp triplet state depopulation in reaction with ground state molecular oxygen is measured to be k{sub q}=1.6±0.3×10{sup 9} M{sup −1} s{sup −1}.

  7. Triplet--Triplet Absorption Spectra of Organic Molecules in Condensed Phases

    International Nuclear Information System (INIS)

    Carmichael, I.; Hug, G.L.

    1986-01-01

    We present a compilation of spectral parameters associated with triplet--triplet absorption of organic molecules in condensed media. The wavelengths of maximum absorbance and the corresponding extinction coefficients, where known, have been critically evaluated. Other data, for example, lifetimes, energies and energy transfer rates, relevant to the triplet states of these molecules are included by way of comments but have not been subjected to a similar scrutiny. Work in the gas phase has been omitted, as have theoretical studies. We provide an introduction to triplet state processes in solution and solids, developing the conceptual background and offering an historical perspective on the detection and measurement of triplet state absorption. Techniques employed to populate the triplet state are reviewed and the various approaches to the estimation of the extinction coefficient of triplet--triplet absorption are critically discussed. A statistical analysis of the available data is presented and recommendations for a hierarchical choice of extinction coefficients are made. Data collection is expected to be complete through the end of 1984. Compound name, molecular formula and author indexes are appended

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

    KAUST Repository

    Samanta, Pralok Kumar

    2017-02-28

    The rates for up-conversion intersystem crossing (UISC) from the T1 state to the S1 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 S1 and T1 states (ΔEST) are evaluated, at the density functional theory (DFT) and time-dependent DFT levels. The calculated UISC rates and ΔEST values are found to be in good agreement with available experimental data. Our results underline that small ΔEST 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 ΔEST; in fact, either a significant charge-transfer (CT) contribution to the T1 state or a minimal energy difference between the local-excitation and charge-transfer triplet states is required to achieve a small ΔEST. Also, having S1 and T1 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 T1 and somewhat different natures of the S1 and T1 states, paves the way toward UISC enhancement and thus TADF efficiency improvement.

  9. Photo-excitation of carotenoids causes cytotoxicity via singlet oxygen production

    International Nuclear Information System (INIS)

    Yoshii, Hiroshi; Yoshii, Yukie; Asai, Tatsuya; Furukawa, Takako; Takaichi, Shinichi; Fujibayashi, Yasuhisa

    2012-01-01

    Highlights: ► Some photo-excited carotenoids have photosensitizing ability. ► They are able to produce ROS. ► Photo-excited fucoxanthin can produce singlet oxygen through energy transfer. -- Abstract: Carotenoids, natural pigments widely distributed in algae and plants, have a conjugated double bond system. Their excitation energies are correlated with conjugation length. We hypothesized that carotenoids whose energy states are above the singlet excited state of oxygen (singlet oxygen) would possess photosensitizing properties. Here, we demonstrated that human skin melanoma (A375) cells are damaged through the photo-excitation of several carotenoids (neoxanthin, fucoxanthin and siphonaxanthin). In contrast, photo-excitation of carotenoids that possess energy states below that of singlet oxygen, such as β-carotene, lutein, loroxanthin and violaxanthin, did not enhance cell death. Production of reactive oxygen species (ROS) by photo-excited fucoxanthin or neoxanthin was confirmed using a reporter assay for ROS production with HeLa Hyper cells, which express a fluorescent indicator protein for intracellular ROS. Fucoxanthin and neoxanthin also showed high cellular penetration and retention. Electron spin resonance spectra using 2,2,6,6-tetramethil-4-piperidone as a singlet oxygen trapping agent demonstrated that singlet oxygen was produced via energy transfer from photo-excited fucoxanthin to oxygen molecules. These results suggest that carotenoids such as fucoxanthin, which are capable of singlet oxygen production through photo-excitation and show good penetration and retention in target cells, are useful as photosensitizers in photodynamic therapy for skin disease.

  10. Synthesis and Exciton Dynamics of Triplet Sensitized Conjugated Polymers

    KAUST Repository

    Andernach, Rolf

    2015-07-22

    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 timescales and investigated the mechanism of triplet exciton formation. During sensitization, single 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 find that 60% of the complex triplet excitons are 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 up-conversion layers.

  11. Favorable performance of the DFT methods in predicting the minimum-energy structure of the lowest triplet state of WF4

    International Nuclear Information System (INIS)

    Gutowski, M.; Univ. of Utah, Salt Lake City, UT

    1999-01-01

    The tetrahedral structure of the lowest triplet state of the WF 4 complex was examined using different variants of the density functional theory (DFT) and conventional ab initio methods. The low-level, conventional, ab initio methods, such as SCF, MP2, MP3, and CISD, predict the tetrahedral structure to be a minimum, whereas the DFT schemes predict an imaginary frequency for the e vibrational mode. Only after recovering electron correlation effects at the MP4 and higher levels, the conventional electronic structure methods also predict the T d structure to be a second-order stationary point. This is not the correlation but the exchange part of the DFT functionals which is responsible for the discrepancy between the DFT and low-level, conventional, ab initio predictions. The lowering of symmetry to C 2v leads to a minimum on the lowest triplet potential energy surface and the electronic energy difference between the T d and C 2v stationary points amounts to 0.85 and 0.96 kcal/mol at the B3LYP and CCSD(T) levels, respectively

  12. Identification of excited states in conjugated polymers

    International Nuclear Information System (INIS)

    Hartwell, Lewis John

    2003-01-01

    This thesis reports quasi steady state photoinduced absorption measurements from three conjugated polymers: polypyridine (PPy), polyfluorene (PFO) and the emeraldine base (EB) form of polyaniline. The aim of these experiments was to determine the nature of the photoexcited states existing in these materials in the millisecond time domain, as this has important consequences for the operation of real devices manufactured using these materials. The results from the photoinduced absorption experiments are closely compared with published results from pulse radiolysis experiments. In all cases there is very good correspondence between the two data sets, which has enabled the photoexcited states to be assigned with a high degree of confidence. Quasi steady-state photoinduced absorption involves the measurement of the change in absorption of a material in response to optical excitation with a laser beam. The changes in absorption are small, so a dedicated instrument was developed and optimised for each different sample. Lock-in techniques were used to recover the small signals from the samples. The samples involved were thin films of the polymer spin coated onto sapphire substrates in the cases of PPy and EB. Solution state experiments were conducted on EB. The experiments on PFO were conducted on aligned and unaligned thin films provided by Sony. In the case of the aligned PFO samples, the photoinduced absorption spectrometer was modified to enable polarisation-sensitive data collection. In PPy, both triplet excitons and polarons have been shown to be long-lived photoexcitations, with photoinduced absorption features at 2.29 eV (triplet exciton transition), 1.5 eV and 0.8 eV (polaron transitions). In PFO, the one observed photoinduced band at 1.52 eV is assigned to a triplet exciton. Two photoinduced absorption bands are observed in EB, at 1.4 eV and 0.8 eV. These are assigned to a self-trapped CT singlet exciton and triplet exciton, respectively. (author)

  13. Characterizing the Solvated Structure of Photoexcited [Os(terpy2]2+ with X-ray Transient Absorption Spectroscopy and DFT Calculations

    Directory of Open Access Journals (Sweden)

    Xiaoyi Zhang

    2016-02-01

    Full Text Available Characterizing the geometric and electronic structures of individual photoexcited dye molecules in solution is an important step towards understanding the interfacial properties of photo-active electrodes. The broad family of “red sensitizers” based on osmium(II polypyridyl compounds often undergoes small photo-induced structural changes which are challenging to characterize. In this work, X-ray transient absorption spectroscopy with picosecond temporal resolution is employed to determine the geometric and electronic structures of the photoexcited triplet state of [Os(terpy2]2+ (terpy: 2,2′:6′,2″-terpyridine solvated in methanol. From the EXAFS analysis, the structural changes can be characterized by a slight overall expansion of the first coordination shell [OsN6]. DFT calculations supports the XTA results. They also provide additional information about the nature of the molecular orbitals that contribute to the optical spectrum (with TD-DFT and the near-edge region of the X-ray spectra.

  14. The importance of a hot-sequential mechanism in triplet-state formation by charge recombination in reaction centers of bacterial photosynthesis

    International Nuclear Information System (INIS)

    Saito, K.; Mukai, K.; Sumi, H.

    2006-01-01

    In photosynthesis, pigment-excitation energies in the antenna system produced by light harvesting are transferred among antenna pigments toward the core antenna, where they are captured by the reaction center and initially fixed in the form of a charge separation. Primary charge separation between an oxidized special pair (P + ) and a reduced bacteriopheohytin (H - ) is occasionally intervened by recombination, and a spin-triplet state ( 3 P*) is formed on P in the bacterial reaction center. The 3 P* state is harmful to bio-organisms, inducing the formation of the highly damaging singlet oxygen species. Therefore, understanding the 3 P*-formation mechanism is important. The 3 P* formation is mediated by a state |m> of intermediate charge separation between P and the accessory chlorophyll, which is located between P and H. It will be shown theoretically in the present work that at room temperature, not only the mechanism of superexchange by quantum-mechanical virtual mediation at |m>, but also a hot-sequential mechanism contributes to the mediation. In the latter, although |m> is produced as a real state, the final state 3 P* is quickly formed during thermalization of phonons in the protein matrix in |m>. In the former, the final state is formed more quickly before dephasing-thermalization of phonons in |m>. 3 P* is unistep formed from the charge-separated state in the both mechanisms

  15. Photoexcited iron porphyrin as biomimetic catalysts

    International Nuclear Information System (INIS)

    Bartocci, C.; Maldotti, A.; Varani, G.; Consiglio Nazionale delle Ricerche, Ferrara

    1996-01-01

    Photoexcited iron porphyrins can be of some interest in both fine and industrial chemistry in view of the preparation of new efficient biomimetic catalysts, working with high selectivity under mild temperature and pressure

  16. Triplet ultrasound growth parameters.

    Science.gov (United States)

    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.

  17. Singlet-triplet annihilation in single LHCII complexes

    NARCIS (Netherlands)

    Gruber, J.M.; Chmeliov, J.; Kruger, T.P.J.; Valkunas, L.; van Grondelle, R.

    2015-01-01

    In light harvesting complex II (LHCII) of higher plants and green algae, carotenoids (Cars) have an important function to quench chlorophyll (Chl) triplet states and therefore avoid the production of harmful singlet oxygen. The resulting Car triplet states lead to a non-linear self-quenching

  18. Direct observation of triplet energy transfer from semiconductor nanocrystals.

    Science.gov (United States)

    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.

  19. Reversal of Hückel (anti)aromaticity in the lowest triplet states of hexaphyrins and spectroscopic evidence for Baird's rule

    Science.gov (United States)

    Sung, Young Mo; Yoon, Min-Chul; Lim, Jong Min; Rath, Harapriya; Naoda, Koji; Osuka, Atsuhiro; Kim, Dongho

    2015-05-01

    The reversal of (anti)aromaticity in a molecule's triplet excited state compared with its closed-shell singlet ground state is known as Baird's rule and has attracted the interest of synthetic, physical organic chemists and theorists because of the potential to modulate the fundamental properties of highly conjugated molecules. Here we show that two closely related bis-rhodium hexaphyrins (R26H and R28H) containing [26] and [28] π-electron peripheries, respectively, exhibit properties consistent with Baird's rule. In the ground state, R26H exhibits a sharp Soret-like band and distinct Q-like bands characteristic of an aromatic porphyrinoid, whereas R28H exhibits a broad absorption spectrum without Q-like bands, which is typical of an antiaromatic porphyrinoid. In contrast, the T-T absorption of R26H is broad, weak and featureless, whereas that of R28H displays an intense and sharp Soret-like band. These spectral signatures, in combination with quantum chemical calculations, are in line with qualitative expectations based on Baird's rule.

  20. Electronic coupling between photo-excited stacked bases in DNA and RNA strands with emphasis on the bright states initially populated

    DEFF Research Database (Denmark)

    Nielsen (Baggesen), Lisbeth Munksgård; Hoffmann, Søren Vrønning; Nielsen, Steen Brøndsted

    2013-01-01

    . In this review paper, we focus on the bright states initially populated and discuss their nature based on information obtained from systematic absorption and circular dichroism experiments on single strands of different lengths. Our results from the last five years are compared with those from other groups......, and are discussed in the context of successive deexcitation schemes. Pieces to the puzzle have come from different experiments and theory but a complete description has yet to emerge. As such the story about DNA/RNA photophysical decay mechanisms resembles the tale about the blind men and the elephant where all see...

  1. Analyzing a steady-state phenomenon using an ensemble of sequential transient events: A proof of concept on photocurrent of bacteriorhodopsin upon continuous photoexcitation

    Energy Technology Data Exchange (ETDEWEB)

    Hung, Chang-Wei; Chu, Li-Kang, E-mail: lkchu@mx.nthu.edu.tw [Department of Chemistry, National Tsing Hua University, 101, Sec. 2, Kuang-Fu Rd., Hsinchu 30013, Taiwan (China); Ho, Ching-Hwa [Interdisplinary Program of Science, National Tsing Hua University, 101, Sec. 2, Kuang-Fu Rd., Hsinchu 30013, Taiwan (China)

    2014-10-14

    The proton pump activity of bacteriorhodopsin in aqueous solution upon excitation with modulated continuous light was monitored electrochemically and analyzed by superimposing a series of transient proton translocation events Hᵢ⁺(t). An evolution function f(t)=(he{sup –lt}+k)/(h+k) , including a decay and a stationary offset, was introduced to weight the contribution of the individual transient events evolving with time in the envelope of the steady-state event. The evolution of the total proton concentration can be treated as an ensemble of weighted sequential transient events, H{sub total}⁺(t)=Σ{{sub i=0}sup n}Hᵢ⁺(t)∙f(t), and the temporal profile of the photocurrent is derived by differentiating the proton concentration with respect to time, (table) . The temporal profiles of the bacteriorhodopsin photocurrent in pH range of 6.3–8.1 were analyzed using a well-defined kinetics model and restricted mathematical formulization, and fitted temporal behaviors agreed with the observations. This successful proof-of-concept study on analyzing a steady-state phenomenon using an ensemble of sequential transient events can be generalized to quantify other phenomena upon continuous stimulation, such as estimation of the light-driven ion pump activities of the photosynthetic proteins upon illumination.

  2. Roles of singlet oxygen and triplet excited state of dissolved organic matter formed by different organic matters in bacteriophage MS2 inactivation

    KAUST Repository

    Rosado-Lausell, Sahid L.; Wang, Hanting; Gutié rrez, Leonardo A.; Romero-Maraccini, Ofelia C.; Niu, Xi-Zhi; Gin, Karina; Croue, Jean-Philippe; Nguyen, Thanh Ha

    2013-01-01

    Inactivation of bacteriophage MS2 by reactive oxygen species (ROS) and triplet excited state of dissolved organic matter (3DOM*) produced by irradiation of natural and synthetic sensitizers with simulated sunlight of wavelengths greater than 320nm was investigated. Natural sensitizers included purified DOM isolates obtained from wastewater and river waters, and water samples collected from Singapore River, Stamford Canal, and Marina Bay Reservoir in Singapore. Linear correlations were found between MS2 inactivation rate constants (kobs) and the photo-induced reaction rate constants of 2,4,6-trimethylphenol (TMP), a probe compound shown to react mainly with 3DOM*. Linear correlations between MS2 kobs and singlet oxygen (1O2) concentrations were also found for both purified DOM isolates and natural water samples. These correlations, along with data from quenching experiments and experiments with synthetic sensitizers, Rose Bengal (RB), 3'-methoxyacetophenone (3'-MAP), and nitrite (NO2-), suggest that 1O2, 3DOM*, and hydroxyl radicals (•OH) could inactivate bacteriophage MS2. Linear correlations between MS2 kobs and Specific Ultraviolet Absorption determined at 254nm (SUVA254) were also found for both purified DOM isolates and natural samples. These results suggest the potential use of TMP as a chemical probe and SUVA254 as an indicator for virus inactivation in natural and purified DOM water samples. © 2013 Elsevier Ltd.

  3. Roles of singlet oxygen and triplet excited state of dissolved organic matter formed by different organic matters in bacteriophage MS2 inactivation

    KAUST Repository

    Rosado-Lausell, Sahid L.

    2013-09-01

    Inactivation of bacteriophage MS2 by reactive oxygen species (ROS) and triplet excited state of dissolved organic matter (3DOM*) produced by irradiation of natural and synthetic sensitizers with simulated sunlight of wavelengths greater than 320nm was investigated. Natural sensitizers included purified DOM isolates obtained from wastewater and river waters, and water samples collected from Singapore River, Stamford Canal, and Marina Bay Reservoir in Singapore. Linear correlations were found between MS2 inactivation rate constants (kobs) and the photo-induced reaction rate constants of 2,4,6-trimethylphenol (TMP), a probe compound shown to react mainly with 3DOM*. Linear correlations between MS2 kobs and singlet oxygen (1O2) concentrations were also found for both purified DOM isolates and natural water samples. These correlations, along with data from quenching experiments and experiments with synthetic sensitizers, Rose Bengal (RB), 3\\'-methoxyacetophenone (3\\'-MAP), and nitrite (NO2-), suggest that 1O2, 3DOM*, and hydroxyl radicals (•OH) could inactivate bacteriophage MS2. Linear correlations between MS2 kobs and Specific Ultraviolet Absorption determined at 254nm (SUVA254) were also found for both purified DOM isolates and natural samples. These results suggest the potential use of TMP as a chemical probe and SUVA254 as an indicator for virus inactivation in natural and purified DOM water samples. © 2013 Elsevier Ltd.

  4. Electron Transfer from Triplet State of TIPS-Pentacene Generated by Singlet Fission Processes to CH3NH3PbI3 Perovskite.

    Science.gov (United States)

    Lee, Sangsu; Hwang, Daesub; Jung, Seok Il; Kim, Dongho

    2017-02-16

    To reveal the applicability of singlet fission processes in perovskite solar cell, we investigated electron transfer from TIPS-pentacene to CH 3 NH 3 PbI 3 (MAPbI 3 ) perovskite in film phase. Through the observation of the shorter fluorescence lifetime in TIPS-pentacene/MAPbI 3 perovskite bilayer film (5 ns) compared with pristine MAPbI 3 perovskite film (20 ns), we verified electron-transfer processes between TIPS-pentacene and MAPbI 3 perovskite. Furthermore, the observation of singlet fission processes, a faster decay rate, TIPS-pentacene cations, and the analysis of kinetic profiles of the intensity ratio between 500 and 525 nm in the TA spectra of the TIPS-pentacene/MAPbI 3 perovskite bilayer film indicate that electron transfer occurs from triplet state of TIPS-pentacene generated by singlet fission processes to MAPbI 3 perovskite conduction band. We believe that our results can provide useful information on the design of solar cells sensitized by singlet fission processes and pave the way for new types of perovskite solar cells.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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 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.

  7. Experimental Investigation of Triplet Correlation Approximations for Fluid Water.

    Science.gov (United States)

    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.

  8. A new phosphine oxide host based on ortho-disubstituted dibenzofuran for efficient electrophosphorescence: towards high triplet state excited levels and excellent thermal, morphological and efficiency stability.

    Science.gov (United States)

    Han, Chunmiao; Xie, Guohua; Li, Jing; Zhang, Zhensong; Xu, Hui; Deng, Zhaopeng; Zhao, Yi; Yan, Pengfei; Liu, Shiyong

    2011-08-01

    An efficient host for blue and green electrophosphorescence, 4,6-bis(diphenylphosphoryl)dibenzofuran (o-DBFDPO), with the structure of a short-axis-substituted dibenzofuran was designed and synthesised. It appears that the greater density of the diphenylphosphine oxide (DPPO) moieties in the short-axis substitution configuration effectively restrains the intermolecular interactions, because only very weak π-π stacking interactions could be observed, with a centroid-to-centroid distance of 3.960 Å. The improved thermal stability of o-DBFDPO was corroborated by its very high glass transition temperature (T(g)) of 191 °C, which is the result of the symmetric disubstitution structure. Photophysical investigation showed o-DBFDPO to be superior to the monosubstituted derivative, with a longer lifetime (1.95 ns) and a higher photoluminescent quantum efficiency (61 %). The lower first singlet state excited level (3.63 eV) of o-DBFDPO demonstrates the stronger polarisation effect attributable to the greater number of DPPO moieties. Simultaneously, an extremely high first triplet state excited level (T(1)) of 3.16 eV is observed, demonstrating the tiny influence of short-axis substitution on T(1). The improved carrier injection ability, which contributed to low driving voltages of blue- and green-emitting phosphorescent organic light-emitting diodes (PHOLEDs), was further confirmed by Gaussian calculation. Furthermore, the better thermal and morphological properties of o-DBFDPO and the matched frontier molecular orbital (FMO) levels in the devices significantly reduced efficiency roll-offs. Efficient blue and green electrophosphorescence based on the o-DBFDPO host was demonstrated. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Highly efficient visible-light driven photochromism: developments towards a solid-state molecular switch operating through a triplet-sensitised pathway.

    Science.gov (United States)

    Brayshaw, Simon K; Schiffers, Stephanie; Stevenson, Anna J; Teat, Simon J; Warren, Mark R; Bennett, Robert D; Sazanovich, Igor V; Buckley, Alastair R; Weinstein, Julia A; Raithby, Paul R

    2011-04-11

    We introduce a new highly efficient photochromic organometallic dithienylethene (DTE) complex, the first instance of a DTE core symmetrically modified by two Pt(II) chromophores [Pt(PEt(3))(2)(C≡C)(DTE)(C≡C)Pt(PEt(3))(2)Ph] (1), which undergoes ring-closure when activated by visible light in solvents of different polarity, in thin films and even in the solid state. Complex 1 has been synthesised and fully photophysically characterised by (resonance) Raman and transient absorption spectroscopy complemented by calculations. The ring-closing photoconversion in a single crystal of 1 has been followed by X-ray crystallography. This process occurs with the extremely high yield of 80%--considerably outperforming the other DTE derivatives. Remarkably, the photocyclisation of 1 occurs even under visible light (>400 nm), which is not absorbed by the non-metallated DTE core HC≡C(DTE)C≡CH (2) itself. This unusual behaviour and the high photocyclisation yields in solution are attributed to the presence of a heavy atom in 1 that enables a triplet-sensitised photocyclisation pathway, elucidated by transient absorption spectroscopy and DFT calculations. The results of resonance Raman investigation confirm the involvement of the alkynyl unit in the frontier orbitals of both closed and open forms of 1 in the photocyclisation process. The changes in the Raman spectra upon cyclisation have permitted the identification of Raman marker bands, which include the acetylide stretching vibration. Importantly, these bands occur in the spectral region unobstructed by other vibrations and can be used for non-destructive monitoring of photocyclisation/photoreversion processes and for optical readout in this type of efficiently photochromic thermally stable systems. This study indicates a strategy for generating efficient solid-state photoswitches in which modification of the Pt(II) units has the potential to tune absorption properties and hence operational wavelength across the visible

  10. Dynamics and configurations of galaxy triplets

    International Nuclear Information System (INIS)

    Anosova, J.P.; Orlov, V.V.; Chernin, A.D.; Ivanov, A.V.; Kiseleva, L.G.

    1990-01-01

    The purpose is to infer the probable dynamical states of galaxy triplets by the observed data on their configurations. Two methods are proposed for describing the distributions of the triplet configuration parameters characterizing a tendency to alignment and hierarchy: (1) obtaining a representative sample of configurations and determining its statistical parameters (moments and percentages); and (2) dividing the region of possible configurations of triple systems (Agekian and Anosova, 1967) into a set of segments and finding the probabilities for the configurations to find themselves in each of them. Both these methods allow representation of the data by numerical simulations as well as observations. The effect of projection was studied. It rather overestimates the alignment and hierarchy of the triple systems. Among the parameters of interest there are found some parameters that are least sensitive to projection effects. The samples consist of simulated galaxy triplets (with hidden mass) as well as of 46 probably physical triple galaxies (Karachentseva et al., 1979). The observed triples as well as numerical models show a tendency to alignment. The triple galaxies do not show any tendency to hierarchy (formation of the temporary binaries), but this tendency may be present for simulated triplets without significant dark matter. The significant hidden mass (of order ten times the total mass of a triplet) decreases the probability of forming a binary and so weakens the hierarchy. Small galaxy groups consisting of 3 to 7 members are probably the most prevalent types of galaxy aggregate (Gorbatsky, 1987). Galaxy triplets are the simplest groups, but dynamically nontrivial ones

  11. Excited-state dynamics of pentacene derivatives with stable radical substituents.

    Science.gov (United States)

    Ito, Akitaka; Shimizu, Akihiro; Kishida, Noriaki; Kawanaka, Yusuke; Kosumi, Daisuke; Hashimoto, Hideki; Teki, Yoshio

    2014-06-23

    The excited-state dynamics of pentacene derivatives with stable radical substituents were evaluated in detail through transient absorption measurements. The derivatives showed ultrafast formation of triplet excited state(s) in the pentacene moiety from a photoexcited singlet state through the contributions of enhanced intersystem crossing and singlet fission. Detailed kinetic analyses for the transient absorption data were conducted to quantify the excited-state characteristics of the derivatives. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Lowest triplet (n, π*) electronic state of acrolein: Determination of structural parameters by cavity ringdown spectroscopy and quantum-chemical methods

    Science.gov (United States)

    Hlavacek, Nikolaus C.; McAnally, Michael O.; Drucker, Stephen

    2013-02-01

    The cavity ringdown absorption spectrum of acrolein (propenal, CH2=CH—CH=O) was recorded near 412 nm, under bulk-gas conditions at room temperature and in a free-jet expansion. The measured spectral region includes the 0^0_0 band of the T1(n, π*) ← S0 system. We analyzed the 0^0_0 rotational contour by using the STROTA computer program [R. H. Judge et al., J. Chem. Phys. 103, 5343 (1995)], 10.1063/1.470569, which incorporates an asymmetric rotor Hamiltonian for simulating and fitting singlet-triplet spectra. We used the program to fit T1(n, π*) inertial constants to the room-temperature contour. The determined values (cm-1), with 2σ confidence intervals, are A = 1.662 ± 0.003, B = 0.1485 ± 0.0006, C = 0.1363 ± 0.0004. Linewidth analysis of the jet-cooled spectrum yielded a value of 14 ± 2 ps for the lifetime of isolated acrolein molecules in the T1(n, π*), v = 0 state. We discuss the observed lifetime in the context of previous computational work on acrolein photochemistry. The spectroscopically derived inertial constants for the T1(n, π*) state were used to benchmark a variety of computational methods. One focus was on complete active space methods, such as complete active space self-consistent field (CASSCF) and second-order perturbation theory with a CASSCF reference function (CASPT2), which are applicable to excited states. We also examined the equation-of-motion coupled-cluster and time-dependent density function theory excited-state methods, and finally unrestricted ground-state techniques, including unrestricted density functional theory and unrestricted coupled-cluster theory with single and double and perturbative triple excitations. For each of the above methods, we or others [O. S. Bokareva et al., Int. J. Quantum Chem. 108, 2719 (2008)], 10.1002/qua.21803 used a triple zeta-quality basis set to optimize the T1(n, π*) geometry of acrolein. We find that the multiconfigurational methods provide the best agreement with fitted inertial

  13. Photodynamic effect of light-harvesting, long-lived triplet excited state Ruthenium(II)-polyimine-coumarin complexes: DNA binding, photocleavage and anticancer studies.

    Science.gov (United States)

    Nomula, Raju; Wu, Xueyan; Zhao, Jianzhang; Munirathnam, Nagegownivari R

    2017-10-01

    Two coumarin based Ru II -polyimine complexes (Ru-1 and Ru-2) showing intense absorption of visible light and long-lived triplet excited states (~12-15μs) were used for study of the interaction with DNA. The binding of the complexes with CT-DNA were studied by UV-vis, fluorescence and time-resolved nanosecond transient absorption (ns-TA) spectroscopy. The results suggesting that the complexes interact with CT-DNA by intercalation mode of binding, showing the binding constants (K b ) 6.47×10 4 for Ru-1 and 5.94×10 4 M -1 for Ru-2, in contrast no such results were found for Ru-0. The nanosecond transient absorption spectra of these systems in the presence of CT-DNA showing a clear perturbation in the bleaching region was observed compare to buffer alone. Visible light photoirradiation DNA cleavage was investigated for these complexes by treating with the supercoiled pUC19 DNA and irradiated at 450nm. The reactive species produced upon irradiation of current agents is singlet oxygen ( 1 O 2 ), which results in the generation of other reactive oxygen species (ROS). The complexes shown efficient cleavage activity, converted complete supercoiled DNA to nicked circular at as low as 20μM concentration in 30min of light irradiation time. Significant amount of linear form was generated by Ru-1 at the same conditions. Even though Ru-0 has significant 1 O 2 quantum yield but shown lower cleavage activity compared to other two analogs is due the miserable interaction (binding) with DNA. The cytotoxicity in vitro of the complexes toward HeLa, BEL-7402 and MG-63 cells was assessed by MTT assay. The cellular uptake was observed on BEL-7402 cells under fluorescence microscope. The complexes shown appreciable cytotoxicity towards the cancer cell lines. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. Photoexcited quantum dots for killing multidrug-resistant bacteria

    Science.gov (United States)

    Courtney, Colleen M.; Goodman, Samuel M.; McDaniel, Jessica A.; Madinger, Nancy E.; Chatterjee, Anushree; Nagpal, Prashant

    2016-05-01

    Multidrug-resistant bacterial infections are an ever-growing threat because of the shrinking arsenal of efficacious antibiotics. Metal nanoparticles can induce cell death, yet the toxicity effect is typically nonspecific. Here, we show that photoexcited quantum dots (QDs) can kill a wide range of multidrug-resistant bacterial clinical isolates, including methicillin-resistant Staphylococcus aureus, carbapenem-resistant Escherichia coli, and extended-spectrum β-lactamase-producing Klebsiella pneumoniae and Salmonella typhimurium. The killing effect is independent of material and controlled by the redox potentials of the photogenerated charge carriers, which selectively alter the cellular redox state. We also show that the QDs can be tailored to kill 92% of bacterial cells in a monoculture, and in a co-culture of E. coli and HEK 293T cells, while leaving the mammalian cells intact, or to increase bacterial proliferation. Photoexcited QDs could be used in the study of the effect of redox states on living systems, and lead to clinical phototherapy for the treatment of infections.

  15. Phage inactivation by triplet acetone

    International Nuclear Information System (INIS)

    Gomes, R.A.

    1985-01-01

    The exposure of lambda phage to triplet acetone is studied. The triplet acetone is obtained from aerobic oxidation of isobutanal catalysed by peroxidase. A decrease of lambda phage ability to infect Escherichia coli is reported, perhaps, partially due to the possible production of lesions in the phage genome. (M.A.C.) [pt

  16. Structure-dependent photophysical properties of singlet and triplet metal-to-ligand charge transfer states in copper(I) bis(diimine) compounds.

    Science.gov (United States)

    Siddique, Zainul Abedin; Yamamoto, Yuichi; Ohno, Takeshi; Nozaki, Koichi

    2003-10-06

    The photophysical properties of singlet and triplet metal-to-ligand charge transfer (MLCT) states of [Cu(I)(diimine)(2)](+), where diimine is 2,9-dimethyl-1,10-phenanthroline (dmphen), 2,9-dibutyl-1,10-phenanthroline (dbphen), or 6,6'-dimethyl-2,2'-bipyridine (dmbpy), were studied. On 400 nm laser excitation of [Cu(dmphen)(2)](+) in CH(2)Cl(2) solution, prompt (1)MLCT fluorescence with a quantum yield of (2.8 +/- 0.8) x 10(-5) was observed using a picosecond time-correlated single photon counting technique. The quantum yield was dependent on the excitation wavelength, suggesting that relaxation of the Franck-Condon state to the lowest (1)MLCT competes with rapid intersystem crossing (ISC). The fluorescence lifetime of the copper(I) compound was 13-16 ps, unexpectedly long despite a large spin-orbit coupling constant of 3d electrons in copper (829 cm(-1) ). Quantum chemical calculations using a density functional theory revealed that the structure of the lowest (1)MLCT in [Cu(dmphen)(2)](+) (1(1)B(1)) was flattened due to the Jahn-Teller effect in 3d(9) electronic configuration, and the dihedral angle between the two phenanthroline planes (dha) was about 75 degrees with the dha around 90 degrees in the ground state. Intramolecular reorganization energy for the radiative transition of 1(1)B(1) was calculated as 2.1 x 10(3) cm(-1), which is responsible for the large Stokes shift of the fluorescence observed (5.4 x 10(3) cm(-1)). To understand the sluggishness of the intersystem crossing (ISC) of (1)MLCT of the copper(I) compounds, the strength of the spin-orbit interaction between the lowest (1)MLCT (1(1)B(1)) and all (3)MLCT states was calculated. The ISC channels induced by strong spin-orbit interactions (ca. 300 cm(-1)) between the metal-centered HOMO and HOMO - 1 were shown to be energetically unfavorable in the copper(I) compounds because the flattening distortion caused large splitting (6.9 x 10(3) cm(-1)) between these orbitals. The possible ISC is therefore

  17. Double photoexcitation of helium in a strong dc electric field

    International Nuclear Information System (INIS)

    Harries, James R.; Sullivan, James P.; Sternberg, James B.; Obara, Satoshi; Suzuki, Tadayuki; Azuma, Yoshiro; Hammond, Peter; Bozek, John; Berrah, Nora; Halka, Monica

    2003-01-01

    We report the first experimental measurements of the effect of an applied field on the photoexcitation and autoionization of doubly excited states of helium. Ground-state photoionization spectra have been measured in the region below the He + (N=2) threshold with static electric fields of up to 84.4 kV/cm across the interaction region. The results are compared to the theoretical calculations of Chung et al. [J. Phys. B10.1088/0953-4075/34/2/304 34, 165 (2001)], which are the only calculations available in this regime. Transitions to several states in the N=2, n=6 manifold are assigned, and a wealth of new structure is observed. Our data show that many more series are mixed in by the field than those predicted by theory

  18. Spin-selective depopulation of triplet sublevels in rapidly rotating triplet exciplexes detected by a heavy-atom-induced magnetic field effect

    OpenAIRE

    Steiner, Ulrich

    1980-01-01

    A mechanism is presented explaining a reported heavy-atom-induced magnetic field effect as a consequence of non-equilibrium triplet sublevel population in an intermediate exciplex. The triplet exciplex spin polarization is induced by sub-level-selective intersystem crossing from the exciplex triplet to its singlet ground state and is decreased by an external magnetic field. The theory accounts almost quantitatively for the observed influence of magnetic field strength and heavy-atom substitue...

  19. Retinopathy of Prematurity in Triplets

    Directory of Open Access Journals (Sweden)

    Mehmet Ali Şekeroğlu

    2016-06-01

    Full Text Available Objectives: To investigate the incidence, severity and risk factors of retinopathy of prematurity (ROP in triplets. Materials and Methods: The medical records of consecutive premature triplets who had been screened for ROP in a single maternity hospital were analyzed and presence and severity of ROP; birth weight, gender, gestational age of the infant; route of delivery and the mode of conception were recorded. Results: A total of 54 triplets (40 males, 14 females who were screened for ROP between March 2010 and February 2013 were recruited for the study. All triplets were delivered by Caesarean section and 36 (66.7% were born following an assisted conception. During follow-up, seven (13% of the infants developed ROP of any stage and two (3.7% required laser photocoagulation. The mean gestational age of triplets with ROP was 27.6±1.5 (27-31 weeks whereas it was 32.0±1.5 (30-34 weeks in those without ROP (p=0.002. The mean birth weights of triplets with and without ROP were 1290.0±295.2 (970-1600 g and 1667.5±222.2 (1130-1960 g, respectively (p<0.001. The presence of ROP was not associated with gender (p=0.358 or mode of conception (p=0.674. Conclusion: ROP in triplets seems to be mainly related to low gestational age and low birth weight. Further prospective randomized studies are necessary to demonstrate risk factors of ROP in triplets and to determine if and how gemelarity plays a role in the development of ROP.

  20. Half-metallic superconducting triplet spin multivalves

    Science.gov (United States)

    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.

  1. Triplets pass their pressure test

    CERN Multimedia

    2007-01-01

    All the LHC inner triplets have now been repaired and are in position. The first ones have passed their pressure tests with flying colours. The repaired inner triplet at LHC Point 1, right side (1R). Ranko Ostojic (on the right), who headed the team responsible for repairing the triplets, shows the magnet to Robert Zimmer, President of the University of Chicago and of Fermi Research Alliance, who visited CERN on 20th August.Three cheers for the triplets! All the LHC inner triplets have now been repaired and are in position in the tunnel. Thanks to the mobilisation of a multidisciplinary team from CERN and Fermilab, assisted by the KEK Laboratory and the Lawrence Berkeley National Laboratory (LBNL), a solution has been found, tested, validated and applied. At the end of March this year, one of the inner triplets at Point 5 failed to withstand a pressure test. A fault was identified in the supports of two out of the three quadruple magne...

  2. Quantum modelling of photo-excited processes

    International Nuclear Information System (INIS)

    Ramos, Marta M.D.; Correia, Helena M.G.

    2005-01-01

    In the framework of quantum field theory and the dipole approximation, a self-consistent quantum molecular dynamics method is used to investigate the effect of chain length on the probability of formation or decay of both singlet and triplet excitons due to photon absorption or emission in isolated poly(p-phenylene vinylene) (PPV) chains. We found that the probability of the photo-induced intra-molecular singlet exciton formation and decay increases linearly with chain length and the probability for triplet exciton formation and decay does not depend on the chain length. Polymers with long chains have thus an advantage over small molecules in solar cell and light-emitting diode (LED) applications because their efficiency depends on the number of intra-molecular singlet excitons formed or emitted in the device, which is expected to increase with the conjugation length

  3. Model of ultrafast demagnetization driven by spin-orbit coupling in a photoexcited antiferromagnetic insulator Cr2O3

    Science.gov (United States)

    Guo, Feng; Zhang, Na; Jin, Wei; Chang, Jun

    2017-06-01

    We theoretically study the dynamic time evolution following laser pulse pumping in an antiferromagnetic insulator Cr2O3. From the photoexcited high-spin quartet states to the long-lived low-spin doublet states, the ultrafast demagnetization processes are investigated by solving the dissipative Schrödinger equation. We find that the demagnetization times are of the order of hundreds of femtoseconds, in good agreement with recent experiments. The switching times could be strongly reduced by properly tuning the energy gaps between the multiplet energy levels of Cr3+. Furthermore, the relaxation times also depend on the hybridization of atomic orbitals in the first photoexcited state. Our results suggest that the selective manipulation of the electronic structure by engineering stress-strain or chemical substitution allows effective control of the magnetic state switching in photoexcited insulating transition-metal oxides.

  4. Fetomaternal outcome in triplet pregnancy

    International Nuclear Information System (INIS)

    Mazhar, S.B.; Furukh, T; Rahim, F.

    2008-01-01

    To determine maternal outcome as antenatal and postnatal complications and neonatal outcome as birth weight, morbidity and mortality in triplet gestation. All the patients with triplet pregnancy beyond 28 weeks gestation, who delivered at the study place during above period were included in the study. The primary outcome measures were frequency of maternal complications and neonatal birth, weight and morbidity. Secondary outcome measures included the frequency of assisted conception in the studied cohart. Eighteen women had triplet pregnancy beyond 28 weeks. Nine were booked, 6 non-booked and 3 of them were referred. Mean duration of gestation was 237.8 days (33.8 weeks). The antenatal complications were preterm delivery in 50%, hypertension in 50%, anemia in 44.4% and obstetric cholestasis in 5.6%. Eight patients (44.4%) suffered postpartum hemorrhage. One patient had peripartum hysterectomy and later expired in intensive care unit after three weeks. Maternal mortality ratio was 5.6%. Fifty five percent women had induction of ovulation with Clomiphene, while none had In Vitro Fertilization (IVF) or Intracytoplasmic Insemination (ICSI) or received gonadotrophins. Fifteen sets of triplets were delivered abdominally. Mean birth weights of 1st, 2nd and 3rd triplet were 1651, 1640 and 1443 grams respectively. Five sets of triplets (27.8%) had more than 25% discordance for birth weight. The mean Apgar scores of the babies at 1 and 10 minutes after birth were 6.0 and 8.0, 5.6 and 7.5; and 5.2 and 7.0 respectively. Of the 54 infants, 18 required Neonatal Intensive Care Unit (NICU) admission and 14 were admitted in nursery. Two died shortly after birth. Total perinatal mortalities were 13 including 4 cases of intra-uterine demise. Three babies suffered from jaundice, 7 had sepsis and 8 had respiratory distress syndrome. Triplet gestation had a high rate of fetomaternal complications. Majority had history of assisted conception. (author)

  5. Suppression of self-interstitials in silicon during ion implantation via in-situ photoexcitation

    International Nuclear Information System (INIS)

    Ravi, J.; Erokhin, Yu.; Christensen, K.; Rozgonyi, G.A.; Patnaik, B.K.; White, C.W.

    1995-02-01

    The influence of in-situ photoexcitation during low temperature implantation on self-interstitial agglomeration following annealing has been investigated using transmission electron microscopy (TEM). A reduction in the level of as-implanted damage determined by RBS and TEM occurs athermally during 150 keV self-ion implantation. The damage reduction following a 300 C anneal suggests that it is mostly divacancy related. Subsequent thermal annealing at 800 C resulted in the formation of (311) rod like defects or dislocation loops for samples with and without in-situ photoexcitation, respectively. Estimation of the number of self-interstitials bound by these defects in the sample without in-situ photoexcitation corresponds to the implanted dose; whereas for the in-situ photoexcitation sample a suppression of ∼2 orders in magnitude is found. The kinetics of the athermal annealing process are discussed within the framework of either a recombination enhanced defect reaction mechanism, or a charge state enhanced defect migration and Coulomb interaction

  6. Proton and hydride affinities in excited states: magnitude reversals in proton and hydride affinities between the lowest singlet and triplet states of annulenyl and benzannulenyl anions and cations

    DEFF Research Database (Denmark)

    Rosenberg, Martin; Ottosson, Henrik; Kilså, Kristine

    2010-01-01

    electron counting rules for aromaticity in the two states. Using quantum chemical calculations at the G3(MP2)//(U)B3LYP/6-311+G(d,p) level we have examined the validity of this hypothesis for eight proton and eight hydride addition reactions of anions and cations, respectively, of annulenyl...

  7. The use of dendrimers as high-performance shells for round-trip energy transfer: efficient trans-cis photoisomerization from an excited triplet state produced within a dendrimer shell.

    Science.gov (United States)

    Miura, Yousuke; Momotake, Atsuya; Takeuchi, Keiichirou; Arai, Tatsuo

    2011-01-01

    A series of stilbene-cored poly(benzyl ether) dendrimers with benzophenone peripheries were synthesized and their photophysical and photochemical properties were studied. Fluorescence studies revealed that singlet-singlet energy transfer (SSET) from the stilbene core to the benzophenone units took place efficiently in dendrimers of all generations. Similarly, phosphorescence and time-resolved spectroscopic measurements indicated efficient triplet-triplet energy transfer (TTET) from the benzophenone periphery to the stilbene core. Upon excitation at 310 nm, the stilbene core isomerizes via an energy round trip within the dendrimer shell. The quantum yields for the energy round trip (Φ(ERT)), defined as the product of the quantum yields of SSET, intersystem crossing, and TTET (Φ(ERT) = Φ(SS)Φ(isc)Φ(TT)), were extremely high for all generations--99%, 95% and 94% for G1, G2, and G3, respectively--which means that the excitation energy of the dendrimer core was transferred to the dendrimer periphery and back to the core almost quantitatively. The quantum yield for photoisomerization of G1-G3 via an energy round trip was higher than for other stilbene-cored dendrimers, which mainly isomerize from the excited singlet state. Photostability in the dendrimers was also demonstrated and discussed.

  8. Stability of singlet and triplet trions in carbon nanotubes

    International Nuclear Information System (INIS)

    Ronnow, Troels F.; Pedersen, Thomas G.; Cornean, Horia D.

    2009-01-01

    We investigate singlet and triplet trion states in semiconducting carbon nanotubes using a one-dimensional model. It is concluded that singlet trion states in bind up to 13.6% stronger than exciton states, and that they lower the optical transition energy with up to 50% of the tight binding band gap energy.

  9. Stability of singlet and triplet trions in carbon nanotubes

    DEFF Research Database (Denmark)

    Rønnow, Troels Frimodt; Pedersen, Thomas Garm; Cornean, Horia

    2009-01-01

    We investigate singlet and triplet trion states in semiconducting carbon nanotubes using a one-dimensional model. It is concluded that singlet trion states in bind up to 13.5% stronger than exciton states, and that they lower the optical transition energy with up to 50% of the tight binding band...

  10. 'Blueberry' Triplets Born in Rock

    Science.gov (United States)

    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.

  11. Convergent modulation of singlet and triplet excited states of phosphine-oxide hosts through the management of molecular structure and functional-group linkages for low-voltage-driven electrophosphorescence.

    Science.gov (United States)

    Han, Chunmiao; Zhang, Zhensong; Xu, Hui; Xie, Guohua; Li, Jing; Zhao, Yi; Deng, Zhaopeng; Liu, Shiyong; Yan, Pengfei

    2013-01-02

    The controllable tuning of the excited states in a series of phosphine-oxide hosts (DPExPOCzn) was realized through introducing carbazolyl and diphenylphosphine-oxide (DPPO) moieties to adjust the frontier molecular orbitals, molecular rigidity, and the location of the triplet excited states by suppressing the intramolecular interplay of the combined multi-insulating and meso linkage. On increasing the number of substituents, simultaneous lowering of the first singlet energy levels (S(1)) and raising of the first triplet energy levels (T(1), about 3.0 eV) were achieved. The former change was mainly due to the contribution of the carbazolyl group to the HOMOs and the extended conjugation. The latter change was due to an enhanced molecular rigidity and the shift of the T(1) states from the diphenylether group to the carbazolyl moieties. This kind of convergent modulation of excited states not only facilitates the exothermic energy transfer to the dopants in phosphorescent organic light-emitting diodes (PHOLEDs), but also realizes the fine-tuning of electrical properties to achieve the balanced carrier injection and transportation in the emitting layers. As the result, the favorable performance of blue-light-emitting PHOLEDs was demonstrated, including much-lower driving voltages of 2.6 V for onset and 3.0 V at 100 cd m(-2), as well as a remarkably improved E.Q.E. of 12.6%. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Benchmarking triplet-triplet annihilation photon upconversion schemes.

    Science.gov (United States)

    Gertsen, Anders S; Koerstz, Mads; Mikkelsen, Kurt V

    2018-05-07

    Photon upconversion facilitated by triplet-triplet annihilation in molecular systems is a promising path toward utilization of sub bandgap photons in photovoltaic devices. Prior to the challenging synthesis of new molecules, quantum chemical computations can aid the design process and provide suggestions for new and optimal systems. Here, we benchmark time-dependent density functional methods by their ability to describe relevant photophysical quantities of a range of different types of sensitizer/annihilator pairs to provide guidelines for future computational studies of potential new pairs. Using meta-GGA, hybrid, and range-separated hybrid functionals, we find that the hybrid functionals B3LYP and PBE0 (incorporating low to medium fractions of exact exchange of 20% and 25%, respectively) describe singlet absorptions the best, while triplet energetics are best described by the meta-GGA functionals M06-L and M11-L (incorporating no exact exchange), respectively. Furthermore, we find that the Tamm-Dancoff approximation of time-dependent density functional theory in general does not improve the description of neither singlet nor triplet energies of sensitizer/annihilator pairs.

  13. cyclo-addition reaction of triplet carbonyl compounds to substituted ...

    Indian Academy of Sciences (India)

    Unknown

    cited state energy of the olefin must be higher than that of the ketone so that ... the first singlet and triplet1,3 (n, π*) excited state of the carbonyl compounds.3,4 ... of the oxetane via carbon–carbon and carbon–oxygen attacks. They found the ...

  14. Photoexcitation circular dichroism in chiral molecules

    Science.gov (United States)

    Beaulieu, S.; Comby, A.; Descamps, D.; Fabre, B.; Garcia, G. A.; Géneaux, R.; Harvey, A. G.; Légaré, F.; Mašín, Z.; Nahon, L.; Ordonez, A. F.; Petit, S.; Pons, B.; Mairesse, Y.; Smirnova, O.; Blanchet, V.

    2018-05-01

    Chiral effects appear in a wide variety of natural phenomena and are of fundamental importance in science, from particle physics to metamaterials. The standard technique of chiral discrimination—photoabsorption circular dichroism—relies on the magnetic properties of a chiral medium and yields an extremely weak chiral response. Here, we propose and demonstrate an orders of magnitude more sensitive type of circular dichroism in neutral molecules: photoexcitation circular dichroism. This technique does not rely on weak magnetic effects, but takes advantage of the coherent helical motion of bound electrons excited by ultrashort circularly polarized light. It results in an ultrafast chiral response and the efficient excitation of a macroscopic chiral density in an initially isotropic ensemble of randomly oriented chiral molecules. We probe this excitation using linearly polarized laser pulses, without the aid of further chiral interactions. Our time-resolved study of vibronic chiral dynamics opens a way to the efficient initiation, control and monitoring of chiral chemical change in neutral molecules at the level of electrons.

  15. Effective photoexcitation cross section of 115In(γ,γ′115mIn from photoactivation data

    Directory of Open Access Journals (Sweden)

    Versteegen M.

    2016-01-01

    Full Text Available Photoexcitation yields of the 115mIn metastable state were measured with Bremsstrahlung γ beams over a range of endpoint energies between 4.5 and 18 MeV. An effective cross section of the 115In(γ,γ′115mIn photoexcitation cross section was determinedto reproduce the data. This cross section is built from a cross section calculated with the TALYS code, to which an enhancement is added at about 8.5 MeV.

  16. Precision spectroscopy with ultracold 87Rb2 triplet molecules

    International Nuclear Information System (INIS)

    Strauss, Christoph

    2011-01-01

    In this thesis I report precision spectroscopy with ultracold 87 Rb 2 triplet molecules where we use lasers to couple the states in different molecular potentials. We study in detail states of the a 3 sum + u and (1) 3 sum + g potentials. These states are of great importance for transferring weakly bound molecules to the ro-vibrational triplet ground state via states of the excited potential. As most experiments start from molecules in their X 1 sum + g ground state, the triplet states were hard to access via dipole transitions and remained largely unexplored. The measurements presented in this thesis are the first detailed study of diatomic 87 Rb 2 molecules in these states. Our experiments start with an ultracold cloud of 87 Rb atoms. We then load this cloud into an optical lattice where we use a magnetic Feshbach resonance at 1007.4 G to perform a Feshbach association. After we have removed all unbound atoms, we end up with a pure sample of weakly bound Feshbach molecules inside the optical lattice. The optical lattice prevents these molecules from colliding with each other which results in molecular lifetimes on the order of a few hundred milliseconds. In the first set of experiments, we use a laser coupling the Feshbach state to the excited (1) 3 sum + g triplet state to map out its low-lying vibrational (v = 0.. 15), rotational, hyperfine, and Zeeman structure. The experimental results are in good agreement with calculations done by Marius Lysebo and Prof. Leif Veseth. We then map out in detail the vibrational, rotational, hyperfine, and Zeeman structure of the a 3 sum + u triplet ground state using dark state spectroscopy with levels in the (1) 3 sum + g potential as an intermediate state. In this scheme we are able to access molecules in triplet states because our Feshbach state has strong triplet character. Interestingly, it happens that some deeply bound states which belong to the X 1 sum + g potential are close to levels in the a 3 sum + u potential. In

  17. Absence of Intramolecular Singlet Fission in Pentacene-Perylenediimide Heterodimers: The Role of Charge Transfer State.

    Science.gov (United States)

    Wang, Long; Wu, Yishi; Chen, Jianwei; Wang, Lanfen; Liu, Yanping; Yu, Zhenyi; Yao, Jiannian; Fu, Hongbing

    2017-11-16

    A new class of donor-acceptor heterodimers based on two singlet fission (SF)-active chromophores, i.e., pentacene (Pc) and perylenediimide (PDI), was developed to investigate the role of charge transfer (CT) state on the excitonic dynamics. The CT state is efficiently generated upon photoexcitation. However, the resulting CT state decays to different energy states depending on the energy levels of the CT state. It undergoes extremely rapid deactivation to the ground state in polar CH 2 Cl 2 , whereas it undergoes transformation to a Pc triplet in nonpolar toluene. The efficient triplet generation in toluene is not due to SF but CT-mediated intersystem crossing. In light of the energy landscape, it is suggested that the deep energy level of the CT state relative to that of the triplet pair state makes the CT state actually serve as a trap state that cannot undergoes an intramolecular singlet fission process. These results provide guidance for the design of SF materials and highlight the requisite for more widely applicable design principles.

  18. Homo- or Hetero- Triplet-Triplet Annihilation? A Case Study with Perylene-Bodipy Dyads/Triads

    KAUST Repository

    Cui, Xiaoneng

    2017-07-06

    The photophysical processes of intramolecular ‘ping-pong’ energy transfers in the iodinated reference dyad BDP-I2-Py, as well as the uniodinated dyad BDP-Py and triad BDP-2Py, were studied. For BDP-I2-Py, a forward Förster resonance energy transfer (FRET) from the perylene (Py) unit to the diiodoBDP unit (7 ps) and a backward triplet energy transfer (TTET, 3 ns) from the diiodoBDP unit to the Py unit were observed. For the BDP-Py and BDP-2Py systems, a FRET (5 ~ 8 ps) and a photo-induced electron transfer (PET) (1-1.5 ns) were observed in acetonitrile. The uniodinated dyad and triad were used as the triplet energy acceptor and emitter for a TTA upconversion with palladium tetraphenyltetrabenzoporphyrin as the triplet photosensitizer. A maximum upconversion quantum yield of 12.6 % was measured. Given that the dyad (BDP-Py) contains one BDP unit and one Py unit, while the triad (BDP-2Py) contains two Py units and one BDP unit, and based on the results from steady-state femtosecond and nanosecond transient optical spectroscopies, it is concluded that neither intramolecular homo- triplet-triplet annihilation (TTA) nor intramolecular hetero-TTA is possible during a TTA upconversion for those upconversion systems.

  19. Infrared photoexcitation spectroscopy of conducting polymer and C60 composites: direct evidence of photo-induced electron transfer

    NARCIS (Netherlands)

    Lee, Kwanghee; Janssen, R.A.J.; Sariciftci, N.S.; Heeger, A.J.

    1994-01-01

    We report direct spectral evidence of photoinduced electron transfer from the excited state of conducting polymer onto C60 by infrared photoexcitation spectroscopy, from 0.01 eV (100 cm-1) to 1.3 eV (11,000 cm-1). The photoinduced absorption spectra of poly(3-octylthiophene) (P30T) and

  20. Bright triplet excitons in caesium lead halide perovskites

    Science.gov (United States)

    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.

  1. Robustness of the charge-ordered phases in IrTe2 against photoexcitation

    Science.gov (United States)

    Monney, C.; Schuler, A.; Jaouen, T.; Mottas, M.-L.; Wolf, Th.; Merz, M.; Muntwiler, M.; Castiglioni, L.; Aebi, P.; Weber, F.; Hengsberger, M.

    2018-02-01

    We present a time-resolved angle-resolved photoelectron spectroscopy study of IrTe2, which undergoes two first-order structural and charge-ordered phase transitions on cooling below 270 K and below 180 K. The possibility of inducing a phase transition by photoexcitation with near-infrared femtosecond pulses is investigated in the charge-ordered phases. We observe changes of the spectral function occurring within a few hundreds of femtoseconds and persisting up to several picoseconds, which we interpret as a partial photoinduced phase transition (PIPT). The necessary time for photoinducing these spectral changes increases with increasing photoexcitation density and reaches time scales longer than the rise time of the transient electronic temperature. We conclude that the PIPT is driven by a transient increase of the lattice temperature following the energy transfer from the electrons. However, the photoinduced changes of the spectral function are small, which indicates that the low-temperature phase is particularly robust against photoexcitation. We suggest that the system might be trapped in an out-of-equilibrium state, for which only a partial structural transition is achieved.

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

    Energy Technology Data Exchange (ETDEWEB)

    Sreearunothai, P.; Miller, J.; Estrada, A.; Asaoka, S.; Kowalczyk, M.; Jang, S.; Cook, A.R.; Preses, J.M.

    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 triplet 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.

  3. Femtosecond Dynamics of Photoexcited C60 Films.

    Science.gov (United States)

    Causa', Martina; Ramirez, Ivan; Martinez Hardigree, Josue F; Riede, Moritz; Banerji, Natalie

    2018-04-19

    The well known organic semiconductor C 60 is attracting renewed attention due to its centimeter-long electron diffusion length and high performance of solar cells containing 95% fullerene, yet its photophysical properties remain poorly understood. We elucidate the dynamics of Frenkel and intermolecular (inter-C 60 ) charge-transfer (CT) excitons in neat and diluted C 60 films from high-quality femtosecond transient absorption (TA) measurements performed at low fluences and free from oxygen or pump-induced photodimerization. We find from preferential excitation of either species that the CT excitons give rise to a strong electro-absorption (EA) signal but are extremely short-lived. The Frenkel exciton relaxation and triplet yield strongly depend on the C 60 aggregation. Finally, TA measurements on full devices with applied electric field allow us to optically monitor the dissociation of CT excitons into free charges for the first time and to demonstrate the influence of cluster size on the spectral signature of the C 60 anion.

  4. Triplet-triplet energy transfer from chlorophylls to carotenoids in two antenna complexes from dinoflagellate Amphidinium carterae

    Czech Academy of Sciences Publication Activity Database

    Kvíčalová, Z.; Alster, J.; Hofmann, E.; Khoroshyy, P.; Litvín, Radek; Bína, David; Polívka, Tomáš; Pšenčík, J.

    2016-01-01

    Roč. 1857, č. 4 (2016), s. 341-349 ISSN 0005-2728 R&D Projects: GA ČR GBP501/12/G055 Institutional support: RVO:60077344 Keywords : Dinoflagellate * Chlorophyll * Carotenoid * Triplet state Subject RIV: BO - Biophysics Impact factor: 4.932, year: 2016

  5. Extrinsic photoresponse enhancement under additional intrinsic photoexcitation in organic semiconductors

    Energy Technology Data Exchange (ETDEWEB)

    Kounavis, P., E-mail: pkounavis@upatras.gr [Department of Electrical and Computer Engineering, School of Engineering, University of Patras, 26504 Patras (Greece)

    2016-06-28

    Dual light beam photoresponse experiments are employed to explore the photoresponse under simultaneous extrinsic and intrinsic photoexcitation of organic semiconductors. The photoresponse of a red modulated light extrinsic photoexcitation is found that can be significantly enhanced under an additional blue bias-light intrinsic photoexcitation in two terminal pentacene films on glass substrates. From the frequency resolved photoresponse, it is deduced that the phenomenon of photoresponse enhancement can be attributed to an increase in the extrinsic photogeneration rate of the red modulated light and/or an improvement of the drift velocity of carriers under an additional blue light intrinsic photoexcitation. The possible predominant extrinsic photogeneration mechanism, which can be compatible with the observed dependence of the photoresponse enhancement on the frequency and on the light intensities of the red and blue light excitation, is the singlet exciton dissociation through electron transfer to acceptor-like traps. Moreover, an improvement in the drift velocity of carriers traversing grain boundaries with potential energy barriers, which may be reduced by trapping of minority carriers created from the intrinsic photoexcitation, may partly contribute to the photoresponse enhancement.

  6. Extrinsic photoresponse enhancement under additional intrinsic photoexcitation in organic semiconductors

    International Nuclear Information System (INIS)

    Kounavis, P.

    2016-01-01

    Dual light beam photoresponse experiments are employed to explore the photoresponse under simultaneous extrinsic and intrinsic photoexcitation of organic semiconductors. The photoresponse of a red modulated light extrinsic photoexcitation is found that can be significantly enhanced under an additional blue bias-light intrinsic photoexcitation in two terminal pentacene films on glass substrates. From the frequency resolved photoresponse, it is deduced that the phenomenon of photoresponse enhancement can be attributed to an increase in the extrinsic photogeneration rate of the red modulated light and/or an improvement of the drift velocity of carriers under an additional blue light intrinsic photoexcitation. The possible predominant extrinsic photogeneration mechanism, which can be compatible with the observed dependence of the photoresponse enhancement on the frequency and on the light intensities of the red and blue light excitation, is the singlet exciton dissociation through electron transfer to acceptor-like traps. Moreover, an improvement in the drift velocity of carriers traversing grain boundaries with potential energy barriers, which may be reduced by trapping of minority carriers created from the intrinsic photoexcitation, may partly contribute to the photoresponse enhancement.

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

    Science.gov (United States)

    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.

  8. Triplet Focusing for Recirculating Linear Muon Accelerators

    CERN Document Server

    Keil, Eberhard

    2001-01-01

    Focusing by symmetrical triplets is studied for the linear accelerator lattices in recirculating muon accelerators with several passes where the ratio of final to initial muon energy is about four. Triplet and FODO lattices are compared. At similar acceptance, triplet lattices have straight sections for the RF cavities that are about twice as long as in FODO lat-tices. For the same energy gain, the total lengths of the linear accelerators with triplet lattices are about the same as of those with FODO lattices.

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

    KAUST Repository

    Samanta, Pralok Kumar; Kim, Dongwook; Coropceanu, Veaceslav; Bredas, Jean-Luc

    2017-01-01

    The rates for up-conversion intersystem crossing (UISC) from the T1 state to the S1 state are calculated for a series of organic emitters with an emphasis on thermally activated delayed fluorescence (TADF) materials. Both the spin-orbit coupling

  10. LHC Inner Triplet Powering Strategy

    CERN Document Server

    Bordry, Frederick

    2001-01-01

    In order to achieve a luminosity in excess of 10**34 cm**-2s**-1 at the Large Hadron Collider (LHC), special high gradient quadrupoles are required for the final focusing triplets. These low-b triplets, located in the four experimental insertions (ATLAS, CMS, ALICE, LHC-B), consist of four wide-aperture superconducting magnets: two outer quadrupoles, Q1 and Q3, with a maximum current of 7 kA and a central one divided into two identical magnets, Q2a and Q2b, with a maximum current of 11.5 kA. To optimise the powering of these mixed quadrupoles, it was decided to use two nested high-current power converters : [8kA, 8V] and [6kA, 8V]. This paper presents the consequence of the interaction between the two galvanically coupled circuits. A control strategy, using two independent, standard, LHC digital controllers, to decouple the two systems is proposed and described. The converter protection during the discharge of the magnet energy due to quenches or interlocks of the magnets are discussed. Simulation and experim...

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

    KAUST Repository

    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

    2017-01-01

    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

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

    KAUST Repository

    Freeman, David M. E.

    2017-06-09

    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

  13. Stimulated emission of photoexcited polarized electrons from GaAs

    International Nuclear Information System (INIS)

    Derbenev, Ya.S.; Melikyan, R.A.

    1986-01-01

    The influence of electric field on the emission of photoexcited polarized electrons is investigated. The thermalization of excited electrons is shown to be prevented at the field intensity in semiconductor of about 3 kV/cm. As a consequence the quantum yield grows up to unity. With the increase of the output energy of electrons the effective operation time of photocathode also increases

  14. System for illuminating a region for isotopically selective photoexcitation

    International Nuclear Information System (INIS)

    Debaryshe, P.G.; Janes, G.S.; Levy, R.H.; Lindenmeier, C.W.

    1979-01-01

    A method is described to improve laser beam utilization in isotope separation techniques (using laser induced isotopically selective photoexcitation) by increasing the probability of photon absorption without extreme beam propagation lengths. For this purpose an optical reflection system has been designed for illuminating substantially all of three-dimensional space of a transversely flowing vapor with multiple traversals of a beam of radiation. (UK)

  15. Density-dependent electron scattering in photoexcited GaAs

    DEFF Research Database (Denmark)

    Mics, Zoltán; D'’Angio, Andrea; Jensen, Søren A.

    2013-01-01

    —In a series of systematic optical pump - terahertz probe experiments we study the density-dependent electron scattering rate in photoexcited GaAs in a large range of carrier densities. The electron scattering time decreases by as much as a factor of 4, from 320 to 60 fs, as the electron density...

  16. Photoexcitation dynamics in organic solar cell donor/acceptor system

    Energy Technology Data Exchange (ETDEWEB)

    Aarnio, H.

    2012-07-01

    In this work, photoinduced absorption techniques have been used in a number of ways to clarify the charge generation and recombination processes in two polymers used in organic solar cells, namely APFO3 and P3HT. Emphasis has been on identifying photoexcitations, modeling their dynamics and determining their lifetimes.

  17. Triplet exciton diffusion in organic semiconductors

    Energy Technology Data Exchange (ETDEWEB)

    Koehler, Anna [Department of Physics, University of Bayreuth (Germany)

    2010-07-01

    Efficient triplet exciton emission has allowed improved operation of organic light-emitting diodes (LEDs). To enhance the device performance, it is necessary to understand what governs the motion of triplet excitons through the organic semiconductor. We use a series of poly(p-phenylene)-type conjugated polymers and oligomers of variable degree of molecular distortion (i.e. polaron formation) and energetic disorder as model systems to study the Dexter-type triplet exciton diffusion in thin films. We show that triplet diffusion can be quantitatively described in the framework of a Holstein small polaron model (Marcus theory) that is extended to include contributions from energetic disorder. The model predicts a tunnelling process at low temperatures followed by a thermally activated hopping process above a transition temperature. In contrast to charge transfer, the activation energy required for triplet exciton transfer can be deduced from the optical spectra. We discuss the implications for device architecture.

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

    Science.gov (United States)

    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.

  19. Confinement sensitivity in quantum dot singlet-triplet relaxation

    Science.gov (United States)

    Wesslén, C. J.; Lindroth, E.

    2017-11-01

    Spin-orbit mediated phonon relaxation in a two-dimensional quantum dot is investigated using different confining potentials. Elliptical harmonic oscillator and cylindrical well results are compared to each other in the case of a two-electron GaAs quantum dot subjected to a tilted magnetic field. The lowest energy set of two-body singlet and triplet states are calculated including spin-orbit and magnetic effects. These are used to calculate the phonon induced transition rate from the excited triplet to the ground state singlet for magnetic fields up to where the states cross. The roll of the cubic Dresselhaus effect, which is found to be much more important than previously assumed, and the positioning of ‘spin hot-spots’ are discussed and relaxation rates for a few different systems are exhibited.

  20. Photophysics of Singlet and Triplet Intraligand Excited States in [ReCl(CO)(3)(1-(2-pyridyl)-imidazo[1,5-alpha]pyridine)] Complexes

    Czech Academy of Sciences Publication Activity Database

    Blanco-Rodríguez, A. M.; Kvapilová, Hana; Sýkora, Jan; Towrie, M.; Nervi, C.; Volpi, G.; Záliš, Stanislav; Vlček, Antonín

    2014-01-01

    Roč. 136, č. 16 (2014), s. 5963-5973 ISSN 0002-7863 R&D Projects: GA ČR GBP208/12/G016; GA MŠk LD11086 Institutional support: RVO:61388955 Keywords : CARBONYL-BIPYRIDINE COMPLEXES * RESOLVED INFRARED-SPECTROSCOPY * CHARGE-TRANSFER STATES Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 12.113, year: 2014

  1. Geometry and bonding in the ground and lowest triplet state of D{sub 6h} symmetric crenellated edged C{sub 6[3m(m-1)+1]}H{sub 6(2m-1)} (m = 2,..., 6) graphene hydrocarbon molecules

    Energy Technology Data Exchange (ETDEWEB)

    Philpott, Michael R., E-mail: philpott@imr.edu [Center for Computational Materials Science, Institute of Materials Science, Tohoku University, 2-1-1 Katahira, Aoba-ku, 980-8577 Sendai (Japan); Kawazoe, Yoshiyuki [Center for Computational Materials Science, Institute of Materials Science, Tohoku University, 2-1-1 Katahira, Aoba-ku, 980-8577 Sendai (Japan)

    2009-03-30

    Ab initio plane wave all valence electron based DFT calculations were used to explore the dichotomy of perimeter vs. interior in the electronic and geometric structure of the D{sub 6h} singlet ground state and D{sub 2h} lowest triplet state of planar graphene hydrocarbon molecules with crenellated (arm chair) edges and the general formula C{sub 6[3m(m-1)+1]} H{sub 6(2m-1)} where m = 2,...,6. The largest molecule C{sub 546}H{sub 66} was 4.78 nm across and contained 2250 valence electrons. These molecules are nominally 'fully benzenoid hydrocarbons'. However with increasing size, the core of central atoms abandoned any fully benzenoid geometry they had in small systems and organized into single layer graphite (graphene) structure. The perimeter atoms of the crenellation adopted a conjugated geometry with unequal bonds and between core and perimeter there were some C{sub 6} rings retaining remnants of aromatic sextet-type properties. Compared to a zigzag edge the crenellated edge conferred stability in all the systems studied as measured by the singlet homo-lumo level gap BG{sub 0} and the singlet-lowest triplet energy gap {Delta}E{sub ST}. For the largest crenellated system (m = 6) BG{sub 0} and {Delta}E{sub ST} were approximately 0.7 eV, larger in value than for similarly sized hexagonal graphenes with zigzag edges. Triplet states were identified for all the molecules in the series and in the case of the m = 2 molecule hexabenzocoronene C{sub 42}H{sub 18}, two conformations with D{sub 2h} symmetry were identified and compared to features on the triplet state potential energy surface of benzene.

  2. Directional phonon-assisted cascading of photoexcited carriers in stepped Inx(Al0.17Ga0.83)1-xAs/Al0.17Ga0.83As multiple quantum wells

    DEFF Research Database (Denmark)

    Machida, S.; Matsuo, M.; Fujiwara, K.

    2002-01-01

    Perpendicular motion of photoexcited electron and hole pairs assisted by phononscattering is investigated in a novel step-graded staircase heterostructure consisting of strained In-1(Al0.17Ga0.83)(1-x). As multiple quantum wells (QWs) with similar widths but five different x values by cw and time...... amplitude in the inter-mediate temperature range, These variations reveal that the photoexcited carriers directionally move from shallower to deeper QWs via phonon-assisted activation above the barrier hand edge state. The PL dynamics directly indicate the perpendicular flowing of photoexcited carriers...

  3. Potential energy and dipole moment surfaces of the triplet states of the O2(X3Σg-) - O2(X3Σg-,a1Δg,b1Σg+) complex.

    Science.gov (United States)

    Karman, Tijs; van der Avoird, Ad; Groenenboom, Gerrit C

    2017-08-28

    We compute four-dimensional diabatic potential energy surfaces and transition dipole moment surfaces of O 2 -O 2 , relevant for the theoretical description of collision-induced absorption in the forbidden X 3 Σ g -  → a 1 Δ g and X 3 Σ g -  → b 1 Σ g + bands at 7883 cm -1 and 13 122 cm -1 , respectively. We compute potentials at the multi-reference configuration interaction (MRCI) level and dipole surfaces at the MRCI and complete active space self-consistent field (CASSCF) levels of theory. Potentials and dipole surfaces are transformed to a diabatic basis using a recent multiple-property-based diabatization algorithm. We discuss the angular expansion of these surfaces, derive the symmetry constraints on the expansion coefficients, and present working equations for determining the expansion coefficients by numerical integration over the angles. We also present an interpolation scheme with exponential extrapolation to both short and large separations, which is used for representing the O 2 -O 2 distance dependence of the angular expansion coefficients. For the triplet ground state of the complex, the potential energy surface is in reasonable agreement with previous calculations, whereas global excited state potentials are reported here for the first time. The transition dipole moment surfaces are strongly dependent on the level of theory at which they are calculated, as is also shown here by benchmark calculations at high symmetry geometries. Therefore, ab initio calculations of the collision-induced absorption spectra cannot become quantitatively predictive unless more accurate transition dipole surfaces can be computed. This is left as an open question for method development in electronic structure theory. The calculated potential energy and transition dipole moment surfaces are employed in quantum dynamical calculations of collision-induced absorption spectra reported in Paper II [T. Karman et al., J. Chem. Phys. 147, 084307 (2017)].

  4. Distinct α subunit variations of the hypothalamic GABAA receptor triplets (αβγ are linked to hibernating state in hamsters

    Directory of Open Access Journals (Sweden)

    Alò Raffaella

    2010-09-01

    Full Text Available Abstract Background The structural arrangement of the γ-aminobutyric acid type A receptor (GABAAR is known to be crucial for the maintenance of cerebral-dependent homeostatic mechanisms during the promotion of highly adaptive neurophysiological events of the permissive hibernating rodent, i.e the Syrian golden hamster. In this study, in vitro quantitative autoradiography and in situ hybridization were assessed in major hypothalamic nuclei. Reverse Transcription Reaction-Polymerase chain reaction (RT-PCR tests were performed for specific GABAAR receptor subunit gene primers synthases of non-hibernating (NHIB and hibernating (HIB hamsters. Attempts were made to identify the type of αβγ subunit combinations operating during the switching ON/OFF of neuronal activities in some hypothalamic nuclei of hibernators. Results Both autoradiography and molecular analysis supplied distinct expression patterns of all α subunits considered as shown by a strong (p 1 ratio (over total α subunits considered in the present study in the medial preoptic area (MPOA and arcuate nucleus (Arc of NHIBs with respect to HIBs. At the same time α2 subunit levels proved to be typical of periventricular nucleus (Pe and Arc of HIB, while strong α4 expression levels were detected during awakening state in the key circadian hypothalamic station, i.e. the suprachiasmatic nucleus (Sch; 60%. Regarding the other two subunits (β and γ, elevated β3 and γ3 mRNAs levels mostly characterized MPOA of HIBs, while prevalently elevated expression concentrations of the same subunits were also typical of Sch, even though this time during the awakening state. In the case of Arc, notably elevated levels were obtained for β3 and γ2 during hibernating conditions. Conclusion We conclude that different αβγ subunits are operating as major elements either at the onset of torpor or during induction of the arousal state in the Syrian golden hamster. The identification of a brain regional

  5. Polaron pair mediated triplet generation in polymer/fullerene blends

    KAUST Repository

    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.

  6. Polaron pair mediated triplet generation in polymer/fullerene blends

    KAUST Repository

    Dimitrov, Stoichko D.

    2015-03-04

    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.

  7. Constructing level-2 phylogenetic networks from triplets

    OpenAIRE

    Iersel, Leo; Keijsper, J.C.M.; Kelk, Steven; Stougie, Leen; Hagen, F.; Boekhout, T.; Vingron, M.; Wong, L.

    2009-01-01

    htmlabstractJansson and Sung showed that, given a dense set of input triplets T (representing hypotheses about the local evolutionary relationships of triplets of taxa), it is possible to determine in polynomial time whether there exists a level-1 network consistent with T, and if so to construct such a network (Inferring a Level-1 Phylogenetic Network from a Dense Set of Rooted Triplets, Theoretical Computer Science, 363, pp. 60-68 (2006)). Here we extend this work by showing that this probl...

  8. Low-energy effective theory, unitarity, and nondecoupling behavior in a model with heavy Higgs-triplet fields

    International Nuclear Information System (INIS)

    Chivukula, R. Sekhar; Christensen, Neil D.; Simmons, Elizabeth H.

    2008-01-01

    We discuss the properties of a model incorporating both a scalar electroweak Higgs doublet and an electroweak Higgs triplet. We construct the low-energy effective theory for the light Higgs doublet in the limit of small (but nonzero) deviations in the ρ parameter from one, a limit in which the triplet states become heavy. For Δρ>0, perturbative unitarity of WW scattering breaks down at a scale inversely proportional to the renormalized vacuum expectation value of the triplet field (or, equivalently, inversely proportional to the square root of Δρ). This result imposes an upper limit on the mass scale of the heavy triplet bosons in a perturbative theory; we show that this upper bound is consistent with dimensional analysis in the low-energy effective theory. Recent articles have shown that the triplet bosons do not decouple, in the sense that deviations in the ρ parameter from one do not necessarily vanish at one-loop in the limit of large triplet mass. We clarify that, despite the nondecoupling behavior of the Higgs triplet, this model does not violate the decoupling theorem since it incorporates a large dimensionful coupling. Nonetheless, we show that if the triplet-Higgs boson masses are of order the grand unified theory scale, perturbative consistency of the theory requires the (properly renormalized) Higgs-triplet vacuum expectation value to be so small as to be irrelevant for electroweak phenomenology

  9. Taking snapshots of photoexcited molecules in disordered media using pulsed synchrotron x-rays

    International Nuclear Information System (INIS)

    Chen, L.X.

    2004-01-01

    Photoexcited molecules are quintessential reactants in photochemistry. Structures of these photoexcited molecules in disordered media in which a majority of photochemical reactions take place remained elusive for decades owing to a lack of suitable X-ray sources, despite their importance in understanding fundamental aspects in photochemistry. As new pulsed X-ray sources become available, short-lived excited-state molecular structures in disordered media can now be captured by using laser-pulse pump, X-ray pulse-probe techniques of third-generation synchrotron sources with time resolutions of 30-100 ps, as demonstrated by examples in this review. These studies provide unprecedented information on structural origins of molecular properties in the excited states. By using other ultrafast X-ray facilities that will be completed in the near future, time-resolution for the excited-state structure measurements should reach the femtosecond timescales, which will make 'molecular movies' of bond breaking or formation, and vibrational relaxation, a reality.

  10. Photoprotection in the antenna complexes of photosystem II: role of individual xanthophylls in chlorophyll triplet quenching.

    Science.gov (United States)

    Mozzo, Milena; Dall'Osto, Luca; Hienerwadel, Rainer; Bassi, Roberto; Croce, Roberta

    2008-03-07

    In this work the photoprotective role of all xanthophylls in LHCII, Lhcb4, and Lhcb5 is investigated by laser-induced Triplet-minus-Singlet (TmS) spectroscopy. The comparison of native LHCII trimeric complexes with different carotenoid composition shows that the xanthophylls in sites V1 and N1 do not directly contribute to the chlorophyll triplet quenching. The largest part of the triplets is quenched by the lutein bound in site L1, which is located in close proximity to the chlorophylls responsible for the low energy state of the complex. The lutein in the L2 site is also active in triplet quenching, and it shows a longer triplet lifetime than the lutein in the L1 site. This lifetime difference depends on the occupancy of the N1 binding site, where neoxanthin acts as an oxygen barrier, limiting the access of O(2) to the inner domain of the Lhc complex, thereby strongly contributing to the photostability. The carotenoid triplet decay of monomeric Lhcb1, Lhcb4, and Lhcb5 is mono-exponential, with shorter lifetimes than observed for trimeric LHCII, suggesting that their inner domains are more accessible for O(2). As for trimeric LHCII, only the xanthophylls in sites L1 and L2 are active in triplet quenching. Although the chlorophyll to carotenoid triplet transfer is efficient (95%) in all complexes, it is not perfect, leaving 5% of the chlorophyll triplets unquenched. This effect appears to be intrinsically related to the molecular organization of the Lhcb proteins.

  11. Heats of Formation of Triplet Ethylene, Ethylidene, and Acetylene

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen, M.T.; Matus, M.H.; Lester Jr, W.A.; Dixon, David A.

    2007-06-28

    Heats of formation of the lowest triplet state of ethylene and the ground triplet state of ethylidene have been predicted by high level electronic structure calculations. Total atomization energies obtained from coupled-cluster CCSD(T) energies extrapolated to the complete basis set limit using correlation consistent basis sets (CBS), plus additional corrections predict the following heats of formation in kcal/mol: Delta H0f(C2H4,3A1) = 80.1 at 0 K and 78.5 at 298 K, and Delta H0f(CH3CH,3A") = 86.8 at 0 K and 85.1 at 298 K, with an error of less than +-1.0 kcal/mol. The vertical and adiabatic singlet-triplet separation energies of ethylene were calculated as Delta ES-T,vert = 104.1 and Delta ES-T,adia = 65.8 kcal/mol. These results are in excellent agreement with recent quantum Monte Carlo (DMC) values of 103.5 +- 0.3 and 66.4 +- 0.3 kcal/mol. Both sets of computational values differ from the experimental estimate of 58 +- 3 kcal/mol for the adiabatic splitting. The computed singlet-triplet gap at 0 K for acetylene is Delta ES-T,adia(C2H2) = 90.5 kcal/mol, which is in notable disagreement with the experimental value of 82.6 kcal/mol. The heat of formation of the triplet is Delta H0f(C2H2,3B2) = 145.3 kcal/mol. There is a systematic underestimation of the singlet-triplet gaps in recent photodecomposition experiments by ~;;7 to 8 kcal/mol. For vinylidene, we predict Delta H0f(H2CC,1A1) = 98.8 kcal/mol at 298 K (exptl. 100.3 +- 4.0), Delta H0f(H2CC,3B2) = 146.2 at 298 K, and an energy gap Delta ES-T-adia(H2CC) = 47.7 kcal/mol.

  12. Dynamics of photoexcited quasiparticles in heavy electron compounds

    International Nuclear Information System (INIS)

    Demsar, Jure; Sarrao, John L; Taylor, Antoinette J

    2006-01-01

    Femtosecond real-time spectroscopy is an emerging new tool for studying low energy electronic structure in correlated electron systems. Motivated by recent advances in understanding the nature of relaxation phenomena in various correlated electron systems (superconductors, density wave systems) the technique has been applied to heavy electron compounds in comparison with their non-magnetic counterparts. While the dynamics in their non-magnetic analogues are similar to the dynamics observed in noble metals (only weak temperature dependences are observed) and can be treated with a simple two-temperature model, the photoexcited carrier dynamics in heavy electron systems show dramatic changes as a function of temperature and excitation level. In particular, below some characteristic temperature the relaxation rate starts to decrease, dropping by more than two orders of magnitude upon cooling down to liquid He temperatures. This behaviour has been consistently observed in various heavy fermion metals as well as Kondo insulators, and is believed to be quite general. In order to account for the experimental observations, two theoretical models have been proposed. The first treats the heavy electron systems as simple metals with very flat electron dispersion near the Fermi level. An electron-phonon thermalization scenario can account for the observed slowing down of the relaxation provided that there exists a mechanism for suppression of electron-phonon scattering when both the initial and final electronic states lie in the region of flat dispersion. An alternative scenario argues that the relaxation dynamics in heavy electron systems are governed by the Rothwarf-Taylor bottleneck, where the dynamics are governed by the presence of a narrow gap in the density of states near the Fermi level. The so-called hybridization gap results from hybridization between localized moments and the conduction electron background. Remarkable agreement with the model suggests that carrier

  13. TRIO (Triplet Ionospheric Observatory) Mission

    Science.gov (United States)

    Lee, D.; Seon, J.; Jin, H.; Kim, K.; Lee, J.; Jang, M.; Pak, S.; Kim, K.; Lin, R. P.; Parks, G. K.; Halekas, J. S.; Larson, D. E.; Eastwood, J. P.; Roelof, E. C.; Horbury, T. S.

    2009-12-01

    Triplets of identical cubesats will be built to carry out the following scientific objectives: i) multi-observations of ionospheric ENA (Energetic Neutral Atom) imaging, ii) ionospheric signature of suprathermal electrons and ions associated with auroral acceleration as well as electron microbursts, and iii) complementary measurements of magnetic fields for particle data. Each satellite, a cubesat for ion, neutral, electron, and magnetic fields (CINEMA), is equipped with a suprathermal electron, ion, neutral (STEIN) instrument and a 3-axis magnetometer of magnetoresistive sensors. TRIO is developed by three institutes: i) two CINEMA by Kyung Hee University (KHU) under the WCU program, ii) one CINEMA by UC Berkeley under the NSF support, and iii) three magnetometers by Imperial College, respectively. Multi-spacecraft observations in the STEIN instruments will provide i) stereo ENA imaging with a wide angle in local times, which are sensitive to the evolution of ring current phase space distributions, ii) suprathermal electron measurements with narrow spacings, which reveal the differential signature of accelerated electrons driven by Alfven waves and/or double layer formation in the ionosphere between the acceleration region and the aurora, and iii) suprathermal ion precipitation when the storm-time ring current appears. In addition, multi-spacecraft magnetic field measurements in low earth orbits will allow the tracking of the phase fronts of ULF waves, FTEs, and quasi-periodic reconnection events between ground-based magnetometer data and upstream satellite data.

  14. Jahn-Teller distortion in the phosphorescent excited state of three-coordinate Au(I) phosphine complexes.

    Science.gov (United States)

    Barakat, Khaldoon A; Cundari, Thomas R; Omary, Mohammad A

    2003-11-26

    DFT calculations were used to optimize the phosphorescent excited state of three-coordinate [Au(PR3)3]+ complexes. The results indicate that the complexes rearrange from their singlet ground-state trigonal planar geometry to a T-shape in the lowest triplet luminescent excited state. The optimized structure of the exciton contradicts the structure predicted based on the AuP bonding properties of the ground-state HOMO and LUMO. The rearrangement to T-shape is a Jahn-Teller distortion because an electron is taken from the degenerate e' (5dxy, 5dx2-y2) orbital upon photoexcitation of the ground-state D3h complex. The calculated UV absorption and visible emission energies are consistent with the experimental data and explain the large Stokes' shifts while such correlations are not possible in optimized models that constrained the exciton to the ground-state trigonal geometry.

  15. Skirting terahertz waves in a photo-excited nanoslit structure

    Energy Technology Data Exchange (ETDEWEB)

    Shalaby, Mostafa, E-mail: mostafa.shalaby@psi.ch, E-mail: thomas.feurer@iap.unibe.ch [INRS-EMT, Varennes, Quebec J3X 1S2 (Canada); SwissFEL, Paul Scherrer Institut, Villigen 5232 (Switzerland); Fabiańska, Justyna; Feurer, Thomas, E-mail: mostafa.shalaby@psi.ch, E-mail: thomas.feurer@iap.unibe.ch [Institute of Applied Physics, University of Bern, Sidlerstrasse 5, CH-3012 Bern (Switzerland); Peccianti, Marco [INRS-EMT, Varennes, Quebec J3X 1S2 (Canada); Department of Physics and Astronomy, University of Sussex, Pevensey Building II, 3A8, Falmer, Brighton BN1 9QH (United Kingdom); Ozturk, Yavuz; Vidal, Francois; Morandotti, Roberto [INRS-EMT, Varennes, Quebec J3X 1S2 (Canada); Sigg, Hans [LMN, Paul Scherrer Institut, Villigen 5232 (Switzerland)

    2014-04-28

    Terahertz fields can be dramatically enhanced as they propagate through nanometer-sized slits. The enhancement is mediated by a significant accumulation of the induced surface charges on the surrounding metal. This enhancement is shown here to be dynamically modulated while the nanoslits are gradually shunted using a copropagating optical beam. The terahertz fields are found to skirt the nanoscale photo-excited region underneath the slits, scattering to the far field and rigorously mapping the near field.

  16. Photoexcitations in a 1D manganite model: From quasiclassical light absorption to quasiparticle relaxations

    Science.gov (United States)

    Köhler, T.; Schumann, O.; Biebl, F.; Kramer, S.; Kehrein, S.; Manmana, S.; Rajpurohit, S.; Sotoudeh, M.; Blöchl, P.

    We investigate 1D correlated systems following a photoexcitation by combining ab-initio methods, time-dependent matrix product state (MPS) approaches, analytical insights from linearized quantum Boltzmann equations (LBE), and molecular dynamics (MD) simulations to describe the dynamics on different time scales ranging from femto- up to nanoseconds. This is done for manganite systems in the material class Pr1-xCaxMnO3. We derive 1D ab-initio model Hamiltonians for which we compute the ground states at different values of the doping using MD simulations. At half doping, we obtain a magnetic microstructure of alternating dimers from which we derive a 1D Hubbard-type model. The dynamics is analyzed concerning the formation and lifetime of such quasiparticles via a LBE. We find that the magnetic microstructure strongly enhances the lifetime of the excitations. In this way, our work constitutes a first step to building a unifying theoretical framework for the description of photoexcitations in strongly correlated materials over a wide range of time scales, capable of making predictions for ongoing experiments investigating pump-probe situations and unconventional photovoltaics. Financial support from the Deutsche Forschungsgemeinschaft (DFG) through SFB/CRC1073 (Projects B03 and C03) is gratefully acknowledged.

  17. Sensitized Triplet Formation of Chlorophyll-A and beta-Carotene

    DEFF Research Database (Denmark)

    Jensen, Nina Mejlhede; Wilbrandt, Robert Walter; Pagsberg, Palle Bjørn

    1980-01-01

    The naphthalene-sensitized formation of triplet excited chlorophyll-a (Chl-a) and all-transß-carotene has been studied by pulse radiolysis. The rate constants for transfer of triplet energy from naphthalene to Chl-a and all-transß-carotene in benzene at 25°C are (3.6 ± 0.6)·109M-1 s-1 and (10.7 ± 1.......2)·109M-1 s-1, respectively. The decays of the excited triplet states of naphthalene, Chl-a and all-transß-carotene all follow a mixed first-and second-order mechanism. The first-order rate constant for triplet decay is strongly dose dependent for naphthalene but only slightly dependent and independent...

  18. Selectivity and coherence for photoexcitation of atoms

    International Nuclear Information System (INIS)

    Dai Changjian

    1995-01-01

    The results of both analytic and numerical treatments of the four-level Schroedinger equation are displayed. Transition Probabilities to various states for the cases of on-resonance and off-resonance are calculated. Dependences of probability on time and on characteristics of laser fields are investigated. Selectivity and coherence of the interaction between monochromatic laser fields and isotopic atom are examined. The conditions under which the population inversion takes place derived from the analytic solutions are confirmed

  19. Ultrafast Terahertz Conductivity of Photoexcited Nanocrystalline Silicon

    DEFF Research Database (Denmark)

    Cooke, David; MacDonald, A. Nicole; Hryciw, Aaron

    2007-01-01

    The ultrafast transient ac conductivity of nanocrystalline silicon films is investigated using time-resolved terahertz spectroscopy. While epitaxial silicon on sapphire exhibits a free carrier Drude response, silicon nanocrystals embedded in glass show a response that is best described by a class...... in the silicon nanocrystal films is dominated by trapping at the Si/SiO2 interface states, occurring on a 1–100 ps time scale depending on particle size and hydrogen passivation......The ultrafast transient ac conductivity of nanocrystalline silicon films is investigated using time-resolved terahertz spectroscopy. While epitaxial silicon on sapphire exhibits a free carrier Drude response, silicon nanocrystals embedded in glass show a response that is best described...

  20. Dynamic correlation of photo-excited electrons: Anomalous levels induced by light–matter coupling

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, Xiankai [Shanghai Institute of Applied Physics, Chinese Academy of Sciences, P.O. Box 800-204, Shanghai 201800 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Huai, Ping, E-mail: huaiping@sinap.ac.cn [Shanghai Institute of Applied Physics, Chinese Academy of Sciences, P.O. Box 800-204, Shanghai 201800 (China); Song, Bo, E-mail: bosong@sinap.ac.cn [Shanghai Institute of Applied Physics, Chinese Academy of Sciences, P.O. Box 800-204, Shanghai 201800 (China)

    2014-04-01

    Nonlinear light–matter coupling plays an important role in many aspects of modern physics, such as spectroscopy, photo-induced phase transition, light-based devices, light-harvesting systems, light-directed reactions and bio-detection. However, excited states of electrons are still unclear for nano-structures and molecules in a light field. Our studies unexpectedly present that light can induce anomalous levels in the electronic structure of a donor–acceptor nanostructure with the help of the photo-excited electrons transferring dynamically between the donor and the acceptor. Furthermore, the physics underlying is revealed to be the photo-induced dynamical spin–flip correlation among electrons. These anomalous levels can significantly enhance the electron current through the nanostructure. These findings are expected to contribute greatly to the understanding of the photo-excited electrons with dynamic correlations, which provides a push to the development and application of techniques based on photosensitive molecules and nanostructures, such as light-triggered molecular devices, spectroscopic analysis, bio-molecule detection, and systems for solar energy conversion.

  1. Entanglement and Metrology with Singlet-Triplet Qubits

    Science.gov (United States)

    Shulman, Michael Dean

    Electron spins confined in semiconductor quantum dots are emerging as a promising system to study quantum information science and to perform sensitive metrology. Their weak interaction with the environment leads to long coherence times and robust storage for quantum information, and the intrinsic tunability of semiconductors allows for controllable operations, initialization, and readout of their quantum state. These spin qubits are also promising candidates for the building block for a scalable quantum information processor due to their prospects for scalability and miniaturization. However, several obstacles limit the performance of quantum information experiments in these systems. For example, the weak coupling to the environment makes inter-qubit operations challenging, and a fluctuating nuclear magnetic field limits the performance of single-qubit operations. The focus of this thesis will be several experiments which address some of the outstanding problems in semiconductor spin qubits, in particular, singlet-triplet (S-T0) qubits. We use these qubits to probe both the electric field and magnetic field noise that limit the performance of these qubits. The magnetic noise bath is probed with high bandwidth and precision using novel techniques borrowed from the field of Hamiltonian learning, which are effective due to the rapid control and readout available in S-T 0 qubits. These findings allow us to effectively undo the undesired effects of the fluctuating nuclear magnetic field by tracking them in real-time, and we demonstrate a 30-fold improvement in the coherence time T2*. We probe the voltage noise environment of the qubit using coherent qubit oscillations, which is partially enabled by control of the nuclear magnetic field. We find that the voltage noise bath is frequency-dependent, even at frequencies as high as 1MHz, and it shows surprising and, as of yet, unexplained temperature dependence. We leverage this knowledge of the voltage noise environment, the

  2. Photochemical studies of alkylammonium molybdates. Part 12. O→Mo charge-transfer triplet-states-initiated self-assembly to {Mo154} ring- and tube-molybdenum-blues

    Science.gov (United States)

    Yamase, T.; Prokop, P.; Arai, Y.

    2003-08-01

    The chemically induced dynamic electron-spin-polarization technique is employed in order to investigate the primary steps of the photoredox reaction between polyoxomolybdates and alkylammonium cations as both proton and electron-donors in solutions. An observation of emissive electron-spin-polarization signals of alkylamino radical cations for the photoredox reaction between polyoxomolybdates and alkylammonium cations in solutions reveals that the O→Mo ligand-to-metal charge-transfer triplet states are involved in the transfers of both proton and electron from alkylammonium cation to polyoxomolybdate anions. Prolonged photolysis of aqueous solutions containing [Mo36O112(H2O)16]8-, [iPrNH3]+, and LaCl3 at pH 1.0 leads to formation of two kinds of {Mo154} molybdenum-blues, [Mo28VMo126VIO462H28(H2O)70]·156.5H2O (1) and [iPrNH3]8 [Mo28VMo126VIO458H12(H2O)66]·127H2O (2), which were X-ray crystallographically characterized. The former exhibits the intact car-tire-shaped {Mo154} ring structure (with thickness of about 1.1 nm and with outer- and inner-rings of approximately 3.5- and 2.3-nm diameters, respectively) derived formally from the dehydrated cyclic heptamerization of four-electron reduced building blocks of {Mo22} (≡[Mo4VMo18VIO70H12(H2O)10]) with overall symmetry of D7d. The anion for the latter, [Mo28VMo126VIO458H12(H2O)66]8- (2a), exhibits a nanotube structure of {Mo154} rings, each inner ring of which contains a bis(μ-oxo)-linkaged [MoO2(μ-O)(μ-H2O)MoO2]2+ unit replacing one of seven [Mo(H2O)O2(μ-O)Mo(H2O)O2]2+linker units. The neighboring {Mo154} rings are connected by six Mo-O-Mo bridge between inner-rings consisting of 7 head- and 14 linkers-MoO6 octahedra for each.

  3. Fuzzy tricentric pharmacophore fingerprints. 1. Topological fuzzy pharmacophore triplets and adapted molecular similarity scoring schemes.

    Science.gov (United States)

    Bonachéra, Fanny; Parent, Benjamin; Barbosa, Frédérique; Froloff, Nicolas; Horvath, Dragos

    2006-01-01

    This paper introduces a novel molecular description--topological (2D) fuzzy pharmacophore triplets, 2D-FPT--using the number of interposed bonds as the measure of separation between the atoms representing pharmacophore types (hydrophobic, aromatic, hydrogen-bond donor and acceptor, cation, and anion). 2D-FPT features three key improvements with respect to the state-of-the-art pharmacophore fingerprints: (1) The first key novelty is fuzzy mapping of molecular triplets onto the basis set of pharmacophore triplets: unlike in the binary scheme where an atom triplet is set to highlight the bit of a single, best-matching basis triplet, the herein-defined fuzzy approach allows for gradual mapping of each atom triplet onto several related basis triplets, thus minimizing binary classification artifacts. (2) The second innovation is proteolytic equilibrium dependence, by explicitly considering all of the conjugated acids and bases (microspecies). 2D-FPTs are concentration-weighted (as predicted at pH=7.4) averages of microspecies fingerprints. Therefore, small structural modifications, not affecting the overall pharmacophore pattern (in the sense of classical rule-based assignment), but nevertheless triggering a pKa shift, will have a major impact on 2D-FPT. Pairs of almost identical compounds with significantly differing activities ("activity cliffs" in classical descriptor spaces) were in many cases predictable by 2D-FPT. (3) The third innovation is a new similarity scoring formula, acknowledging that the simultaneous absence of a triplet in two molecules is a less-constraining indicator of similarity than its simultaneous presence. It displays excellent neighborhood behavior, outperforming 2D or 3D two-point pharmacophore descriptors or chemical fingerprints. The 2D-FPT calculator was developed using the chemoinformatics toolkit of ChemAxon (www.chemaxon.com).

  4. Femtosecond time-resolved hot carrier energy distributions of photoexcited semiconductor quantum dots

    International Nuclear Information System (INIS)

    Chuang, Chi-Hung; Burda, Clemens; Chen, Xiaobo

    2013-01-01

    Using femtosecond transient absorption spectroscopy, we investigated hot carrier distributions in semiconductor cadmium selenide quantum dots. The relaxation processes represent the behavior of an ensemble of QDs. This concept is applied for analysis with the Fermi-Dirac distribution and relaxation processes among different electron-hole pair states. By extracting the experimental hot carrier distribution and fitting with the Fermi-Dirac function, we resolved the rapid thermalization processes, such as carrier-carrier and carrier-phonon interactions was resolved within one picosecond upon photoexcitation. The analysis, using the Fermi-Dirac distribution modulated by the density of states, provides a general route to understanding the carrier cooling and heat dissipation processes in quantum dot-based systems. (copyright 2012 by WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  5. Intermolecular interaction of photoexcited Cu(/TMpy-P4) with water studied by transient resonance Raman and picosecond absorption spectroscopies

    NARCIS (Netherlands)

    Kruglik, S.; Kruglik, Sergei G.; Ermolenkov, Vladimir V.; Shvedko, Alexander G.; Orlovich, Valentine A.; Galievsky, Victor A.; Chirvony, Vladimir S.; Otto, Cornelis; Turpin, Pierre-Yves

    1997-01-01

    photoinduced complex between Cu(TMpy-P4) and water molecules, reversibly axially coordinated to the central metal, was observed in picosecond transient absorption and nanosecond resonance Raman experiments. This complex is rapidly created (τ1 = 15 ± 5 ps) in the excited triplet (π, π*) state of

  6. Colored triplets with integral quantum numbers

    International Nuclear Information System (INIS)

    Han, M.Y.

    1974-01-01

    The systematics of low-lying hadron spectra and the relations between mass, cross-section and magnetic moment in terms of ''constituent'' quarks on one hand, and abstraction of the properties of hadronic weak and electromagnetic current in terms of ''current'' quarks on the other hand have been extremely useful. In the category of three triplet models, there are several versions with the varying degree of similarity and difference among them. These include; (1) the paraquarks of order three, (2) the three triplets with SU(3)' x SU(3)'' symmetry, (3) SUB version by Cabibbo et al., and (4) perfect ''color'' symmetry by Gell-Mann. The physical difference among these various versions of the three triplet models and their consequence are discussed with respect to some of the current theoretical and experimental topics. (Iwase, T.)

  7. A code for optimising triplet layout

    CERN Document Server

    AUTHOR|(CDS)2141109; Seryi, Andrei; Abelleira, Jose; Cruz Alaniz, Emilia

    2017-01-01

    One of the main challenges when designing final focus systems of particle accelerators is maximising the beam stay clear in the strong quadrupole magnets of the inner triplet. Moreover it is desirable to keep the quadrupoles in the inner triplet as short as possible for space and costs reasons but also to reduce chromaticity and simplify corrections schemes. An algorithm that explores the triplet parameter space to optimise both these aspects was written. It uses thin lenses as a first approximation for a broad parameter scan and MADX for more precise calculations. The thin lens algorithm is significantly faster than a full scan using MADX and relatively precise at indicating the approximate area where the optimum solution lies.

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

    Science.gov (United States)

    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.

  9. Birth weight in a large series of triplets

    Directory of Open Access Journals (Sweden)

    van Beijsterveldt Catharina EM

    2011-04-01

    Full Text Available Abstract Background Triplets are often born premature and with a low birth weight. Because the incidence of triplet births is rare, there are relatively few studies describing triplet birth weight characteristics. Earlier studies are often characterized by small sample sizes and lack information on important background variables such as zygosity. The objective of this study is to examine factors associated with birth weight in a large, population-based sample of triplets registered with the Netherlands Twin Register (NTR. Methods In a sample of 1230 triplets from 410 families, the effects of assisted reproductive techniques, zygosity, birth order, gestational age, sex, maternal smoking and alcohol consumption during pregnancy on birth weight were assessed. The resemblance among triplets for birth weight was estimated as a function of zygosity. Birth weight discordance within families was studied by the pair-wise difference between triplets, expressed as a percentage of the birth weight of the heaviest child. We compare data from triplets registered with the NTR with data from population records, which include live births, stillbirths and children that have deceased within days after birth. Results There was no effect of assisted reproductive techniques on triplet birth weight. At gestational age 24 to 40 weeks triplets gained on average 130 grams per week; boys weighed 110 grams more than girls and triplets of smoking mothers weighted 104 grams less than children of non-smoking mothers. Monozygotic triplets had lower birth weights than di- and trizygotic triplets and birth weight discordance was smaller in monozygotic triplets than in di- and trizygotic triplets. The correlation in birth weight among monozygotic and dizygotic triplets was 0.42 and 0.32, respectively. In nearly two-thirds of the families, the heaviest and the lightest triplet had a birth weight discordance over 15%. The NTR sample is representative for the Dutch triplet

  10. Capturing triplet emission in white organic light emitting devices

    Energy Technology Data Exchange (ETDEWEB)

    Singh, Jai [Faculty of EHSE, School of Engineering and IT, B-purple-12, Charles Darwin University, Darwin, NT 0909 (Australia)

    2011-08-15

    The state-of-the art in the white organic light emitting devices (WOLEDs) is reviewed for further developments with a view to enhance the capture of triplet emission. In particular, applying the new exciton-spin-orbit-photon interaction operator as a perturbation, rates of spontaneous emission are calculated in a few phosphorescent materials and compared with experimental results. For iridium based phosphorescent materials the rates agree quite well with the experimental results. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  11. Superconducting spin-triplet-MRAM with infinite magnetoresistance ratio

    Energy Technology Data Exchange (ETDEWEB)

    Lenk, Daniel; Ullrich, Aladin; Obermeier, Guenter; Mueller, Claus; Krug von Nidda, Hans-Albrecht; Horn, Siegfried; Tidecks, Reinhard [Institut fuer Physik, Universitaet Augsburg, D-86159 Augsburg (Germany); Morari, Roman [Institut fuer Physik, Universitaet Augsburg, D-86159 Augsburg (Germany); D. Ghitsu Institute of Electronic Engineering and Nanotechnologies ASM, Academiei Str. 3/3, MD2028 Kishinev (Moldova, Republic of); Solid State Physics Department, Kazan Federal University, 420008 Kazan (Russian Federation); Zdravkov, Vladimir I. [Institut fuer Physik, Universitaet Augsburg, D-86159 Augsburg (Germany); D. Ghitsu Institute of Electronic Engineering and Nanotechnologies ASM, Academiei Str. 3/3, MD2028 Kishinev (Moldova, Republic of); Institute of Applied Physics and Interdisciplinary Nanoscience Center, Universitaet Hamburg, Jungiusstrasse 9A, D-20355 Hamburg (Germany); Sidorenko, Anatoli S. [D. Ghitsu Institute of Electronic Engineering and Nanotechnologies ASM, Academiei Str. 3/3, MD2028 Kishinev (Moldova, Republic of); Tagirov, Lenar R. [Institut fuer Physik, Universitaet Augsburg, D-86159 Augsburg (Germany); Solid State Physics Department, Kazan Federal University, 420008 Kazan (Russian Federation)

    2016-07-01

    We fabricated a nanolayered hybrid superconductor-ferromagnet spin-valve structure, i.e. the superconducting transition temperature of this structure depends on its magnetic history. The observed spin-valve effect is based on the generation of the long range odd in frequency triplet component, arising from a non-collinear relative orientation of the constituent ferromagnetic layers. We investigated the effect both as a function of the sweep amplitude of the magnetic field, determining the magnetic history, and the applied transport current. Moreover, we demonstrate the possibility of switching the system from the normal o the superconducting state by applying field pulses, yielding an infinite magnetoresistance ratio.

  12. Optimal weight gain in triplet pregnancies.

    Science.gov (United States)

    Johnston, Robert C; Erfani, Hadi; Shamshirsaz, Amir A; Spiel, Melissa; Ravangard, Sam F; Shaman, Majid; Allaf, M Baraa; Shamshirsaz, Alireza A; Haeri, Sina

    2017-08-01

    To identify appropriate weight gain in triplet gestations, which may aid in reducing the risk of perinatal morbidity within this high-risk cohort. This retrospective cohort study evaluated all non-anomalous triplet pregnancies between 23 and 40 weeks' gestation resulting in live births at five tertiary-care medical centers between 1991 and 2011. Subjects were divided by pre-pregnancy BMI into underweight, normal-weight, overweight, and obese groups, and then stratified by low (gain (≥1.5 lbs/week). Primary outcomes included spontaneous preterm birth and preeclampsia. We included 116 mothers and 348 corresponding neonates for final analysis. The incidence of preeclampsia and preterm delivery less than 32 weeks' gestation was 37% and 41%, respectively. The incidence of preeclampsia increased with weight gain per week, but was not statistically different from subjects who gained less weight. We found no statistical correlation between weight gain per week and preterm delivery. We found no association between preeclampsia or preterm delivery and increasing weight gain in triplet pregnancies. The association with increased risk for preeclampsia was predominantly due to BMI effect. Based on the current study, recommendations for optimal weight gain in mothers with triplet gestations could not be defined.

  13. Structural basis for triplet repeat disorders

    DEFF Research Database (Denmark)

    Baldi, Pierre; Brunak, Søren; Chauvin, Yves

    1999-01-01

    Motivation: Over a dozen major degenerative disorders, including myotonic distrophy, Huntington's disease and fragile X syndrome result from unstable expansions of particular trinucleotides. Remarkably, only some of all the possible triplets, namely CAG/CTG, CGG/CCG and GAA/TTC, have been associa...

  14. Can the ''doublet-triplet splitting'' problem be solved without doublet-triplet splitting?

    International Nuclear Information System (INIS)

    Dvali, G.R.

    1992-03-01

    We consider a new possible mechanism for the natural solution of the doublet-triplet splitting problem in SUSY GUTs. In contrast to the usually discussed scenarios, in our case the GUT symmetry breaking does not provide any splitting between the Higgs doublet and the triplet masses. The weak doublet and its colour triplet partner both remain light, but the triplet automatically occurs decoupled from the quark and lepton superfields and cannot induce proton decay. The advantage of the above scenarios is the absence at the GUT scale of the baryon number violating the tree level d = 5 and d = 6 operators via the colour-triple exchange. It is shown that in flipped SU(5) GUT they do not appear at any scale. In the SO(10) model, such operators can be induced after SUSY breaking but are strongly suppressed. (author). 22 refs, 2 figs

  15. Birth weight in a large series of triplets

    NARCIS (Netherlands)

    Ponsen-Lamb, D.J.; Middeldorp, C.M.; van Beijsterveldt, C.E.M.; Vink, J.M.; Haak, M.C.; Boomsma, D.I.

    2011-01-01

    Background: Triplets are often born premature and with a low birth weight. Because the incidence of triplet births is rare, there are relatively few studies describing triplet birth weight characteristics. Earlier studies are often characterized by small sample sizes and lack information on

  16. Birth weight in a large series of triplets

    NARCIS (Netherlands)

    Lamb, Diane J.; Middeldorp, Christel M.; van Beijsterveldt, Catharina E. M.; Vink, Jacqueline M.; Haak, Monique C.; Boomsma, Dorret I.

    2011-01-01

    Triplets are often born premature and with a low birth weight. Because the incidence of triplet births is rare, there are relatively few studies describing triplet birth weight characteristics. Earlier studies are often characterized by small sample sizes and lack information on important background

  17. Adaptive port-starboard beamforming of triplet arrays

    NARCIS (Netherlands)

    Beerens, S.P.; Been, R.; Groen, J.; Noutary, E.; Doisy, Y.

    2000-01-01

    Triplet arrays are single line arrays with three hydrophones on a circular section of the array. The triplet structure provides immediate port-starboard (PS) discrimination. This paper discusses the theoretical and experimental performance of triplet arrays. Results are obtained on detection gain

  18. Investigation of Triplet Exciplex Dynamics by Magnetic Field Effects due to the Triplet Mechanism

    OpenAIRE

    Ulrich, T.; Steiner, Ulrich; Föll, Rudolf E.

    1983-01-01

    A reaction scheme is described allowing for magnetic field effects on the chemical kinetics of triplet reactions due to the selective decay of triplet sublevels. The theoretical treatment of this scheme is outlined on the basis of a stochastic Liouville equation, taking into account the rotational diffusion of molecules in liquid solution. Whereas the exact solution of the general case is obtained by a numerical procedure as described by Pedersen and Freed, an approximate analytical expressio...

  19. Photoexcitation and ionization of hydrogen atom confined in Debye environment

    International Nuclear Information System (INIS)

    Lumb, S.; Lumb, S.; Nautiyal, V.

    2015-01-01

    The dynamics of a hydrogen atom confined in an impenetrable spherical box and under the effect of Debye screening, in the presence of intense short laser pulses of few femtosecond is studied in detail. The energy spectra and wave functions have been calculated using Bernstein polynomial (B-polynomial) method. Variation of transition probabilities for various transitions due to changes in Debye screening length, confinement radius as well as the parameters characterizing applied laser pulse is studied and explained. The results are found to be in good agreement with the results obtained by others. The photoexcitation and ionization of the atom strongly depend on confinement radius and screening parameter. For small confinement radii and for some values of screening parameter the atom is found to be ionized easily. The dynamics of the atom can be easily controlled by varying pulse parameters

  20. Explicit role of dynamical and nondynamical electron correlation on singlet-triplet splitting in carbenes

    International Nuclear Information System (INIS)

    Seal, Prasenjit; Chakrabarti, Swapan

    2007-01-01

    Density functional theoretical studies have been performed on carbene systems to determine the singlet-triplet splitting and also to explore the role of electron correlation. Using an approximate method of separation of dynamical and nondynamical correlation, it is found that dynamical and nondynamical electron correlation stabilizes the singlet state relative to the triplet for halo carbenes in both BLYP and B3LYP methods. Calculations performed on higher homologues of methylene suggest that beyond CH(CH 3 ), both the electron correlations have leveling effect in stabilizing the singlet state relative to the triplet. It has also been observed while dynamical electron correlation fails to provide any substantial degree of stabilization to the singlet states of higher homologues of methylene in B3LYP method, an opposite trend is observed for nondynamical counterpart. Among the larger systems studied (9-triptycyl)(α-naphthyl)-carbene has the highest stability of the triplet state whereas bis-imidazol-2-ylidenes has the most stable singlet state. Interestingly, the values of the dynamical electron correlation for each state of each system studied are different for the two methods used. The reason behind this apparent discrepancy lies in the fact that the coefficients of the LYP part in B3LYP and BLYP functionals are different

  1. Precision spectroscopy with ultracold {sup 87}Rb{sub 2} triplet molecules

    Energy Technology Data Exchange (ETDEWEB)

    Strauss, Christoph

    2011-10-19

    In this thesis I report precision spectroscopy with ultracold {sup 87}Rb{sub 2} triplet molecules where we use lasers to couple the states in different molecular potentials. We study in detail states of the a {sup 3} sum {sup +}{sub u} and (1) {sup 3} sum {sup +}{sub g} potentials. These states are of great importance for transferring weakly bound molecules to the ro-vibrational triplet ground state via states of the excited potential. As most experiments start from molecules in their X {sup 1} sum {sup +}{sub g} ground state, the triplet states were hard to access via dipole transitions and remained largely unexplored. The measurements presented in this thesis are the first detailed study of diatomic {sup 87}Rb{sub 2} molecules in these states. Our experiments start with an ultracold cloud of {sup 87}Rb atoms. We then load this cloud into an optical lattice where we use a magnetic Feshbach resonance at 1007.4 G to perform a Feshbach association. After we have removed all unbound atoms, we end up with a pure sample of weakly bound Feshbach molecules inside the optical lattice. The optical lattice prevents these molecules from colliding with each other which results in molecular lifetimes on the order of a few hundred milliseconds. In the first set of experiments, we use a laser coupling the Feshbach state to the excited (1) {sup 3} sum {sup +}{sub g} triplet state to map out its low-lying vibrational (v = 0.. 15), rotational, hyperfine, and Zeeman structure. The experimental results are in good agreement with calculations done by Marius Lysebo and Prof. Leif Veseth. We then map out in detail the vibrational, rotational, hyperfine, and Zeeman structure of the a {sup 3} sum {sup +}{sub u} triplet ground state using dark state spectroscopy with levels in the (1) {sup 3} sum {sup +}{sub g} potential as an intermediate state. In this scheme we are able to access molecules in triplet states because our Feshbach state has strong triplet character. Interestingly, it

  2. Precision spectroscopy with ultracold {sup 87}Rb{sub 2} triplet molecules

    Energy Technology Data Exchange (ETDEWEB)

    Strauss, Christoph

    2011-10-19

    In this thesis I report precision spectroscopy with ultracold {sup 87}Rb{sub 2} triplet molecules where we use lasers to couple the states in different molecular potentials. We study in detail states of the a {sup 3} sum {sup +}{sub u} and (1) {sup 3} sum {sup +}{sub g} potentials. These states are of great importance for transferring weakly bound molecules to the ro-vibrational triplet ground state via states of the excited potential. As most experiments start from molecules in their X {sup 1} sum {sup +}{sub g} ground state, the triplet states were hard to access via dipole transitions and remained largely unexplored. The measurements presented in this thesis are the first detailed study of diatomic {sup 87}Rb{sub 2} molecules in these states. Our experiments start with an ultracold cloud of {sup 87}Rb atoms. We then load this cloud into an optical lattice where we use a magnetic Feshbach resonance at 1007.4 G to perform a Feshbach association. After we have removed all unbound atoms, we end up with a pure sample of weakly bound Feshbach molecules inside the optical lattice. The optical lattice prevents these molecules from colliding with each other which results in molecular lifetimes on the order of a few hundred milliseconds. In the first set of experiments, we use a laser coupling the Feshbach state to the excited (1) {sup 3} sum {sup +}{sub g} triplet state to map out its low-lying vibrational (v = 0.. 15), rotational, hyperfine, and Zeeman structure. The experimental results are in good agreement with calculations done by Marius Lysebo and Prof. Leif Veseth. We then map out in detail the vibrational, rotational, hyperfine, and Zeeman structure of the a {sup 3} sum {sup +}{sub u} triplet ground state using dark state spectroscopy with levels in the (1) {sup 3} sum {sup +}{sub g} potential as an intermediate state. In this scheme we are able to access molecules in triplet states because our Feshbach state has strong triplet character. Interestingly, it

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

    Science.gov (United States)

    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.

  4. Light grand unified theory triplets and Yukawa splitting

    International Nuclear Information System (INIS)

    Rakshit, Subhendu; Shadmi, Yael; Raz, Guy; Roy, Sourov

    2004-01-01

    Triplet-mediated proton decay in grand unified theories (GUTs) is usually suppressed by arranging a large triplet mass. Here we explore instead a mechanism for suppressing the couplings of the triplets to the first and second generations compared to the Yukawa couplings, so that the triplets can be light. This mechanism is based on a 'triplet symmetry' in the context of product-group GUTs. We study two possibilities. The first possibility, which requires the top Yukawa coupling to arise from a nonrenormalizable operator at the GUT scale, is that all triplet couplings to matter are negligible, so that the triplets can be at the weak scale, giving new evidence for grand unification. The second possibility is that some triplet couplings, and in particular Ttb and Tt-barl-bar, are equal to the corresponding Yukawa couplings. This would give a distinct signature of grand unification if the triplets were sufficiently light. However, we derive a model-independent bound on the triplet mass in this case, which is at least 10 6 GeV. Finally, we construct an explicit viable GUT model based on Yukawa splitting, with the triplets at 10 14 GeV, as required for coupling unification to work. This model requires no additional thresholds below the GUT scale

  5. BVRI SURFACE PHOTOMETRY OF ISOLATED GALAXY TRIPLETS

    International Nuclear Information System (INIS)

    Hernandez-Toledo, H. M.; Mendez-Hernandez, H.; Aceves, H.; OlguIn, L.

    2011-01-01

    Optical broadband BVRI observations of 54 galaxies selected from the Catalog of Isolated Triplets of Galaxies in the Northern Hemisphere have been carried out at San Pedro Martir National Observatory to evaluate their photometric and morphological properties. We complement our analysis with Two-Micron All Sky Survey (2MASS) and Sloan Digital Sky Survey (SDSS) images and look for signatures likely related to interactions/mergers. We report apparent/absolute BVRI magnitudes and colors for the 54 galaxies. The membership of these galaxies is re-evaluated by imposing a reasonable condition of concordant redshifts upon the original selection criteria, rendering a final sample of 34 galaxies in 13 triplets, 12 galaxies in close pairs, and 8 galaxy outliers. The triplets are spiral-dominated systems in different dynamical stages from loosely interacting to almost merged objects. The incidence fraction of features likely associated with interactions is ∼56%, similar to those found in northern and southern compact groups. The average fraction of bars is 35% with a mean value of maximum bar ellipticity ε max ∼ 0.4. Bars are hosted in the late-type triplet spirals, almost twice more than in early-type spirals. The global fraction of rings is 20%, all in the late-type components. The overdensity of triplets with respect to the background and their current dynamical status, as devised from our estimate of their dynamical parameters, namely the harmonic radius R H , velocity dispersion σ, dimensionless crossing time H 0 τ c , and virial mass M V , appear to be sufficient to favor galaxy transformations similar to those seen in dense groups and clusters. By contrast, the lower fraction of bonafide ellipticals and the relatively higher fraction of late-type spirals make these triplets essentially different from the Hickson Compact Groups and more representative of the field. A modest 1.6 enhancement factor in the optical luminosity of the late-type triplet components

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

    Science.gov (United States)

    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.

  7. Heavy atoms as molecular probes in studying the solvent dependence of the dynamics of triplet exciplexes

    International Nuclear Information System (INIS)

    Steiner, U.; Winter, G.

    1981-01-01

    Electron transfer reactions between thiopyronine triplet (acceptor 3 A + ) and the electron donors (D), aniline, p-Br-aniline and p-I-aniline, are investigated by flash spectroscopy in solvents of different viscosity and polarity. Due to the heavy-atom effect the radical yield becomes very sensitive to the solvent influence, which can be explained by the dynamic properties of a triplet exciplex ( 3 (AD + )) formed as a primary product in the reaction between acceptor triplet and donor. Whereas on variation of solvent viscosity the solvent cage effect on the dissociation of 3 (AD + ) is observed, a change in solvent polarity is suggested to affect the radiationless deactivation of 3 (AD + ) to the ground state of the components. (author)

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

    Science.gov (United States)

    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.

  9. Spectrally tunable mollow triplet emission from a coherently excited quantum dot in a microcavity

    DEFF Research Database (Denmark)

    Ulrich, Sven M.; Ates, Serkan; Reitzenstein, Stephan

    2010-01-01

    Resonance fluorescence of excitonic s-shell emission from a coherently pumped single InGaAs/GaAs quantum dot inside a micropillar cavity has been investigated in dependence on optical pump power and laser detuning, respectively. For strong purely resonant excitation, Mollow triplet spectra with l...... with large Rabi splittings of j~­j » 60¹eV have been observed. Laser detuning-dependent series revealed the pronounced asymmetry of the emission triplet as predicted by theory. From our data, an electrical dipole moment of ¹ » 17:8§0:5 Debye could be derived for the excitonic state....

  10. Toward Singlet-Triplet Bistable Nonalternant Kekulé Hydrocarbons: Azulene-to-Naphthalene Rearrangement.

    Science.gov (United States)

    Das, Soumyajit; Wu, Jishan

    2015-12-04

    Recent developments of open-shell singlet diradicaloids motivated the search for stable singlet-triplet bistable nonalternant polycyclic hydrocarbons. During the synthesis of this type of molecule, such as the dibenzo-cyclohepta[def]fluorene 3, an unexpected azulene-to-naphthalene rearrangement was observed at room temperature, which resulted in new nonalternant hydrocarbons 8a/8b with a closed-shell singlet ground state. These studies provided insight into the unique chemistry of azulene and challenges for the synthesis of singlet-triplet bistable polycyclic hydrocarbons.

  11. Electrochemical detection of DNA triplet repeat expansion

    Czech Academy of Sciences Publication Activity Database

    Fojta, Miroslav; Havran, Luděk; Vojtíšková, Marie; Paleček, Emil

    2004-01-01

    Roč. 126, č. 21 (2004), s. 6532-6533 ISSN 0002-7863 R&D Projects: GA AV ČR IAA4004402; GA AV ČR IBS5004355; GA AV ČR KJB4004302; GA AV ČR KSK4055109 Institutional research plan: CEZ:AV0Z5004920 Keywords : DNA triplet repeat expansion * PCR amplification * neurodegenerative diseases Subject RIV: BO - Biophysics Impact factor: 6.903, year: 2004

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  14. Photoexcited carrier trapping and recombination at Fe centers in GaN

    International Nuclear Information System (INIS)

    Uždavinys, T. K.; Marcinkevičius, S.; Leach, J. H.; Evans, K. R.; Look, D. C.

    2016-01-01

    Fe doped GaN was studied by time-resolved photoluminescence (PL) spectroscopy. The shape of PL transients at different temperatures and excitation powers allowed discrimination between electron and hole capture to Fe"3"+ and Fe"2"+ centers, respectively. Analysis of the internal structure of Fe ions and intra-ion relaxation rates suggests that for high repetition rates of photoexciting laser pulses the electron and hole trapping takes place in the excited state rather than the ground state of Fe ions. Hence, the estimated electron and hole capture coefficients of 5.5 × 10"−"8 cm"3/s and 1.8 × 10"−"8 cm"3/s should be attributed to excited Fe"3"+ and Fe"2"+ states. The difference in electron capture rates determined for high (MHz) and low (Hz) (Fang et al., Appl. Phys. Lett. 107, 051901 (2015)) pulse repetition rates may be assigned to the different Fe states participating in the carrier capture. A weak temperature dependence of the electron trapping rate shows that the potential barrier for the multiphonon electron capture is small. A spectral feature observed at ∼420 nm is assigned to the radiative recombination of an electron in the ground Fe"2"+ state and a bound hole.

  15. Density-dependent electron scattering in photoexcited GaAs in strongly diffusive regime

    DEFF Research Database (Denmark)

    Mics, Zoltán; D’Angio, Andrea; Jensen, Søren A.

    2013-01-01

    In a series of systematic optical pump–terahertz probe experiments, we study the density-dependent electron scattering rate in photoexcited GaAs in the regime of strong carrier diffusion. The terahertz frequency-resolved transient sheet conductivity spectra are perfectly described by the Drude...... model, directly yielding the electron scattering rates. A diffusion model is applied to determine the spatial extent of the photoexcited electron-hole gas at each moment after photoexcitation, yielding the time-dependent electron density, and hence the density-dependent electron scattering time. We find...

  16. Finite-bias conductance anomalies at a singlet-triplet crossing

    DEFF Research Database (Denmark)

    Stevanato, Chiara; Leijnse, Martin Christian; Flensberg, Karsten

    2012-01-01

    at the crossing. Here we show that, in addition, level crossings can give rise to a nearly vertical step-edge, ridge or even a Fano-like ridge-valley feature in the dierential conductance inside the relevant Coulomb diamond. We study a gate-tunable quasidegeneracy between singlet and triplet ground states...

  17. A novel frequency domain fluorescence technique for determination of triplet decay times

    NARCIS (Netherlands)

    Sterenborg, H. J.; Janson, M. E.; van Gemert, M. J.

    1999-01-01

    Frequency domain fluorescence measurement using two diode lasers with amplitude modulation in the kHz range yields a signal component at the sum frequency. This intermodulation phenomenon was observed in an aqueous solution of haematoporphyrin (HP) and could be related to triplet state population

  18. Experimental confirmation of photon-induced spin-flip transitions in helium via triplet metastable yield spectra

    International Nuclear Information System (INIS)

    Rubensson, Jan-Erik; Moise, Angelica; Richter, Robert; Mihelic, Andrej; Bucar, Klemen; Zitnik, Matjaz

    2010-01-01

    Doubly excited states below the N=2 ionization threshold are populated by exciting helium atoms in a supersonic beam with monochromatized synchrotron radiation. The fluorescence decay of these states triggers a radiative cascade back to the ground state with large probability to populate long lived singlet and triplet helium metastable states. The yield of metastables is measured using a multichannel plate detector after the beam has passed a singlet-quenching discharge lamp. The variation of the yield observed with the lamp switched on or off is related to the triplet-singlet mixing of the doubly excited states.

  19. Diphenylcarbene Protected by Four ortho-Iodine Groups: An Unusually Persistent Triplet Carbene

    Directory of Open Access Journals (Sweden)

    Katsuyuki Hirai

    2016-11-01

    Full Text Available Diphenyldiazomethane with four iodine groups at the ortho positions and two tert-butyl groups at the para positions, i.e., bis(4-tert-butyl-2,6-diiodophenyldiazomethane (1a-N2, was synthesized as a sterically hindered triplet carbene precursor. Irradiation of 1a-N2 in solution effectively generated the corresponding triplet diphenylcarbene 31a, which was characterized by UV-vis spectroscopy at low temperature, along with laser flash photolysis techniques at room temperature. The UV-vis spectrum of 31a was obtained by irradiating 1a-N2 in a 2-methyltetrahydrofuran matrix at 77 K. The ESR spectrum showed no triplet carbene signals, while a radical species was observed at the anticipated temperature of the decomposition of triplet carbene 31a. Transient absorption bands ascribable to 31a were observed by laser flash photolysis of 1a-N2 in a degassed benzene solution and decayed very slowly with a second-order rate constant (2k/εl of 5.5 × 10−3·s−1. Steady-state irradiation of 1a-N2 in degassed benzene afforded 9,10-diarylphenanthrene derivative 2a in a 31% yield. Triplet carbene 31a was also trapped by either oxygen (kO2 = 6.5 × 105 M−1·s−1 or 1,4-cyclohexadiene (kCHD = 1.5 M−1·s−1 to afford the corresponding ketone 1a-O or the diarylmethane 1a-H2. The carbene was shown to be much less reactive than the triplet diphenylcarbene that is protected by two ortho-iodo and two ortho-bromo groups, 31b.

  20. MTGAN: Speaker Verification through Multitasking Triplet Generative Adversarial Networks

    OpenAIRE

    Ding, Wenhao; He, Liang

    2018-01-01

    In this paper, we propose an enhanced triplet method that improves the encoding process of embeddings by jointly utilizing generative adversarial mechanism and multitasking optimization. We extend our triplet encoder with Generative Adversarial Networks (GANs) and softmax loss function. GAN is introduced for increasing the generality and diversity of samples, while softmax is for reinforcing features about speakers. For simplification, we term our method Multitasking Triplet Generative Advers...

  1. Powering the High-Luminosity Triplets

    Science.gov (United States)

    Ballarino, A.; Burnet, J. P.

    The powering of the magnets in the LHC High-Luminosity Triplets requires production and transfer of more than 150 kA of DC current. High precision power converters will be adopted, and novel High Temperature Superconducting (HTS) current leads and MgB2 based transfer lines will provide the electrical link between the power converters and the magnets. This chapter gives an overview of the systems conceived in the framework of the LHC High-Luminosity upgrade for feeding the superconducting magnet circuits. The focus is on requirements, challenges and novel developments.

  2. Resonant Ni and Fe KLL Auger spectra photoexcited from NiFe alloys

    International Nuclear Information System (INIS)

    Koever, L.; Cserny, I.; Berenyi, Z.; Egri, S.; Novak, M.

    2005-01-01

    Complete text of publication follows. KLL Auger spectra of 3d transition metal atoms in solid environment, measured using high energy resolution, give an insight into the details of the local electronic structure surrounding the particular atoms emitting the signal Auger electrons. Fine tuning the energy of the exciting monochromatic photons across the K-absorption edge, features characteristic to resonant phenomena can be identified in the spectra. The shapes of the resonantly photoexcited KLL Auger spectra induced from 3d transition metals and alloys are well interpreted by the single step model of the Auger process, based on the resonant scattering theory. The peak shapes are strongly influenced by the 4p partial density of unoccupied electronic states around the excited atom. High energy resolution studies of KLL Auger spectra of 3d transition metals using laboratory X-ray sources, however, request very demanding experiments and yield spectra of limited statistical quality making the evaluation of the fine details in the spectra difficult. The Tunable High Energy XPS (THE- XPS) instrument at BW2 offers optimum photon x and energy resolution for spectroscopy of deep core Auger transitions. For the present measurements high purity polycrystalline Ni and Fe sheets as well as NiFe alloy samples of different compositions (Ni 80 Fe 20 , Ni 50 Fe 50 , Ni 20 Fe 80 ) were used. The surfaces of the samples were cleaned by in-situ argon ion sputtering. The measurements of the Ni and Fe KL 23 L 23 Auger spectra of the metal and alloy samples were performed with the THE-XPS instrument using high electron energy resolution (0.2 eV). In Fig.1, the measured Fe KL 23 L 23 spectrum, photoexcited at the Fe K absorption edge from Fe metal, is compared with the respective spectrum excited from a Ni 50 Fe 50 alloy. A significant broadening of the 1 D 2 peak and an enhancement of the spectral intensity at the low energy loss part of this peak observed in the alloy sample, while the

  3. Proximity effects and Josephson currents in ferromagnet. Spin-triplet superconductors junctions

    International Nuclear Information System (INIS)

    Terrade, Damien

    2015-01-01

    Spin-triplet superconductivity, first attached to the description of 3 He, is now generally considered to also occur in heavy-fermions compounds and in perovskite ruthenium oxide Sr 2 RuO 4 . The latter material is especially interesting since many experiments show strong evidences for a unitary chiral spin-triplet state. Moreover, the recent fabrication of thin heterostructures made of ferromagnetic SrRuO 3 on the top of Sr 2 RuO 4 strongly encourages new theoretical studies on the interplay between spin-triplet superconductor and ferromagnet in similar fashion to spin-singlet superconductors. Using an extended tight-binding Hamiltonian to model the superconductor, we discuss in this thesis the specific proximity effects of such interface by solving self-consistently the Bogoliubov-De Gennes equations on two- and three-dimensional lattices in the ballistic limit. We obtain the spatial profile of the superconducting order parameters at the interface as well as the spin-polarisation and the current across the Josephson junctions. In contrast to heterostructures made of spin-singlet superconductor, we show that the physical properties at the interface are not only controlled by the strength of the magnetization inside the ferromagnet but also by its orientation due to the existence of a finite pair spin projection of the spin-triplet Cooper pairs. We analyse in the first part the spin-polarisation and the Gibbs free energy at the three-dimensional ferromagnet-chiral spin-triplet superconductor interface. Then, the second part of the thesis is dedicated to the study of the Josephson junctions made of a chiral spin-triplet superconductor and a ferromagnetic barrier. More precisely, we analyse the existence of 0-π state transitions in two- and three-dimensional junctions with respect to the strength and the orientation of the magnetization. Finally, we study the proximity effects at the interface of helical spin-triplet superconductors. They differ from the chiral

  4. Tetralogy of Fallot in monozygotic triplets

    Energy Technology Data Exchange (ETDEWEB)

    Victorica, B.E.; Kumar, A.; Zori, R.T. [Univ. of Florida, Gainesville, FL (United States)

    1994-09-01

    Tetralogy of Fallot (TOF), like most other congenital heart defects, is considered to be of multifactorial inheritance. Occasional families with multiple affected members in one or more generations above been described. A stronger genetic influence in the causation of isolated TOF is also supported by recent demonstration of microdeletions in chromosome 22q11 region. Deletions in this region are also responsible for DiGeorge and velocardiofacial syndrome as well as CHARGE association. We report a set of monozygotic triplets born to healthy parents at 35 weeks of gestation. There was no family history of congenital heart defects. All three had TOF with left aortic arch (documented by cardiac catheterization in 2 and echocardiography in all 3). The degree of right ventricular outflow obstruction varied from mild to complete atresia needing prostaglandin infusion and a subsequent Blalock-Taussig shunt in one. No features of DiGeorge syndrome or any other congenital defects were present. High resolution chromosome analysis of peripheral blood lymphocytes of these infants revealed normal 46,XY male karyotype. Fluorescent in situ hybridization (FISH) using probe D22S75, which maps to chromosome 22q11.2 did not detect any deletion. This pedigree suggests a de novo mutation causing TOF in all 3 monozygotic triplets. Although there is no deletion demonstrable in DiGeorge critical region, a smaller deletion or mutation in this region cannot be excluded.

  5. The neonatal outcome in twin versus triplet and quadruplet pregnancies

    Directory of Open Access Journals (Sweden)

    Fatemeh Nasseri

    2009-02-01

    Full Text Available

    • BACKGROUND: To assess the risk of neonatal mortality and morbidity in twin, triplet and quadruplet pregnancies.
    • METHODS: In a retrospective study, the neonatal outcome of all twin, triplet and quadruplet gestations delivered from October 2001 to September 2006 was reviewed. The neonatal outcome of triples and quadruplets was compared with a matched group of twins for gestational age.
    • RESULTS: During a 5-year period, 511 sets of twin pregnancies, 42 sets of triplet and 5 sets of quadruplet pregnancies were studied. The mean of gestational age for twins, triplets and quadruplets were 33.92 ± 3.5 weeks, 30.92 ± 3.8 weeks and 31.60 ± 2.0 weeks, respectively, (P = 0.0001. Triplets and quadruplets weighed less than twins, (P = 0.0001. Neonatal mortality was 13.5% for twins, 26.8% for triplets and 30% for quadruplets. In vitro fertilization, use of ovulation induction agents, and cesarean delivery in the women with triplet and quadruplet were significantly higher than in those with twin pregnancies, (P = 0.0001. The mean age of mothers with triplets and quadruplets was significantly higher than with twins (P = 0.026. There was not a significant difference in respiratory and non-respiratory short outcomes between triplets, quadruplets and twins when matched for gestational age. Apgar score at 1 and 5 minutes was significantly lower in triplets and quadruplets than twins. There was no influence of birth order on neonatal mortality of triplet pregnancy. Neonatal mortality of triplet births was significantly decreased over the 5 years of the study period.
    • CONCLUSIONS: Triplets and quadruplets have a similar neonatal outcome as twins when matched for gestational age. There is no influence of birth on the neonatal mortality of triplet pregnancy. It appears that outcome is mainly dependent on gestational age.
    • KEYWORDS: Neonatal

    • Does interchain stacking morphology contribute to the singlet-triplet interconversion dynamics in polymer heterojunctions?

      Energy Technology Data Exchange (ETDEWEB)

      Bittner, Eric R. [Department of Chemistry and Texas Center for Superconductivity, University of Houston, Houston, TX 77204 (United States)], E-mail: bittner@uh.edu; Burghardt, Irene [Departement de Chimie, Ecole Normale Superieure, 24 rue Lhomond, F-75231 Paris cedex 05 (France); Friend, Richard H. [Cavendish Laboratory, Madingley Road, Cambridge CB3 0HE (United Kingdom)

      2009-02-23

      Time-dependent density functional theory (TD-DFT) is used to examine the effect of stacking in a model semiconducting polymer hetrojunction system consisting of two co-facially stacked oligomers. We find that the excited electronic states are highly sensitive to the alignment of the monomer units of the two chains. In the system we examined, the exchange energy is nearly identical to both the and band off-set at the heterojunction and to the exciton binding energy. Our results indicate that the triplet excitonic states are nearly degenerate with the singlet exciplex states opening the possibility for the interconversion of singlet and triplet electronic states at the heterojunction interface via spin-orbit coupling localized on the heteroatoms. Using Russell-Saunders theory, we estimate this interconversion rate to be approximately 700-800 ps, roughly a 5-10-fold increase compared to isolated organic polymer chains.

    • Excited-state dynamics of a ruthenium(II) catalyst studied by transient photofragmentation in gas phase and transient absorption in solution

      Energy Technology Data Exchange (ETDEWEB)

      Imanbaew, D.; Nosenko, Y. [Fachbereich Chemie, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 52–54, 67663 Kaiserslautern (Germany); Forschungszentrum OPTIMAS, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern (Germany); Kerner, C. [Fachbereich Chemie, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 52–54, 67663 Kaiserslautern (Germany); Chevalier, K.; Rupp, F. [Fachbereich Physik, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern (Germany); Riehn, C., E-mail: riehn@chemie.uni-kl.de [Fachbereich Chemie, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 52–54, 67663 Kaiserslautern (Germany); Forschungszentrum OPTIMAS, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern (Germany); Thiel, W.R. [Fachbereich Chemie, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 52–54, 67663 Kaiserslautern (Germany); Diller, R. [Fachbereich Physik, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern (Germany)

      2014-10-17

      Graphical abstract: - Highlights: • Ultrafast dynamics of new Ru(II) catalysts investigated in gas phase and solution. • Catalyst activation (HCl loss) achieved in ion trap by UV photoexcitation. • Electronic relaxation proceeds by IVR and IC followed by ground state dissociation. • No triplet formation in contrast to other Ru-polypyridine complexes. • Solvent prohibits catalyst activation in solution by fast vibrational cooling. - Abstract: We report studies on the excited state dynamics of new ruthenium(II) complexes [(η{sup 6}-cymene)RuCl(apypm)]PF{sub 6} (apypm=2-NR{sub 2}-4-(pyridine-2-yl)-pyrimidine, R=CH{sub 3} (1)/H (2)) which, in their active form [1{sup +}-HCl] and [2{sup +}-HCl], catalyze the transfer hydrogenation of arylalkyl ketones in the absence of a base. The investigations encompass femtosecond pump–probe transient mass spectrometry under isolated conditions and transient absorption spectroscopy in acetonitrile solution, both on the cations [(η{sup 6}-cymene)RuCl(apypm)]{sup +} (1{sup +}, 2{sup +}). Gas phase studies on mass selected ions were performed in an ESI ion trap mass spectrometer by transient photofragmentation, unambiguously proving the formation of the activated catalyst species [1{sup +}-HCl] or [2{sup +}-HCl] after photoexcitation being the only fragmentation channel. The primary excited state dynamics in the gas phase could be fitted to a biexponential decay, yielding time constants of <100 fs and 1–3 ps. Transient absorption spectroscopy performed in acetonitrile solution using femtosecond UV/Vis and IR probe laser pulses revealed additional deactivation processes on longer time scales (∼7–12 ps). However, the formation of the active catalyst species after photoexcitation could not be observed in solution. The results from both studies are compared to former CID investigations and DFT calculations concerning the activation mechanism.

    • Reliable Prediction with Tuned Range-Separated Functionals of the Singlet-Triplet Gap in Organic Emitters for Thermally Activated Delayed Fluorescence (TADF)

      KAUST Repository

      Sun, Haitao; Zhong, Cheng; Bredas, Jean-Luc

      2015-01-01

      excited states. Here, we demonstrate that time-dependent density functional theory (TD-DFT) in the Tamm-Dancoff Approximation can be very successful in the calculations of the lowest singlet and triplet excitation energies and the corresponding singlet

    • Thickness dependence of the triplet spin-valve effect in superconductor-ferromagnet heterostructures

      Energy Technology Data Exchange (ETDEWEB)

      Lenk, Daniel; Zdravkov, Vladimir I.; Kehrle, Jan; Obermeier, Guenther; Krug von Nidda, Hans-Albrecht; Mueller, Claus; Horn, Siegfried; Tidecks, Reinhard [Institut fuer Physik, Universitaet Augsburg (Germany); Morari, Roman [Institut fuer Physik, Universitaet Augsburg (Germany); D. Ghitsu Institute of Electronic Engineering and Nanotechnologies ASM, Kishinev (Moldova, Republic of); Sidorenko, Anatolie S. [D. Ghitsu Institute of Electronic Engineering and Nanotechnologies ASM, Kishinev (Moldova, Republic of); Tagirov, Lenar [Solid State Physics Department, Kazan Federal University (Russian Federation)

      2015-07-01

      We investigated the triplet spin-valve effect in nanoscale layered S/F{sub 1}/N/F{sub 2}/AF heterostructures with varying F{sub 1}-layer thickness (where S=Nb is a singlet superconducting, F{sub 1}=Cu{sub 41}Ni{sub 59} and F{sub 2}=Co a ferromagnetic, and N a normal-conducting, non-magnetic layer). The theory predicts a long-range, odd-in-frequency triplet component of superconductivity at non-collinear alignment of the magnetizations of F{sub 1} and F{sub 2}. This triplet component exhausts the singlet state and, thus, lowers the superconducting transition temperature, T{sub c}, yielding a global minimum of T{sub c} close to the perpendicular mutual orientations of the magnetizations. We found an oscillating decay of T{sub c} suppression, due to the generation of the triplet component, with increasing F{sub 1} layer thickness, which we discuss in the framework of recent theories.

    • Non-linear advanced control of the LHC inner triplet heat exchanger test unit

      International Nuclear Information System (INIS)

      Vinuela, E. Blanco; Cubillos, J. Casas; Prada Moraga, C. de; Cristea, S.

      2002-01-01

      The future Large Hadron Collider (LHC) at CERN will include eight interaction region final focus magnet systems, the so-called 'Inner Triplet', one on each side of the four beam collision points. The Inner Triplets will be cooled in a static bath of pressurized He II nominally at 1.9 K. This temperature is a control parameter and has very severe constraints in order to avoid the transition from the superconducting to normal resistive state. The main difference in these special zones with respect to a regular LHC cell is higher dynamic heat load unevenly distributed which modifies largely the process characteristics and hence the controller performance. Several control strategies have already been tested at CERN in a pilot plant (LHC String Test) which reproduced a LHC half-cell. In order to validate a common control structure along the whole LHC ring, a Nonlinear Model Predictive Control (NMPC) has been developed and implemented in the Inner Triplet Heat Exchanger Unit (IT-HXTU) at CERN. Automation of the Inner Triplet setup and the advanced control techniques deployed based on the Model Based Predictive Control (MBPC) principle are presented

    • Triplet pregnancies in a southeastern Nigerian Hospital: Before the ...

      African Journals Online (AJOL)

      of triplet pregnancy of 0.1% or 1 triplet pregnancy in 1051 deliveries. ... The babies had a weight range of 0.6–3.4 kg, with an average weight of 1.73 kg. ... outcome of these pregnancies, especially now that the incidence is bound to increase ...

    • Quantum Monte Carlo study of the singlet-triplet transition in ethylene

      International Nuclear Information System (INIS)

      El Akramine, Ouafae; Kollias, Alexander C.; Lester, William A. Jr.

      2003-01-01

      A theoretical study is reported of the transition between the ground state ( 1 A g ) and the lowest triplet state (1 3 B 1u ) of ethylene based on the diffusion Monte Carlo (DMC) variant of the quantum Monte Carlo method. Using DMC trial functions constructed from Hartree-Fock, complete active space self-consistent field and multi-configuration self-consistent field wave functions, we have computed the atomization energy and the heat of formation of both states, and adiabatic and vertical energy differences between these states using both all-electron and effective core potential DMC. The ground state atomization energy and heat of formation are found to agree with experiment to within the error bounds of the computation and experiment. Predictions by DMC of the triplet state atomization energy and heat of formation are presented. The adiabatic singlet-triplet energy difference is found to differ by 5 kcal/mol from the value obtained in a recent photodissociation experiment

    • Triplet leptogenesis in left–right symmetric seesaw models

      International Nuclear Information System (INIS)

      Hällgren, Tomas; Konstandin, Thomas; Ohlsson, Tommy

      2008-01-01

      We discuss scalar triplet leptogenesis in a specific left–right symmetric seesaw model. We show that the Majorana phases that are present in the model can be effectively used to saturate the existing upper limit on the CP-asymmetry of the triplets. We solve the relevant Boltzmann equations and analyze the viability of triplet leptogenesis. It is known for this kind of scenario that the efficiency of leptogenesis is maximal if there exists a hierarchy between the branching ratios of the triplet decays into leptons and Higgs particles. We show that triplet leptogenesis typically favors branching ratios with not too strong hierarchies, since maximal efficiency can only be obtained at the expense of suppressed CP-asymmetries

    • Photo-excited charge collection spectroscopy probing the traps in field-effect transistors

      CERN Document Server

      Im, Seongil; Kim, Jae Hoon

      2013-01-01

      Solid state field-effect devices such as organic and inorganic-channel thin-film transistors (TFTs) have been expected to promote advances in display and sensor electronics. The operational stabilities of such TFTs are thus important, strongly depending on the nature and density of charge traps present at the channel/dielectric interface or in the thin-film channel itself. This book contains how to characterize these traps, starting from the device physics of field-effect transistor (FET). Unlike conventional analysis techniques which are away from well-resolving spectral results, newly-introduced photo-excited charge-collection spectroscopy (PECCS) utilizes the photo-induced threshold voltage response from any type of working transistor devices with organic-, inorganic-, and even nano-channels, directly probing on the traps. So, our technique PECCS has been discussed through more than ten refereed-journal papers in the fields of device electronics, applied physics, applied chemistry, nano-devices and materia...

    • In-Situ Photoexcitation-Induced Suppression of Point Defect Generation in Ion Implanted Silicon

      International Nuclear Information System (INIS)

      Cho, C.R.; Rozgonyi, G.A.; Yarykin, N.; Zuhr, R.A.

      1999-01-01

      The formation of vacancy-related defects in n-type silicon has been studied immediately after implantation of He, Si, or Ge ions at 85 K using in-situ DLTS. A-center concentrations in He-implanted samples reach a maximum immediately after implantation, whereas, with Si or Ge ion implanted samples they continuously increase during subsequent anneals. It is proposed that defect clusters, which emit vacancies during anneals, are generated in the collision cascades of Si or Ge ions. An illumination-induced suppression of A-center formation is seen immediately after implantation of He ions at 85 K. This effect is also observed with Si or Ge ions, but only after annealing. The suppression of vacancy complex formation via photoexcitation is believed to occur due to an enhanced recombination of defects during ion implantation, and results in reduced number of vacancies remaining in the defect clusters. In p-type silicon, a reduction in K-center formation and an enhanced migration of defects are concurrently observed in the illuminated sample implanted with Si ions. These observations are consistent with a model where the injection of excess carriers modifies the defect charge state and impacts their diffusion

    • Photoexcitation electron paramagnetic resonance studies on nickel-related defects in diamond

      CERN Document Server

      Pereira, R N; Neves, A J; Sobolev, N A

      2003-01-01

      Measurements of the electron paramagnetic resonance (EPR) upon photoexcitation are reported on Ni defects in diamonds grown with Ni-containing solvent/catalysts. The temperature dependence of the W8 EPR spectrum photoquenching shows that the relaxation of substitutional Ni sub s sup - upon electron ionization is very small, corroborating the interpretation that the previously reported photoinduced effects with thresholds at 2.5 and 3.0 eV correspond to two complementary photoionization transitions involving Ni sub s. Photoinduced behaviour of the NIRIM1 EPR centre favours the interstitial Ni sub i sup + model for this defect and suggests that the Ni sub i sup 0 sup / sup + level is located at 1.98 +- 0.03 eV below the conduction band. In N-doped diamond, Ni sub i is more likely to appear in the neutral state, undetectable by EPR, whereas at substitutional sites Ni sub s sup - is revealed. Observation of a strong AB2 EPR signal photoquenching and simultaneous detection of different spectral dependencies of the...

    • Even-parity spin-triplet pairing by purely repulsive interactions for orbitally degenerate correlated fermions

      International Nuclear Information System (INIS)

      Zegrodnik, M; Bünemann, J; Spałek, J

      2014-01-01

      We demonstrate the stability of the spin-triplet paired s-wave (with an admixture of extended s-wave) state for the limit of purely repulsive interactions in a degenerate two-band Hubbard model of correlated fermions. The repulsive interactions limit represents an essential extension of our previous analysis (2013 New J. Phys. 15 073050), regarded here as I. We also show that near the half-filling the considered type of superconductivity can coexist with antiferromagnetism. The calculations have been carried out with the use of the so-called statistically consistent Gutzwiller approximation (SGA) for the case of a square lattice. We suggest that the electron correlations in conjunction with the Hund's rule exchange play the crucial role in stabilizing the real-space spin-triplet superconducting state. A sizable hybridization of the bands suppresses the homogeneous paired state. (paper)

    • The effect of gold nanoparticles on exchange processes in collision complexes of triplet and singlet oxygen molecules with excited eosin molecules

      Science.gov (United States)

      Bryukhanov, V. V.; Minaev, B. M.; Tsibul'nikova, A. V.; Slezhkin, V. A.

      2015-07-01

      We have studied exchange processes in contact complexes of triplet eosin molecules with oxygen molecules in the triplet (3Σ{/g -}) and singlet (1Δ g ) states in thin polyvinylbutyral films in the presence of gold nanoparticles. Upon resonant excitation of surface plasmons in gold nanoparticles into the absorption band of eosin molecules-singlet oxygen sensitizers-we have obtained an increase in the intensity of the delayed fluorescence and an increase in the lifetime of the dye with simultaneous quenching of the luminescence of singlet oxygen. The kinetics of the delayed fluorescence of the dye as a result of singlet-triplet annihilation of triplet eosin molecules with singlet oxygen molecules has been investigated. To compare theoretical and experimental data, we have numerically simulated energy transfer processes. Rate constants of energy transfer and of singlet-triplet annihilation, as well as quenching constants of triplet states of the dye by molecular oxygen, have been calculated. Luminescence quantum yield 1Δ g of polyvinylbutyral has been estimated. We have analyzed quantum-chemically electronic mechanisms of singlet-triplet annihilation of oxygen and eosin.

    • Triplet-triplet annihilation photon-upconversion: towards solar energy applications.

      Science.gov (United States)

      Gray, Victor; Dzebo, Damir; Abrahamsson, Maria; Albinsson, Bo; Moth-Poulsen, Kasper

      2014-06-14

      Solar power production and solar energy storage are important research areas for development of technologies that can facilitate a transition to a future society independent of fossil fuel based energy sources. Devices for direct conversion of solar photons suffer from poor efficiencies due to spectrum losses, which are caused by energy mismatch between the optical absorption of the devices and the broadband irradiation provided by the sun. In this context, photon-upconversion technologies are becoming increasingly interesting since they might offer an efficient way of converting low energy solar energy photons into higher energy photons, ideal for solar power production and solar energy storage. This perspective discusses recent progress in triplet-triplet annihilation (TTA) photon-upconversion systems and devices for solar energy applications. Furthermore, challenges with evaluation of the efficiency of TTA-photon-upconversion systems are discussed and a general approach for evaluation and comparison of existing systems is suggested.

    • Higgs triplets in the standard model

      International Nuclear Information System (INIS)

      Gunion, J.F.; Vega, R.; Wudka, J.

      1990-01-01

      Even though the standard model of the strong and electroweak interactions has proven enormously successful, it need not be the case that a single Higgs-doublet field is responsible for giving masses to the weakly interacting vector bosons and the fermions. In this paper we explore the phenomenology of a Higgs sector for the standard model which contains both doublet and triplet fields [under SU(2) L ]. The resulting Higgs bosons have many exotic features and surprising experimental signatures. Since a critical task of future accelerators will be to either discover or establish the nonexistence of Higgs bosons with mass below the TeV scale, it will be important to keep in mind the alternative possibilities characteristic of this and other nonminimal Higgs sectors

  1. Triplet to Singleton-A Successful Outcome

    Directory of Open Access Journals (Sweden)

    Priya Varshney

    2014-07-01

    Full Text Available We are presenting a case report of triplet pregnancy in a 25 years old lady, in whom single fetal reduction was done at 10 weeks. At 29 weeks, ultrasonography showed fetal demise of second twin. Conservative management was done, after evaluating the status of second twin. Maternal and fetal monitoring was done with PT INR, Ultrasound Doppler weekly till 33 weeks when an emergency cesarean was done due to preterm labour pains. A healthy baby of 1.8 kg was born along with a macerated IUD of 500 gms. Mother and baby are healthy on follow up till date. Hence conservative management should be followed in single fetus demise in twin pregnancy with proper monitoring.

  2. Terahertz radiation from accelerating charge carriers in graphene under ultrafast photoexcitation

    Science.gov (United States)

    Rustagi, Avinash; Stanton, C. J.

    2016-11-01

    We study the generation of terahertz (THz) radiation from the acceleration of ultrafast photoexcited charge carriers in graphene in the presence of a dc electric field. Our model is based on calculating the transient current density from the time-dependent distribution function which is determined using the Boltzmann transport equation (BTE) within a relaxation time approximation. We include the time-dependent generation of carriers by the pump pulse by solving for the carrier generation rate using the optical Bloch equations in the rotating wave approximation (RWA). The linearly polarized pump pulse generates an anisotropic distribution of photoexcited carriers in the kx-ky plane. The collision integral in the Boltzmann equation includes a term that leads to the thermalization of carriers via carrier-carrier scattering to an effective temperature above the lattice temperature, as well as a cooling term, which leads to energy relaxation via inelastic carrier-phonon scattering. The radiated signal is proportional to the time derivative of the transient current density. In spite of the fact that the magnitude of the velocity is the same for all the carriers in graphene, there is still emitted radiation from the photoexcited charge carriers with frequency components in the THz range due to a change in the direction of velocity of the photoexcited carriers in the external electric field as well as cooling of the photoexcited carriers on a subpicosecond time scale.

  3. Theoretical rationalization of the singlet-triplet gap in OLEDs materials: impact of charge-transfer character.

    Science.gov (United States)

    Moral, M; Muccioli, L; Son, W-J; Olivier, Y; Sancho-García, J C

    2015-01-13

    New materials for OLED applications with low singlet-triplet energy splitting have been recently synthesized in order to allow for the conversion of triplet into singlet excitons (emitting light) via a Thermally Activated Delayed Fluorescence (TADF) process, which involves excited-states with a non-negligible amount of Charge-Transfer (CT). The accurate modeling of these states with Time-Dependent Density Functional Theory (TD-DFT), the most used method so far because of the favorable trade-off between accuracy and computational cost, is however particularly challenging. We carefully address this issue here by considering materials with small (high) singlet-triplet gap acting as emitter (host) in OLEDs and by comparing the accuracy of TD-DFT and the corresponding Tamm-Dancoff Approximation (TDA), which is found to greatly reduce error bars with respect to experiments thanks to better estimates for the lowest singlet-triplet transition. Finally, we quantitatively correlate the singlet-triplet splitting values with the extent of CT, using for it a simple metric extracted from calculations with double-hybrid functionals, that might be applied in further molecular engineering studies.

  4. Steady-state photoconductivity and multi-particle interactions in high-mobility organic semiconductors.

    Science.gov (United States)

    Irkhin, P; Najafov, H; Podzorov, V

    2015-10-19

    Fundamental understanding of photocarrier generation, transport and recombination under a steady-state photoexcitation has been an important goal of organic electronics and photonics, since these processes govern such electronic properties of organic semiconductors as, for instance, photoconductivity. Here, we discovered that photoconductivity of a highly ordered organic semiconductor rubrene exhibits several distinct regimes, in which photocurrent as a function of cw (continuous wave) excitation intensity is described by a power law with exponents sequentially taking values 1, 1/3 and ¼. We show that in pristine crystals this photocurrent is generated at the very surface of the crystals, while the bulk photocurrent is drastically smaller and follows a different sequence of exponents, 1 and ½. We describe a simple experimental procedure, based on an application of "gauge effect" in high vacuum, that allows to disentangle the surface and bulk contributions to photoconductivity. A model based on singlet exciton fission, triplet fusion and triplet-charge quenching that can describe these non-trivial effects in photoconductivity of highly ordered organic semiconductors is proposed. Observation of these effects in photoconductivity and modeling of the underlying microscopic mechanisms described in this work represent a significant step forward in our understanding of electronic properties of organic semiconductors.

  5. Vibrational Spectroscopy on Photoexcited Dye-Sensitized Films via Pump-Degenerate Four-Wave Mixing.

    Science.gov (United States)

    Abraham, Baxter; Fan, Hao; Galoppini, Elena; Gundlach, Lars

    2018-03-01

    Molecular sensitization of semiconductor films is an important technology for energy and environmental applications including solar energy conversion, photocatalytic hydrogen production, and water purification. Dye-sensitized films are also scientifically complex and interesting systems with a long history of research. In most applications, photoinduced heterogeneous electron transfer (HET) at the molecule/semiconductor interface is of critical importance, and while great progress has been made in understanding HET, many open questions remain. Of particular interest is the role of combined electronic and vibrational effects and coherence of the dye during HET. The ultrafast nature of the process, the rapid intramolecular vibrational energy redistribution, and vibrational cooling present complications in the study of vibronic coupling in HET. We present the application of a time domain vibrational spectroscopy-pump-degenerate four-wave mixing (pump-DFWM)-to dye-sensitized solid-state semiconductor films. Pump-DFWM can measure Raman-active vibrational modes that are triggered by excitation of the sample with an actinic pump pulse. Modifications to the instrument for solid-state samples and its application to an anatase TiO 2 film sensitized by a Zn-porphyrin dye are discussed. We show an effective combination of experimental techniques to overcome typical challenges in measuring solid-state samples with laser spectroscopy and observe molecular vibrations following HET in a picosecond time window. The cation spectrum of the dye shows modes that can be assigned to the linker group and a mode that is localized on the Zn-phorphyrin chromophore and that is connected to photoexcitation.

  6. Structure analysis of photo-induced triplet phenylnitrene using synchrotron radiation

    CERN Document Server

    Kawano, M; Uekusa, H; Ohashi, Y; Ozawa, Y; Matsubara, K; Imabayashi, H; Mitsumi, M; Toriumi, K

    2003-01-01

    The crystal structures of [(PhCH sub 2) sub 2 NH sub 2] sup + [m-C sub 6 H sub 4 (N sub 3)-(COO)] sup - before and after UV-irradiation were analyzed at 25 K by using an X-ray vacuum camera set up at the synchrotron laboratory (SPring-8). The C-N (nitrene) bond distance in the triplet state of the photo-induced m-carboxyphenylnitrene is determined to be 1.34(4) A.

  7. Resonance tunneling of charge carriers in photoexcited type-II ZnSe/BeTe heterostructures

    International Nuclear Information System (INIS)

    Zaitsev, S. V.; Maksimov, A. A.; Tartakovskii, I. I.; Yakovlev, D. R.; Waag, A.

    2008-01-01

    In is shown that, at high densities of spatially separated electrons and holes in type-II ZnSe/BeTe heterostructures, the conditions for resonance tunneling of photoexcited holes from the ZnSe layer to the BeTe layer are attainable. Nonlinear behavior of the intensity of the photoluminescence band corresponding to spatially direct optical transitions with photoexcitation intensity is observed. Numerical calculations are carried out, and the results are in good agreement with the experimental data in a wide region of variation of the optical pumping intensity

  8. Third-order spontaneous parametric down-conversion in thin optical fibers as a photon-triplet source

    Energy Technology Data Exchange (ETDEWEB)

    Corona, Maria [Instituto de Ciencias Nucleares, Universidad Nacional Autonoma de Mexico, apdo. postal 70-543, DF 04510 Mexico City (Mexico); Departamento de Optica, Centro de Investigacion Cientifica y de Educacion Superior de Ensenada, Apartado Postal 2732, BC 22860 Ensenada (Mexico); Garay-Palmett, Karina; U' Ren, Alfred B. [Instituto de Ciencias Nucleares, Universidad Nacional Autonoma de Mexico, apdo. postal 70-543, DF 04510 Mexico City (Mexico)

    2011-09-15

    We study the third-order spontaneous parametric down-conversion (TOSPDC) process, as a means to generate entangled photon triplets. Specifically, we consider thin optical fibers as the nonlinear medium to be used as the basis for TOSPDC in configurations where phase matching is attained through the use of more than one fiber transverse modes. Our analysis in this paper, which follows from our earlier paper [Opt. Lett. 36, 190-192 (2011)], aims to supply experimentalists with the details required in order to design a TOSPDC photon-triplet source. Specifically, our analysis focuses on the photon triplet state, on the rate of emission, and on the TOSPDC phase-matching characteristics for the cases of frequency-degenerate and frequency nondegenerate TOSPDC.

  9. Comparison of the Minutiae Quadruplets and Minutiae Triplets

    African Journals Online (AJOL)

    Identifying distorted fingerprint images is a major problem in fingerprint recog- nition systems. Several techniques, such as the minutiae triplets technique, have been proposed ..... ference on Biometric Technology for Human. Identification IV.

  10. Higher-Spin Triplet Fields and String Theory

    Directory of Open Access Journals (Sweden)

    D. Sorokin

    2010-01-01

    Full Text Available We review basic properties of reducible higher-spin multiplets, called triplets, and demonstrate how they naturally appear as part of the spectrum of String Field Theory in the tensionless limit. We show how in the frame-like formulation the triplet fields are endowed with the geometrical meaning of being components of higher-spin vielbeins and connections and present actions describing their free dynamics.

  11. Singlet-triplet splittings from the virial theorem and single-particle excitation energies

    Science.gov (United States)

    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.

  12. Delocalization of Coherent Triplet Excitons in Linear Rigid Rod Conjugated Oligomers.

    Science.gov (United States)

    Hintze, Christian; Korf, Patrick; Degen, Frank; Schütze, Friederike; Mecking, Stefan; Steiner, Ulrich E; Drescher, Malte

    2017-02-02

    In this work, the triplet state delocalization in a series of monodisperse oligo(p-phenyleneethynylene)s (OPEs) is studied by pulsed electron paramagnetic resonance (EPR) and pulsed electron nuclear double resonance (ENDOR) determining zero-field splitting, optical spin polarization, and proton hyperfine couplings. Neither the zero-field splitting parameters nor the optical spin polarization change significantly with OPE chain length, in contrast to the hyperfine coupling constants, which showed a systematic decrease with chain length n according to a 2/(1 + n) decay law. The results provide striking evidence for the Frenkel-type nature of the triplet excitons exhibiting full coherent delocalization in the OPEs under investigation with up to five OPE repeat units and with a spin density distribution described by a nodeless particle in the box wave function. The same model is successfully applied to recently published data on π-conjugated porphyrin oligomers.

  13. Theoretical study of the triplet excited state of PtPOP and the exciplexes M-PtPOP (M = Tl, Ag) in solution and comparison with ultrafast X-ray scattering results

    DEFF Research Database (Denmark)

    Kong, Qingyu; Kjær, Kasper S.; Haldrup, Martin Kristoffer

    2012-01-01

    The [Pt2(H2P2O5)4]4− ions in the ground and excited states and the excited-state complexes M-[Pt2(H2P2O5)4]3− and M2-[Pt2(H2P2O5)4]2− (M = Ag, Tl) were studied in solution with various density functional theory (DFT) functionals from Gaussian 09 and Amsterdam Density Functional (ADF) programs. Ca...

  14. Quasiclassical treatment and odd-parity/triplet correspondence in topological superconductors

    International Nuclear Information System (INIS)

    Nagai, Yuki; Nakamura, Hiroki; Machida, Masahiko

    2014-01-01

    We construct a quasiclassical framework for topological superconductors with a strong spin–orbit coupling such as Cu x Bi 2 Se 3 . In a manner of the quasiclassical treatment, by decomposing the slowly varying component from a total quasiparticle wave function, the original massive Dirac Bogoliubov–de Gennes (BdG) Hamiltonian derived from a tight-binding model represented by an 8 × 8 matrix is reduced to a 4 × 4 matrix. The resultant equations are equivalent to Andreev-type equations of singlet or triplet superconductors, in which the apparent spin–orbit coupling vanishes. Using this formalism, we find that the odd-parity superconductivity in topological superconductors turns to the spin-triplet one. Moreover, in terms of quasiclassical treatment, we show that the topologically-protected zero-energy states in topological superconductors have correspond to the Andreev bound states established in a long history of studies of unconventional superconductors. This clearly indicates that low-energy nontrivial superconducting properties in the topological superconductors can be analyzed using established theoretical descriptions of the spin-triplet superconductors. (author)

  15. Analysis of Triplet Exciton Loss Pathways in PTB7:PC71BM Bulk Heterojunction Solar Cells

    Science.gov (United States)

    Kraus, Hannes; Heiber, Michael C.; Väth, Stefan; Kern, Julia; Deibel, Carsten; Sperlich, Andreas; Dyakonov, Vladimir

    2016-07-01

    A strategy for increasing the conversion efficiency of organic photovoltaics has been to increase the VOC by tuning the energy levels of donor and acceptor components. However, this opens up a new loss pathway from an interfacial charge transfer state to a triplet exciton (TE) state called electron back transfer (EBT), which is detrimental to device performance. To test this hypothesis, we study triplet formation in the high performing PTB7:PC71BM blend system and determine the impact of the morphology-optimizing additive 1,8-diiodoctane (DIO). Using photoluminescence and spin-sensitive optically detected magnetic resonance (ODMR) measurements at low temperature, we find that TEs form on PC71BM via intersystem crossing from singlet excitons and on PTB7 via EBT mechanism. For DIO blends with smaller fullerene domains, an increased density of PTB7 TEs is observed. The EBT process is found to be significant only at very low temperature. At 300 K, no triplets are detected via ODMR, and electrically detected magnetic resonance on optimized solar cells indicates that TEs are only present on the fullerenes. We conclude that in PTB7:PC71BM devices, TE formation via EBT is impacted by fullerene domain size at low temperature, but at room temperature, EBT does not represent a dominant loss pathway.

  16. On static triplet structures in fluids with quantum behavior

    Science.gov (United States)

    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.

  17. Abnormal maternal echocardiographic findings in triplet pregnancies presenting with dyspnoea.

    Science.gov (United States)

    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 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.

  18. Impact of Dielectric Constant on the Singlet-Triplet Gap in Thermally Activated Delayed Fluorescence (TADF) Materials

    KAUST Repository

    Sun, Haitao; Hu, Zhubin; Zhong, Cheng; Chen, Xiankai; Sun, Zhenrong; Bredas, Jean-Luc

    2017-01-01

    Thermally activated delayed fluorescence (TADF) relies on the presence of a very small energy gap, ΔEST, between the lowest singlet and triplet excited states. ΔEST is thus a key factor in the molecular design of more efficient materials. However

  19. Comparative analysis of magnetic resonance in the polaron pair recombination and the triplet exciton-polaron quenching models

    Science.gov (United States)

    Mkhitaryan, V. V.; Danilović, D.; Hippola, C.; Raikh, M. E.; Shinar, J.

    2018-01-01

    We present a comparative theoretical study of magnetic resonance within the polaron pair recombination (PPR) and the triplet exciton-polaron quenching (TPQ) models. Both models have been invoked to interpret the photoluminescence detected magnetic resonance (PLDMR) results in π -conjugated materials and devices. We show that resonance line shapes calculated within the two models differ dramatically in several regards. First, in the PPR model, the line shape exhibits unusual behavior upon increasing the microwave power: it evolves from fully positive at weak power to fully negative at strong power. In contrast, in the TPQ model, the PLDMR is completely positive, showing a monotonic saturation. Second, the two models predict different dependencies of the resonance signal on the photoexcitation power, PL. At low PL, the resonance amplitude Δ I /I is ∝PL within the PPR model, while it is ∝PL2 crossing over to PL3 within the TPQ model. On the physical level, the differences stem from different underlying spin dynamics. Most prominently, a negative resonance within the PPR model has its origin in the microwave-induced spin-Dicke effect, leading to the resonant quenching of photoluminescence. The spin-Dicke effect results from the spin-selective recombination, leading to a highly correlated precession of the on-resonance pair partners under the strong microwave power. This effect is not relevant for TPQ mechanism, where the strong zero-field splitting renders the majority of triplets off resonance. On the technical level, the analytical evaluation of the line shapes for the two models is enabled by the fact that these shapes can be expressed via the eigenvalues of a complex Hamiltonian. This bypasses the necessity of solving the much larger complex linear system of the stochastic Liouville equations. Our findings pave the way towards a reliable discrimination between the two mechanisms via cw PLDMR.

  20. Relationship between the catalytic activity of Pt/alumina and the relaxation process of the photoexcited electrons

    Energy Technology Data Exchange (ETDEWEB)

    Ito, Junji, E-mail: j-itou@mail.nissan.co.jp [Advanced Materials Laboratory, Nissan Research Center, NISSAN MOTOR CO., LTD., 1 Natsushima-cho, Yokosuka-shi, Kanagawa 237-8523 (Japan); Department of Applied Physics and Chemistry, The University of Electro-Communications, 1-5-1 Chofugaoka, Chofu, Tokyo 182-8585 (Japan); Hanaki, Yasunari [Advanced Materials Laboratory, Nissan Research Center, NISSAN MOTOR CO., LTD., 1 Natsushima-cho, Yokosuka-shi, Kanagawa 237-8523 (Japan); Shen, Qing [Department of Applied Physics and Chemistry, The University of Electro-Communications, 1-5-1 Chofugaoka, Chofu, Tokyo 182-8585 (Japan); Department of Engineering Science, The University of Electro-Communications, 1-5-1 Chofugaoka, Chofu, Tokyo 182-8585 (Japan); PRESTO, Japan Science and Technology Agency (JST), 4-1-8 Honcho, Kawaguchi, Saitama 332-0012 (Japan); Toyoda, Taro [Department of Applied Physics and Chemistry, The University of Electro-Communications, 1-5-1 Chofugaoka, Chofu, Tokyo 182-8585 (Japan); Department of Engineering Science, The University of Electro-Communications, 1-5-1 Chofugaoka, Chofu, Tokyo 182-8585 (Japan)

    2012-12-15

    Highlights: Black-Right-Pointing-Pointer We determined the decay time of photoexcited electrons of Pt/Al{sub 2}O{sub 3}. Black-Right-Pointing-Pointer Faster decay of excited electrons in Pt/Al{sub 2}O{sub 3} leads to its faster oxidation rate. Black-Right-Pointing-Pointer Decreasing excited electron lifetime in Pt/Al{sub 2}O{sub 3} may decrease Pt consumption in catalytic convertors. - Abstract: In order to decrease the consumption of precious metals used in the catalytic converters used in automobiles, we studied the relationship between the catalytic activity of Pt/alumina (Pt/Al{sub 2}O{sub 3}) and the relaxation process of photoexcited electrons. Firstly, we studied the relationship between the size of the Pt particles in Pt/Al{sub 2}O{sub 3} and catalytic performance. Secondly, the relationship between the size of the Pt particles in Pt/Al{sub 2}O{sub 3} and the decay time of the excited electrons was studied using an improved transient grating (TG) technique. The results showed that faster decay of the excited electrons leads to greater oxidation rates. The decay time obtained with the improved TG technique gives an indication of the time that the exited electrons take to return to the ground state. According to studies utilizing FT-IR, one of the processes necessary for quickly generating CO{sub 2} with Pt is that the electron in the Pt-O bond moves to the Pt side and that the Pt{sup +} becomes Pt metal. Thus, the decay time obtained with the improved TG technique corresponds to the process whereby Pt{sup +} returns to Pt metal. Thus, we found that the consumption of precious metals can be reduced by increasing the speed of the decay of the excited electrons.

  1. Relationship between the catalytic activity of Pt/alumina and the relaxation process of the photoexcited electrons

    International Nuclear Information System (INIS)

    Ito, Junji; Hanaki, Yasunari; Shen, Qing; Toyoda, Taro

    2012-01-01

    Highlights: ► We determined the decay time of photoexcited electrons of Pt/Al 2 O 3 . ► Faster decay of excited electrons in Pt/Al 2 O 3 leads to its faster oxidation rate. ► Decreasing excited electron lifetime in Pt/Al 2 O 3 may decrease Pt consumption in catalytic convertors. - Abstract: In order to decrease the consumption of precious metals used in the catalytic converters used in automobiles, we studied the relationship between the catalytic activity of Pt/alumina (Pt/Al 2 O 3 ) and the relaxation process of photoexcited electrons. Firstly, we studied the relationship between the size of the Pt particles in Pt/Al 2 O 3 and catalytic performance. Secondly, the relationship between the size of the Pt particles in Pt/Al 2 O 3 and the decay time of the excited electrons was studied using an improved transient grating (TG) technique. The results showed that faster decay of the excited electrons leads to greater oxidation rates. The decay time obtained with the improved TG technique gives an indication of the time that the exited electrons take to return to the ground state. According to studies utilizing FT-IR, one of the processes necessary for quickly generating CO 2 with Pt is that the electron in the Pt-O bond moves to the Pt side and that the Pt + becomes Pt metal. Thus, the decay time obtained with the improved TG technique corresponds to the process whereby Pt + returns to Pt metal. Thus, we found that the consumption of precious metals can be reduced by increasing the speed of the decay of the excited electrons.

  2. Bond Shortening (1.4 Å) in the Singlet and Triplet Excited States of [Ir2(dimen)4]2+ in Solution Determined by Time-Resolved X-ray Scattering

    DEFF Research Database (Denmark)

    Haldrup, Martin Kristoffer; Harlang, Tobias; Christensen, Morten

    2011-01-01

    Ground- and excited-state structures of the bimetallic, ligand-bridged compound Ir2(dimen)42+ are investigated in acetonitrile by means of time-resolved X-ray scattering. Following excitation by 2 ps laser pulses at 390 nm, analysis of difference scattering patterns obtained at eight different ti...

  3. Singlet and Triplet Excitation Management in a Bichromophoric Near-Infrared-Phosphorescent BODIPY-Benzoporphyrin Platinum Complex

    KAUST Repository

    Whited, Matthew 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 transfer processes (k ST(1BDP→1Por) = 7.8×1011 s-1, kTT(3Por→3BDP) = 1.0×1010 s-1, kTT(3BDP→ 3Por) = 1.6×1010 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 (λem = 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. © 2010 American Chemical Society.

  4. Butterfly Deformation Modes in a Photoexcited Pyrazolate-Bridged Pt Complex Measured by Time-Resolved X-Ray Scattering in Solution

    DEFF Research Database (Denmark)

    Haldrup, Kristoffer; Dohn, Asmus Ougaard; Shelby, Megan L.

    2016-01-01

    the monochromatic X-ray pulses at Beamline 11IDD of the Advanced Photon Source. The excited-state structural analysis of 1 was performed based on the results from both transient WAXS measurements and density functional theory calculations to shed light on the primary structural changes in its triplet metal-metal...... excited state has remained scarce. Using time-resolved wide-angle X-ray scattering (WAXS), the excited triplet state molecular structure of [Pt(ppy)(μ-t-Bu2pz)]2 (ppy = 2-phenylpyridine; t-Bu2pz = 3,5-di-tert-butylpyrazolate), complex 1, was obtained in a dilute (0.5 mM) toluene solution utilizing...

  5. TDDFT study on intramolecular hydrogen bond of photoexcited methyl salicylate.

    Science.gov (United States)

    Qu, Peng; Tian, Dongxu

    2014-01-01

    The equilibrium geometries, IR-spectra and transition mechanism of intramolecular hydrogen-bonded methyl salicylate in excited state were studied using DFT and TDDFT with 6-31++G (d, p) basis set. The length of hydrogen bond OH⋯OC is decreased from 1.73 Å in the ground state to 1.41 and 1.69 Å in the excited S1 and S3 states. The increase of bond length for HO and CO group also indicates that in excited state the hydrogen bond OH⋯OC is strengthened. IR spectra show HO and CO stretching bands are strongly redshifted by 1387 and 67 cm(-1) in the excited S1 and S3 states comparing to the ground state. The excitation energy and the absorption spectrum show the S3 state is the main excited state of the low-lying excited states. By analyzing the frontier molecular orbitals, the transition from the ground state to the excited S1 and S3 states was predicted to be the π→π∗ mode. Copyright © 2013 Elsevier B.V. All rights reserved.

  6. Superconductivity switch from spin-singlet to -triplet pairing in a topological superconducting junction

    Science.gov (United States)

    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.

  7. Interplanetary medium and geomagnetic activity after compact flare triplets 1966-1981

    International Nuclear Information System (INIS)

    Ivanov, K.G.; Mikerina, N.V.; Pavlov, P.P.

    1986-01-01

    The interplanetary medium state and geomagnetic activity when the Earth is getting into this or that interplanetary disturbance zone after flare triplets, i.e. trains of three solar flares out of an active zone, are considered. There are the following conditionally differentiated zones in the interplanetary disturbance configuration: a forbidden (F), a perturbed (P) and a normal (N) zones of interplanetary disturbance. The interplanetary medium disturbances and geomagnetic activity after trains of three flares of class 2 and higher out of one of active zones depend on the following factors: the magnetic axis orientation of a bipolar group of active zone spots appeared after flares, time interval between the first and second flares in the train, flare intensity. The conditions of maximum disturbance occurrence pointed out. The interplanetary and geomagnetic disturbance intensity in the N zone is higher than that of the F and P zones (i.e. in the proximity of the great circle planes passing through the flares parallel with tha active zone magnetic axes), and it is higher after quasicompact rather than after compact triplets (i.e. it considerably grows when passing over the critical value of the time interval betwenn the first and second triplet flares, τ 12 =16 h)

  8. Photochemical transformation of benzotriazole, relevant to sunlit surface waters: Assessing the possible role of triplet-sensitised processes

    Energy Technology Data Exchange (ETDEWEB)

    Bianco, Angelica [Clermont Université, Université Blaise Pascal, Institut de Chimie de Clermont-Ferrand, BP 10448, F-63000 Clermont-Ferrand (France); Fabbri, Debora; Minella, Marco [Università degli Studi di Torino, Dipartimento di Chimica, Via P. Giuria 5, 10125 Turin (Italy); Brigante, Marcello, E-mail: marcello.brigante@univ-bpclermont.fr [Clermont Université, Université Blaise Pascal, Institut de Chimie de Clermont-Ferrand, BP 10448, F-63000 Clermont-Ferrand (France); CNRS, UMR 6296, ICCF, BP 80026, F-63177 Aubière (France); Mailhot, Gilles [Clermont Université, Université Blaise Pascal, Institut de Chimie de Clermont-Ferrand, BP 10448, F-63000 Clermont-Ferrand (France); CNRS, UMR 6296, ICCF, BP 80026, F-63177 Aubière (France); Maurino, Valter; Minero, Claudio [Università degli Studi di Torino, Dipartimento di Chimica, Via P. Giuria 5, 10125 Turin (Italy); Vione, Davide, E-mail: davide.vione@unito.it [Università degli Studi di Torino, Dipartimento di Chimica, Via P. Giuria 5, 10125 Turin (Italy); Università degli Studi di Torino, Centro Interdipartimentale NatRisk, Via L. Da Vinci 44, 10095 Grugliasco (Italy)

    2016-10-01

    The corrosion inhibitor 1H-benzotriazole (pK{sub a} = 8.4) can exist in two different forms in natural waters, and photochemical transformation is a potentially significant attenuation pathway for both of them. Depending on conditions, the modelled half-life times range from some days/weeks to several months. In sunlit water bodies, the acidic (neutral) form would undergo direct photolysis (accounting for up to 7% of total phototransformation) and, most notably, reaction with the hydroxyl radicals ({sup ·}OH) and the triplet states of chromophoric dissolved organic matter ({sup 3}CDOM*). The basic (anionic) form would undergo significant transformation with {sup ·}OH and {sup 3}CDOM*. The {sup ·}OH reactions would be more important at low dissolved organic carbon (DOC) and the {sup 3}CDOM* processes at high DOC. In the presence of highly reactive triplet-state model compounds, the two benzotriazole forms react with similar rate constants. In this case, they would show comparable half-life times in surface-water environments. With less reactive triplet states, the rate constant of the anionic form can be a couple of orders of magnitude higher than that of the neutral one. Under these circumstances, the neutral form could be considerably more photostable than the anionic one at high DOC. Therefore, depending on {sup 3}CDOM* reactivity, the solution pH may or may not play an important role in the photoattenuation kinetics of 1H-benzotriazole in sunlit natural waters, especially at high DOC. Both forms of benzotriazole yield hydroxyderivatives as their main transformation intermediates under all the relevant photochemical reaction pathways. These intermediates could be formed via {sup ·}OH-induced hydroxylation, or upon electron abstraction followed by reaction with water. Differently from UVC irradiation data reported in previous studies, the concentration of aniline upon excitation of 1H-benzotriazole under environmentally significant UV wavelengths was always

  9. Photochemical transformation of benzotriazole, relevant to sunlit surface waters: Assessing the possible role of triplet-sensitised processes

    International Nuclear Information System (INIS)

    Bianco, Angelica; Fabbri, Debora; Minella, Marco; Brigante, Marcello; Mailhot, Gilles; Maurino, Valter; Minero, Claudio; Vione, Davide

    2016-01-01

    The corrosion inhibitor 1H-benzotriazole (pK a = 8.4) can exist in two different forms in natural waters, and photochemical transformation is a potentially significant attenuation pathway for both of them. Depending on conditions, the modelled half-life times range from some days/weeks to several months. In sunlit water bodies, the acidic (neutral) form would undergo direct photolysis (accounting for up to 7% of total phototransformation) and, most notably, reaction with the hydroxyl radicals ( · OH) and the triplet states of chromophoric dissolved organic matter ( 3 CDOM*). The basic (anionic) form would undergo significant transformation with · OH and 3 CDOM*. The · OH reactions would be more important at low dissolved organic carbon (DOC) and the 3 CDOM* processes at high DOC. In the presence of highly reactive triplet-state model compounds, the two benzotriazole forms react with similar rate constants. In this case, they would show comparable half-life times in surface-water environments. With less reactive triplet states, the rate constant of the anionic form can be a couple of orders of magnitude higher than that of the neutral one. Under these circumstances, the neutral form could be considerably more photostable than the anionic one at high DOC. Therefore, depending on 3 CDOM* reactivity, the solution pH may or may not play an important role in the photoattenuation kinetics of 1H-benzotriazole in sunlit natural waters, especially at high DOC. Both forms of benzotriazole yield hydroxyderivatives as their main transformation intermediates under all the relevant photochemical reaction pathways. These intermediates could be formed via · OH-induced hydroxylation, or upon electron abstraction followed by reaction with water. Differently from UVC irradiation data reported in previous studies, the concentration of aniline upon excitation of 1H-benzotriazole under environmentally significant UV wavelengths was always below the detection limit of the analytical

  10. Birth weight discordance and perinatal mortality among triplets

    Directory of Open Access Journals (Sweden)

    Egić Amira

    2005-01-01

    Full Text Available INTRODUCTION. The incidence of multiple births has increased in the last decade. Perinatal mortality in triplets is significantly greater than in twin and singleton births. OBJECTIVE. The objective of this study was to describe the extent of birth weight discordance among triplets and to identify its association with an increased risk of perinatal mortality. METHOD A retrospective analysis of triplet births, for the period 1993-2003, was conducted at the Gynaecological-Obstetric Clinic "Narodni Front" in Belgrade. Birth weight discordance was defined as the difference in birth weight between the largest and the smallest triplet's weight of more than 20%. RESULTS. The rate of triplets has increased by almost 75% between the first (7.7% and the last (29.6% 5-year period of the last decade. Triplets are becoming more common because of the frequent use of assisted reproductive technology as a treatment for infertility. In the period 1993-2003, there were a total of 40 triplet live births (24 weeks and greater with incidence of 0.06%. There was no clear association between maternal age, parity, method of conception, birth gestational age, and disorders complicating pregnancy with birth discordance more than 20%. Regarding birth weight groups, statistical significance occurred only in the <999 grams group for discordant and in the 2000-2499 grams group for concordant triplets. Overall, the perinatal mortality rate in the group was 10.8%, the foetal mortality rate was 1.7% (2/120, and the neonatal (0-28 days mortality rate was 9.1% (11/120. An odds ratio of 95% confidence interval shows 3 times greater risk for adverse perinatal outcome in the discordant group. However, the difference was not significant. CONCLUSION. Increasing birth weight discordance may increase the risk of adverse perinatal outcome. Triplet pregnancies, being high risk, require intensive antenatal care in order to prevent preterm delivery and ultrasound in order to diagnose foetal

  11. Analysis of generic insertions made of two symmetric triplets

    CERN Document Server

    D'Amico, T E

    1998-01-01

    This paper reports on the study undertaken to explore the capabilities of a symmetric triplet to achieve the optics constraints required by the inner triplet of an insertion and more generally of a co mplete insertion made of two symmetric triplets to match a double focus to a FODO lattice. It is based on analytical treatment formulating a number of constraints equal to the parameters available. Th is thorough and systematic analysis made it possible to establish for an inner triplet as well as for a complete insertion the existence of solutions and to explicitly find out all the solutions, with out resorting to unguided numerical searches. As a by-product, a lattice transformer, made of a single triplet, that matches two different FODO cells has been singled out and studied in details. The r esults should be profitable in a number of cases. Here, the method is applied to an insertion of the type of an experimental LHC insertion in order to investigate its domain of validity and tunability .

  12. Hybrid spin and valley quantum computing with singlet-triplet qubits.

    Science.gov (United States)

    Rohling, Niklas; Russ, Maximilian; Burkard, Guido

    2014-10-24

    The valley degree of freedom in the electronic band structure of silicon, graphene, and other materials is often considered to be an obstacle for quantum computing (QC) based on electron spins in quantum dots. Here we show that control over the valley state opens new possibilities for quantum information processing. Combining qubits encoded in the singlet-triplet subspace of spin and valley states allows for universal QC using a universal two-qubit gate directly provided by the exchange interaction. We show how spin and valley qubits can be separated in order to allow for single-qubit rotations.

  13. 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

    Science.gov (United States)

    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

  14. Linking photochemistry in the gas and solution phase: S-H bond fission in p-methylthiophenol following UV photoexcitation.

    Science.gov (United States)

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

    2011-01-01

    Gas-phase H (Rydberg) atom photofragment translational spectroscopy and solution-phase femtosecond-pump dispersed-probe transient absorption techniques are applied to explore the excited state dynamics of p-methylthiophenol connecting the short time reactive dynamics in the two phases. The molecule is excited at a range of UV wavelengths from 286 to 193 nm. The experiments clearly demonstrate that photoexcitation results in S-H bond fission--both in the gas phase and in ethanol solution-and that the resulting p-methythiophenoxyl radical fragments are formed with significant vibrational excitation. In the gas phase, the recoil anisotropy of the H atom and the vibrational energy disposal in the p-MePhS radical products formed at the longer excitation wavelengths reveal the operation of two excited state dissociation mechanisms. The prompt excited state dissociation motif appears to map into the condensed phase also. In both phases, radicals are produced in both their ground and first excited electronic states; characteristic signatures for both sets of radical products are already apparent in the condensed phase studies after 50 fs. No evidence is seen for either solute ionisation or proton coupled electron transfer--two alternate mechanisms that have been proposed for similar heteroaromatics in solution. Therefore, at least for prompt S-H bond fissions, the direct observation of the dissociation process in solution confirms that the gas phase photofragmentation studies indeed provide important insights into the early time dynamics that transfer to the condensed phase.

  15. sl(2)-1/2 and the triplet model

    International Nuclear Information System (INIS)

    Ridout, David

    2010-01-01

    Conformal field theories with sl(2) -1/2 symmetry are studied with a view to investigating logarithmic structures. Applying the parafermionic coset construction to the non-logarithmic theory, a part of the structure of the triplet model is uncovered. In particular, the coset theory is shown to admit the triplet W-algebra as a chiral algebra. This motivates the introduction of an augmented sl(2) -1/2 -theory for which the corresponding coset theory is precisely the triplet model. This augmentation is envisaged to lead to a precise characterisation of the 'logarithmic lift' of the non-logarithmic sl(2) -1/2 -theory that has been proposed by Lesage et al.

  16. Triplet Tellurophene-Based Acceptors for Organic Solar Cells.

    Science.gov (United States)

    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.

  17. Effects of triplet Higgs bosons in long baseline neutrino experiments

    Science.gov (United States)

    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.

  18. The activity of 3- and 7-hydroxyflavones as scavengers of superoxide radical anion generated from photo-excited riboflavin

    International Nuclear Information System (INIS)

    Montana, P.; Pappano, N.; Debattista, N.; Avila, V.; Posadaz, A.; Bertolotti, S.G.; Garcia, N.A.

    2003-01-01

    The visible-light irradiation of the system Riboflavin plus 3-hydroxyflavone or plus 7-hydroxyflavone, under aerobic conditions, produces a series of competitive processes that depend on the relative concentrations of the pigment and the flavones. The picture comprises photochemical mechanisms that potentially operate in nature. They mainly include the quenching of Rf singlet ( 1 Rf*) and triplet ( 3 Rf*) excited states (with bimolecular rate constants in the order of 10 9 M -1 s -1 ) and superoxide radical anion-mediated reactions. The participation of the oxidative species singlet molecular oxygen was not detected. The overall result shows chemical transformations in both Rf and 3-hydroxyflavone. No experimental evidence was found indicating any chemical reaction involving 7-hydroxyflavone. The fate of the pigment also depends on the amount of the dissolved flavonoid. At 50 mM concentrations of these compounds or higher, practically no photochemistry occurs, owing to the extensive quenching of ( 1 Rf*) When the concentration of the flavones is in the mM range or lower, ( 3 Rf*) is photogenerated. Then, the excited triplet species can be quenched mainly by the flavones through an electron-transfer process, yielding the semireduced pigment. The latter interacts with dissolved oxygen producing O 2 .- , which reacts with both the pigment and 3-hydroxyflavone. In summary, 3-hydroxyflavone and 7-hydroxyflavone participate in the generation of superoxide ion in an Rf-sensitized process, and simultaneously 3-hydroxyflavone constitutes a degradable quencher of the oxidative species. (author)

  19. Wave fronts, pulses and wave trains in photoexcited superlattices behaving as excitable or oscillatory media

    International Nuclear Information System (INIS)

    Arana, J I; Bonilla, L L; Grahn, H T

    2011-01-01

    Undoped and strongly photoexcited semiconductor superlattices with field-dependent recombination behave as excitable or oscillatory media with spatially discrete nonlinear convection and diffusion. Infinitely long, dc-current-biased superlattices behaving as excitable media exhibit wave fronts with increasing or decreasing profiles, whose velocities can be calculated by means of asymptotic methods. These superlattices can also support pulses of the electric field. Pulses moving downstream with the flux of electrons can be constructed from their component wave fronts, whereas pulses advancing upstream do so slowly and experience saltatory motion: they change slowly in long intervals of time separated by fast transitions during which the pulses jump to the previous superlattice period. Photoexcited superlattices can also behave as oscillatory media and exhibit wave trains. (paper)

  20. Measurements with an ultrafast scanning tunnelling microscope on photoexcited semiconductor layers

    DEFF Research Database (Denmark)

    Keil, Ulrich Dieter Felix; Jensen, Jacob Riis; Hvam, Jørn Märcher

    1998-01-01

    Summary form only given. We demonstrate the use of a ultrafast scanning tunnelling microscopes (USTM) for detecting laser-induced field transients on semiconductor layers. In principle, the instrument can detect transient field changes thus far observed as far-field THz radiation in the near......-field regime and resolve small signal sources. For photoexcited low temperature (LT) GaAs we can explain the signal by a diffusion current driven by the laser-induced carrier density gradient...

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

    Science.gov (United States)

    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.

  2. Accurate adiabatic singlet-triplet gaps in atoms and molecules employing the third-order spin-flip algebraic diagrammatic construction scheme for the polarization propagator

    Energy Technology Data Exchange (ETDEWEB)

    Lefrancois, Daniel; Dreuw, Andreas, E-mail: dreuw@uni-heidelberg.de [Interdisciplinary Center for Scientific Computing, Ruprecht-Karls University, Im Neuenheimer Feld 205, 69120 Heidelberg (Germany); Rehn, Dirk R. [Departments of Physics, Chemistry and Biology, Linköping University, SE-581 83 Linköping (Sweden)

    2016-08-28

    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 were 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.

  3. Ultrafast Control of Magnetism in Ferromagnetic Semiconductors via Photoexcited Transient Carriers

    Energy Technology Data Exchange (ETDEWEB)

    Cotoros, Ingrid A. [Univ. of California, Berkeley, CA (United States)

    2008-12-01

    The field of spintronics offers perspectives for seamless integration of coupled and inter-tunable electrical and magnetic properties in a single device. For integration of the spin degree of freedom with current electronic technology, new semiconductors are needed that show electrically-tunable magnetic properties at room temperature and above. Dilute magnetic semiconductors derived from III-V compounds, like GaMnAs and InMnAs, show coupled and tunable magnetic, transport, and optical properties, due to the fact that their ferromagnetism is hole-mediated. These unconventional materials are ideal systems for manipulating the magnetic order by changing the carrier polarization, population density, and energy band distribution of the complementary subsystem of holes. This is the main theme we cover in this thesis. In particular, we develop a unique setup by use of ultraviolet pump, near-infrared probe femtosecond laser pulses, that allows for magneto-optical Kerr effect (MOKE) spectroscopy experiments. We photo-excite transient carriers in our samples, and measure the induced transient magnetization dynamics. One set of experiments performed allowed us to observe for the first time enhancement of the ferromagnetic order in GaMnAs, on an ultrafast time scale of hundreds of picoseconds. The corresponding transient increase of Curie temperature (Tc, the temperature above which a ferromagnetic material loses its permanent magnetism) of about 1 K for our experimental conditions is a very promising result for potential spintronics applications, especially since it is seconded by observation of an ultrafast ferromagnetic to paramagnetic phase transition above Tc. In a different set of experiments, we "write" the magnetization in a particular orientation in the sample plane. Using an ultrafast scheme, we alter the distribution of holes in the system and detect signatures of the particular memory state in the subsequent magnetization dynamics, with unprecedented hundreds of

  4. Gas-phase hydrolysis of triplet SO2: A possible direct route to atmospheric acid formation

    Science.gov (United States)

    Donaldson, D. James; Kroll, Jay A.; Vaida, Veronica

    2016-07-01

    Sulfur chemistry is of great interest to the atmospheric chemistry of several planets. In the presence of water, oxidized sulfur can lead to new particle formation, influencing climate in significant ways. Observations of sulfur compounds in planetary atmospheres when compared with model results suggest that there are missing chemical mechanisms. Here we propose a novel mechanism for the formation of sulfurous acid, which may act as a seed for new particle formation. In this proposed mechanism, the lowest triplet state of SO2 (3B1), which may be accessed by near-UV solar excitation of SO2 to its excited 1B1 state followed by rapid intersystem crossing, reacts directly with water to form H2SO3 in the gas phase. For ground state SO2, this reaction is endothermic and has a very high activation barrier; our quantum chemical calculations point to a facile reaction being possible in the triplet state of SO2. This hygroscopic H2SO3 molecule may act as a condensation nucleus for water, giving rise to facile new particle formation (NPF).

  5. Dark Matter from the Supersymmetric Custodial Triplet Model

    CERN Document Server

    Delgado, Antonio; Ostdiek, Bryan; Quiros, Mariano

    2015-01-01

    The Supersymmetric Custodial Triplet Model (SCTM) adds to the particle content of the MSSM three $SU(2)_L$ triplet chiral superfields with hypercharge $Y=(0,\\pm1)$. At the superpotential level the model respects a global $SU(2)_L \\otimes SU(2)_R$ symmetry only broken by the Yukawa interactions. The pattern of vacuum expectation values of the neutral doublet and triplet scalar fields depends on the symmetry pattern of the Higgs soft breaking masses. We study the cases where this symmetry is maintained in the Higgs sector, and when it is broken only by the two doublets attaining different vacuum expectation values. In the former case, the symmetry is spontaneously broken down to the vectorial subgroup $SU(2)_V$ and the $\\rho$ parameter is protected by the custodial symmetry. However in both situations the $\\rho$ parameter is protected at tree level, allowing for light triplet scalars with large vacuum expectation values. We find that over a large range of parameter space, a light neutralino can supply the corre...

  6. X(3872) and Its Iso-Triplet Partners

    OpenAIRE

    Kunihiko, TERASAKI; Yukawa Institute for Theoretical Physics, Kyoto University:Institute for Theoretical Physics, Kanazawa University

    2012-01-01

    Decays of X(3872) and its partners as hidden-charm axial-vector tetra-quark mesons are studied. As the result, it is seen that the iso-triplet partners of X(3872) can be broad, and therefore, higher statistics will be needed to find them.

  7. Spin-triplet supercurrent in Co-based Josephson junctions

    International Nuclear Information System (INIS)

    Khasawneh, Mazin A; Khaire, Trupti S; Klose, Carolin; Pratt, William P Jr; Birge, Norman O

    2011-01-01

    In the past year several groups have reported experimental evidence for spin-triplet supercurrents in Josephson junctions containing strong ferromagnetic materials. In this paper we present several new experimental results that follow up on our previous work. We study Josephson junctions of the form S/X/N/SAF/N/X/S, where S is a superconductor (Nb), N is a normal metal, SAF is a synthetic antiferromagnet of the form Co/Ru/Co and X is an ferromagnetic layer necessary to induce spin-triplet correlations in the structure. Our work is distinguished by the fact that the generation of spin-triplet correlations is tuned by the type and thickness of the X layers. The most important new result reported here is the discovery that a conventional, strong ferromagnetic material, Ni, performs well as the X layer, if it is sufficiently thin. This discovery rules out our earlier hypothesis that out-of-plane magnetocrystalline anisotropy is an important attribute of the X layers. These results suggest that the spin-triplet correlations are most likely induced by noncollinear magnetization between the X layers and adjacent Co layers.

  8. Adaptive Port-Starboard Beamforming of Triplet Sonar Arrays

    NARCIS (Netherlands)

    Groen, J.; Beerens, S.P.; Been, R.; Doisy, Y.

    2005-01-01

    Abstract—For a low-frequency active sonar (LFAS) with a triplet receiver array, it is not clear in advance which signal processing techniques optimize its performance. Here, several advanced beamformers are analyzed theoretically, and the results are compared to experimental data obtained in sea

  9. Ramsauer effect in triplet neutron-neutron scattering

    International Nuclear Information System (INIS)

    Pupyshev, V.V.; Solovtsova, O.P.

    1995-01-01

    As we show, due to interplay of pure nuclear and magnetic moment interactions, the total cross section of triplet neutron-neutron scattering should possess a non-zero limit at E cm = 0 and a local minimum at ∼ 20 keV. 17 refs., 1 fig

  10. Triplet superconductivity in PrOs4Sb12

    International Nuclear Information System (INIS)

    Maki, K.; Won, H.; Parker, David; Haas, Stephan; Izawa, K.; Matsuda, Y.

    2005-01-01

    Here we propose spin triplet superconductors for the A- and B-phase in PrOs 4 Sb 12 . The present model describes consistently the thermal conductivity κ zz data obtained by Izawa et al. for T>=150mK

  11. EVALUATION OF PLEIADES-1A TRIPLET ON TRENTO TESTFIELD

    Directory of Open Access Journals (Sweden)

    D. Poli

    2013-05-01

    Full Text Available The Pleiades mission is part of the French-Italian ORFEO system (Optical and Radar Federated Earth Observation and has the aim to provide very-high resolution optical imagery from space for civilian and military needs. Within the Pleiades evaluation program, the 3DOM Unit at the Bruno Kessler Foundation in Trento (Italy received a triplet by Pleiades-1A over Trento testfield for research purposes. The images composing the triplet were acquired on August 28, 2012 with across-track angles close to nadir and alongtrack angles of 18°, -13° and 13° in average with respect to the flight direction (Fig. 1 and a mean GSD between 0.72 m and 0.78 m. The aim of this paper is to investigate the quality of the Pleiades triplet and derived Digital Surface Model (DSM. The image analysis was conducted by evaluating the radiometric properties of the images (noise characteristics, image artifacts, spilling and the geometric accuracy. After image orientation, three DSMs were generated with advanced image matching algorithms using two image combinations and the triplet. The DSMs were compared to the reference Lidar DSM (1 m grid spacing for quality analysis in areas with different characteristics (land use and cover, topography. Thanks to the availability of other very high resolution satellite imagery in the testfield, the results were compared to those previously obtained using WorldView-2 ad GeoEye-1 stereopairs acquired on the same area.

  12. Synthesis and Exciton Dynamics of Triplet Sensitized Conjugated Polymers

    KAUST Repository

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

    2015-01-01

    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

  13. Triplet repeat DNA structures and human genetic disease: dynamic ...

    Indian Academy of Sciences (India)

    Unknown

    formed at the loop-outs. [Sinden R R, Potaman V N, Oussatcheva E A, Pearson C E, Lyubchenko Y L and Shlyakhtenko L S 2002 Triplet repeat DNA structures .... 36–39. 40–121 Huntingtin/polyglutamine expansion. Spinocerebellar ataxia 1. SCA1. 6p23. (CAG)n. 6–44. –. 39–82 (pure) Ataxin-1/polyglutamine expansion.

  14. Dynamics of photoexcited Ba+ cations in 4He nanodroplets

    International Nuclear Information System (INIS)

    2UB, Universitat de Barcelona, Diagonal 645, 08028 Barcelona (Spain))" data-affiliation=" (Departament ECM, Facultat de Física, and IN2UB, Universitat de Barcelona, Diagonal 645, 08028 Barcelona (Spain))" >Leal, Antonio; 2UB, Universitat de Barcelona, Diagonal 645, 08028 Barcelona (Spain))" data-affiliation=" (Departament ECM, Facultat de Física, and IN2UB, Universitat de Barcelona, Diagonal 645, 08028 Barcelona (Spain))" >Pi, Martí; Zhang, Xiaohang; Drabbels, Marcel; 2UB, Universitat de Barcelona, Diagonal 645, 08028 Barcelona (Spain); Laboratoire des Collisions, Agrégats, Réactivité, IRSAMC, UMR 5589, CNRS et Université Paul Sabatier-Toulouse 3, 118 route de Narbonne, F-31062 Toulouse Cedex 09 (France))" data-affiliation=" (Departament ECM, Facultat de Física, and IN2UB, Universitat de Barcelona, Diagonal 645, 08028 Barcelona (Spain); Laboratoire des Collisions, Agrégats, Réactivité, IRSAMC, UMR 5589, CNRS et Université Paul Sabatier-Toulouse 3, 118 route de Narbonne, F-31062 Toulouse Cedex 09 (France))" >Barranco, Manuel; Cargnoni, Fausto; Hernando, Alberto; Mateo, David; Mella, Massimo

    2016-01-01

    We present a joint experimental and theoretical study on the desolvation of Ba + cations in 4 He nanodroplets excited via the 6p ← 6s transition. The experiments reveal an efficient desolvation process yielding mainly bare Ba + cations and Ba + He n exciplexes with n = 1 and 2. The speed distributions of the ions are well described by Maxwell-Boltzmann distributions with temperatures ranging from 60 to 178 K depending on the excitation frequency and Ba + He n exciplex size. These results have been analyzed by calculations based on a time-dependent density functional description for the helium droplet combined with classical dynamics for the Ba + . In agreement with experiment, the calculations reveal the dynamical formation of exciplexes following excitation of the Ba + cation. In contrast to experimental observation, the calculations do not reveal desolvation of excited Ba + cations or exciplexes, even when relaxation pathways to lower lying states are included.

  15. Impacts of electronically photo-excited NO2 on air pollution in the South Coast Air Basin of California

    Directory of Open Access Journals (Sweden)

    D. Dabdub

    2010-02-01

    Full Text Available A new path for hydroxyl radical formation via photo-excitation of nitrogen dioxide (NO2 and the reaction of photo-excited NO2 with water is evaluated using the UCI-CIT model for the South Coast Air Basin of California (SoCAB. Two separate studies predict different reaction rates, which differ by nearly an order of magnitude, for the reaction of photo-excited NO2 with water. Impacts of this new chemical mechanism on ozone and particulate matter formation, while utilizing both reaction rates, are quantified by simulating two summer episodes. First, sensitivity simulations are conducted to evaluate the uncertainty in the rate of reaction of photo-excited NO2 with water reported in the literature. Results indicate that the addition of photo-excited NO2 chemistry increases peak 8-h average ozone and particulate matter concentrations. The importance of this new chemistry is then evaluated in the context of pollution control strategies. A series of simulations are conducted to generate isopleths for ozone and particulate matter concentrations, varying baseline nitrogen oxides (NOx and volatile organic compounds (VOC emissions. Isopleths are obtained using 1987 emissions, to represent past conditions, and 2005, to represent current conditions in the SoCAB. Results show that the sensitivity of modeled pollutant control strategies due to photoexcitation decreases with the decrease in baseline emissions from 1987 to 2005. Results show that including NO2 photo-excitation, increases the sensitivity of ozone concentration with respect to changes in NOx emissions for both years. In particular, decreasing NOx emissions in 2005 when NO2 photo-excitation is included, while utilizing the higher reaction rate, leads to ozone relative reduction factors that are 15% lower than in a case without photo-excited NO2. This implies that photoexcitation increases the effectiveness in reducing ozone through NOx emissions reductions alone, which has implications for the

  16. Fetomaternal Outcome in Triplet and Quadruplet Pregnancies: A Retrospective Study

    Directory of Open Access Journals (Sweden)

    Maasoumeh Mirzamoradi

    2017-06-01

    Full Text Available Background: In recent decades, there has been a dramatic increase in the prevalence of multiple pregnancies. An important reason is the increased use of assisted reproductive techniques for conception. Despite the advances in prenatal care, maternal and neonatal morbidity and mortality caused by multiple pregnancies are still high. Aim: This study aimed to evaluate the fetomaternal complications in higher order multiple pregnancies. Design: The design is a retrospective study. Setting: Triplet and quadruplet pregnancies were investigated in this study. Methods: This study investigated the outcome of triplet and quadruplet pregnancies born alive at the Mahdiyeh hospital, Tehran, Iran from 2006 to 2015. Results: In this study, 111 triplet pregnancies and 24 quadruplet pregnancies were studied, 80% of which resulted from assisted reproductive technology. The average age of pregnancy termination was 31 weeks, the average weight of the first to third neonates was 1400 g and the average weight of the fourth neonate was 700 g. The most common reason for early termination of pregnancy was preterm labor, the most maternal complication was uterine atony and the most common neonatal complication was pre-maturity and then respiratory distress syndrome (RDS. The mean age of mother in triplets’ deliveries was significantly lower than in the quadruplets. The average weight of the first to third neonates, the average of 1st and 5th minutes Apgar score of the first neonates and the average gestational age of termination for the first and second neonates in triplets was significantly higher than in the quadruplets. Hospitalization due to preterm labor in quadruplets’ delivery was significantly higher than in triplets. Conclusion: Higher order multiple pregnancies are associated with higher maternal and neonatal complications. Mothers with such pregnancies needs more care in the prenatal period, during labor and in the postpartum period, and also their

  17. Effect of iodine impurity on relaxation of photoexcited silver chloride

    International Nuclear Information System (INIS)

    Vostrikova, Yu. V.; Klyuev, V. G.

    2008-01-01

    The time and temperature dependences of relaxation of excited AgCl and AgCl:I crystals is studied by the method of photostimulated flash of luminescence. The presence of iodine impurity in silver chloride gives rise to hole recombination (luminescence) centers and hole traps in the band gap. It is shown that the main contribution to the decrease in the concentration of electrons localized at deep traps is made by the recombination of electrons with holes released thermally from shallow localization levels (iodine-related centers). Estimation of activation energy for the relaxation process showed that these energies for the AgCl and AgCl:I samples under study are the same within the experimental error and are equal to E rel1 = 0.01 ± 0.0005 eV for the initial stage of relaxation and E rel2 = 0.09 ± 0.005 eV for the final state. This fact indicates that the majority of hole traps involved in the relaxation process in AgCl are related to iodine impurity. In the course of thermal relaxation in AgCl, relocalization of nonequilibrium charge carriers from shallow levels to deep levels is observed. The depth of the corresponding trap is E arl = 0.174 ± 0.03 eV.

  18. Singlet and triplet polaron relaxation in doubly charged self-assembled quantum dots

    International Nuclear Information System (INIS)

    Grange, T; Zibik, E A; Ferreira, R; Bastard, G; Carpenter, B A; Phillips, P J; Stehr, D; Winnerl, S; Helm, M; Steer, M J; Hopkinson, M; Cockburn, J W; Skolnick, M S; Wilson, L R

    2007-01-01

    Polaron relaxation in self-assembled InAs/GaAs quantum dot samples containing 2 electrons per dot is studied using far-infrared, time-resolved pump-probe measurements for transitions between the s-like ground and p-like first excited conduction band states. Spin-flip transitions between singlet and triplet states are observed experimentally in the decay of the absorption bleaching, which shows a clear biexponential dependence. The initial fast decay (∼30 ps) is associated with the singlet polaron decay, while the decay component with the longer time constant (∼5 ns) corresponds to the excited state triplet lifetime. The results are explained by considering the intrinsic Dresselhaus spin-orbit interaction, which induces spin-flip transitions by acoustic phonon emission or phonon anharmonicity. We have calculated the spin-flip decay times, and good agreement is obtained between the experiment and the simulation of the pump-probe signal. Our results demonstrate the importance of spin-mixing effects for intraband energy relaxation in InAs/GaAs quantum dots

  19. Effect of tert-Butyl Functionalization on the Photoexcited Decay of a Fe(II)-N-Heterocyclic Carbene Complex

    DEFF Research Database (Denmark)

    Pápai, Mátyás Imre; Penfold, Thomas J.; Møller, Klaus Braagaard

    2016-01-01

    -vibronic quantum dynamics simulations on the Fe-N-heterocyclic carbene complex, [Fe(btbip)2]2+ (btbip = 2,6-bis(3-tert-butyl-imidazole-1-ylidene)pyridine). The results demonstrate that a relatively minor structural change compared to its parent complex, [Fe(bmip)2]2+ (bmip = 2,6-bis(3-methyl-imidazole-1-ylidene....... This occurs because the tert-butyl functionalization stabilizes the 1MC states, enabling the 1,3MLCT → 1MC population transfer to occur close to the Franck-Condon geometry, making the conversion very efficient. Subsequently, a spin cascade occurs within the MC manifold, leading to the population of triplet...

  20. Impact of Dielectric Constant on the Singlet-Triplet Gap in Thermally Activated Delayed Fluorescence (TADF) Materials

    KAUST Repository

    Sun, Haitao

    2017-04-28

    Thermally activated delayed fluorescence (TADF) relies on the presence of a very small energy gap, ΔEST, between the lowest singlet and triplet excited states. ΔEST is thus a key factor in the molecular design of more efficient materials. However, its accurate theoretical estimation remains challenging, especially in the solid state due to the influence of polarization effects. We have quantitatively studied ΔEST as a function of dielectric constant, ε, for four representative organic molecules using the methodology we recently proposed at the Tamm-Dancoff approximation ωB97X level of theory, where the range-separation parameter ω is optimized with the polarizable continuum model. The results are found to be in very good agreement with experimental data. Importantly, the polarization effects can lead to a marked reduction in the ΔEST value, which is favorable for TADF applications. This ΔEST decrease in the solid state is related to the hybrid characters of the lowest singlet and triplet excited states, whose dominant contribution switches to charge-transfer-like with increasing ε. The present work provides a theoretical understanding on the influence of polarization effect on the singlet-triplet gap and confirms our methodology to be a reliable tool for the prediction and development of novel TADF materials.

  1. Spin-triplet excitons and anisotropy effects in the S=12 gapped antiferromagnet BaCuSi2O6

    International Nuclear Information System (INIS)

    Zvyagin, S.A.; Wosnitza, J.; Krzystek, J.; Stern, R.; Jaime, M.; Sasago, Y.; Uchinokura, K.

    2007-01-01

    BaCuSi 2 O 6 can be regarded as an almost ideal realization of an S=12 system of weakly interacting spin dimers with spin-singlet ground state and gapped excitation spectrum. We argue that the fine structure observed in low-temperature EPR spectra of BaCuSi 2 O 6 is a fingerprint of triplet excitations (excitons). Analyzing the angular dependence of the exciton modes allows us to precisely calculate the zero-field splitting within the triplet states and, correspondingly, the anisotropy parameter, D=0.07cm -1 . The proposed procedure can be applied for studying anisotropy effects in a large number of S=12 gapped quantum antiferromagnets with dimerized or alternating spin structure

  2. Mesoscopic structural phase progression in photo-excited VO2 revealed by time-resolved x-ray diffraction microscopy

    Science.gov (United States)

    Zhu, Yi; Cai, Zhonghou; Chen, Pice; Zhang, Qingteng; Highland, Matthew J.; Jung, Il Woong; Walko, Donald A.; Dufresne, Eric M.; Jeong, Jaewoo; Samant, Mahesh G.; Parkin, Stuart S. P.; Freeland, John W.; Evans, Paul G.; Wen, Haidan

    2016-02-01

    Dynamical phase separation during a solid-solid phase transition poses a challenge for understanding the fundamental processes in correlated materials. Critical information underlying a phase transition, such as localized phase competition, is difficult to reveal by measurements that are spatially averaged over many phase separated regions. The ability to simultaneously track the spatial and temporal evolution of such systems is essential to understanding mesoscopic processes during a phase transition. Using state-of-the-art time-resolved hard x-ray diffraction microscopy, we directly visualize the structural phase progression in a VO2 film upon photoexcitation. Following a homogenous in-plane optical excitation, the phase transformation is initiated at discrete sites and completed by the growth of one lattice structure into the other, instead of a simultaneous isotropic lattice symmetry change. The time-dependent x-ray diffraction spatial maps show that the in-plane phase progression in laser-superheated VO2 is via a displacive lattice transformation as a result of relaxation from an excited monoclinic phase into a rutile phase. The speed of the phase front progression is quantitatively measured, and is faster than the process driven by in-plane thermal diffusion but slower than the sound speed in VO2. The direct visualization of localized structural changes in the time domain opens a new avenue to study mesoscopic processes in driven systems.

  3. Catalyst-free activation of peroxides under visible LED light irradiation through photoexcitation pathway

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Yaowen [Department of Environmental Engineering, Wuhan University, Wuhan, 430079 (China); Shenzhen Research Institute of Wuhan University, Shenzhen, 518057 (China); Li, Yixi; Yao, Linyu; Li, Simiao; Liu, Jin [Department of Environmental Engineering, Wuhan University, Wuhan, 430079 (China); Zhang, Hui, E-mail: eeng@whu.edu.cn [Department of Environmental Engineering, Wuhan University, Wuhan, 430079 (China); Shenzhen Research Institute of Wuhan University, Shenzhen, 518057 (China)

    2017-05-05

    Highlights: • Persulfate could decolorize Rhodamine B (RhB) directly via non-radical reactions. • LED lamps emitting white light were utilized as the visible light source. • Dyes could activate peroxides through photoexcitation pathway. • Decolorization of dyes and production of radicals were achieved simultaneously. • The catalyst-free peroxide/dye/Vis process was effective in a broad pH range. - Abstract: Catalysts are known to activate peroxides to generate active radicals (i.e., hydroxyl radical (·OH) and sulfate radical (SO{sub 4}·{sup −})) under certain conditions, but the activation of peroxides in the absence of catalysts under visible light irradiation has been rarely reported. This work demonstrates a catalyst-free activation of peroxides for the generation of ·OH and/or SO{sub 4}·{sup −} through photoexcited electron transfer from organic dyes to peroxides under visible LED light irradiation, where Rhodamine B (RhB) and Eosin Y (EY) were selected as model dyes. The formation of ·OH and/or SO{sub 4}·{sup −} in the reactions and the electron transfer from the excited dyes to peroxides were validated via electron paramagnetic resonance (EPR), photoluminescence (PL) spectra and cyclic voltammetry (CV). The performance of the peroxide/dye/Vis process was demonstrated to be altered depending on the target substrate. Meanwhile, the peroxide/dye/Vis process was effective for simultaneous decolorization of dyes and production of active radicals under neutral even or basic conditions. The findings of this study clarified a novel photoexcitation pathway for catalyst-free activation of peroxides under visible light irradiation, which could avoid the secondary metal ion (dissolved or leached) pollution from the metal-based catalysts and expand the application range of the peroxide-based catalytic process.

  4. Reliable Prediction with Tuned Range-Separated Functionals of the Singlet-Triplet Gap in Organic Emitters for Thermally Activated Delayed Fluorescence (TADF)

    KAUST Repository

    Sun, Haitao

    2015-07-09

    The thermally activated delayed fluorescence (TADF) mechanism has recently attracted much interest in the field of organic light-emitting diodes (OLEDs). TADF relies on the presence of a very small energy gap between the lowest singlet and triplet excited states. Here, we demonstrate that time-dependent density functional theory (TD-DFT) in the Tamm-Dancoff Approximation can be very successful in the calculations of the lowest singlet and triplet excitation energies and the corresponding singlet-triplet gap when using nonempirically tuned range-separated functionals. Such functionals provide very good estimates in a series of 17 molecules used in TADF-based OLED devices, with mean absolute deviations of 0.15 eV for the vertical singlet excitation energies and 0.09 eV [0.07 eV] for the adiabatic [vertical] singlet-triplet energy gaps as well as low relative errors and high correlation coefficients compared to the corresponding experimental values. They significantly outperform conventional functionals, a feature which is rationalized on the basis of the amount of exact-exchange included and the delocalization error. The present work provides a reliable theoretical tool for the prediction and development of novel TADF-based materials with low singlet-triplet energetic splittings.

  5. Molecular control of photoexcited charge transfer and recombination at a quaterthiophene/zinc oxide interface

    International Nuclear Information System (INIS)

    Mou Weiwei; Nakano, Aiichiro; Ohmura, Satoshi; Shimojo, Fuyuki

    2012-01-01

    Nonadiabatic quantum molecular dynamics simulations are performed to study photoexcited charge transfer (CT) and charge recombination (CR) at an interface between a conjugated oligomer donor, quaterthiophene (QT), and an inorganic acceptor (ZnO). Simulations reveal a detrimental effect of static disorder in QT conformation on the efficiency of hybrid QT/ZnO solar cells due to increased CR. On the contrary, dynamic disorder (i.e., fluctuation of carbon-hydrogen bonds in QT) is essential for high efficiency by assisting CT. The separate controllability of CT and CR at the molecular level has impacts on molecular design for efficient solar cells and explains recent experimental observations.

  6. Photoexcitation by gamma-ray scattering near threshold and giant dipole resonance

    International Nuclear Information System (INIS)

    Lakosi, L.; Safar, J.; Veres, A.; Sekine, T.; Kaji, H.; Yoshihara, K.

    1993-01-01

    Photoexcitation of 4.5 h half-life 115m In and 56 min half-life 103m Rh isomers by inelastic gamma-ray scattering near threshold and in the giant dipole resonance region has been reviewed. In disagreement with earlier experimental results available in the literature, but in good agreement with our experiments published recently, present calculations indicate that above the photoneutron emission threshold the isomer excitation drops abruptly and remains orders of magnitude smaller than at the threshold, even around resonance maximum. (author)

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

    Energy Technology Data Exchange (ETDEWEB)

    Eersel, H. van [Simbeyond B.V., P.O. Box 513, NL-5600 MB Eindhoven (Netherlands); Bobbert, P. A.; Janssen, R. A. J.; Coehoorn, R., E-mail: r.coehoorn@tue.nl [Department of Applied Physics and Institute for Complex Molecular Systems, Eindhoven University of Technology, P.O. Box 513, NL-5600 MB Eindhoven (Netherlands)

    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: 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.

  8. Influence of relaxation processes in polymers on energy transfer by triplet levels

    International Nuclear Information System (INIS)

    Ibraev, N.Kh.; Zhunusbekov, A.M.

    1996-01-01

    Temperature influence on triplet-triplet (T-T) energy transfer between molecules of eosin and 3,4-benzopyrene is studied. Polyvenylbuteryl films have been used in capacity of polymer matrix. Calculation has being carried out on spectral-kinetic unit. It is revealed, that 3,4-benzopyrene triplets have been formed in polymer matrix after end of T-T energy transfer. These triplets join in a reaction of mixed triplet-triplet annihilation with non-blow out triplets of eosin and its sensitize slowed fluorescence (SF) of donor. This explains non-exponent character of eosin's dumping kinetics. Non-linear dependence of SF output ration to eosin phosphorescence output under presence of 3,4-benzopyrene molecules in film indicates on process of mixed annihilation. Fractal character of SF donor and acceptor has been evidenced about microscopical distribution of phosphor in polymer. 13 refs., 5 figs

  9. Triplet scalars and dark matter at the LHC

    International Nuclear Information System (INIS)

    Fileviez Perez, Pavel; Patel, Hiren H.; Ramsey-Musolf, Michael J.; Wang, Kai

    2009-01-01

    We investigate the predictions of a simple extension of the standard model where the Higgs sector is composed of one SU(2) L doublet and one real triplet. We discuss the general features of the model, including its vacuum structure, theoretical and phenomenological constraints, and expectations for Higgs collider studies. The model predicts the existence of a pair of light charged scalars and, for vanishing triplet vacuum expectation value, contains a cold dark matter candidate. When the latter possibility occurs, the charged scalars are long-lived, leading to a prediction of distinctive single charged track with missing transverse energy or double charged track events at the large hadron collider. The model predicts a significant excess of two-photon events compared to SM expectations due to the presence of a light charged scalar.

  10. A kinetically blocked 1,14:11,12-dibenzopentacene: A persistent triplet diradical of a non-Kekulé polycyclic benzenoid hydrocarbon

    KAUST Repository

    Li, Yuan; Huang, Kuo-Wei; Sun, Zhe; Webster, Richard D.; Zeng, Zebing; Zeng, Wangdong; Chi, Chunyan; Furukawa, Ko; Wu, Jishan

    2014-01-01

    The synthesis of high-spin polycyclic hydrocarbons is very challenging due to their extremely high reactivity. Herein, we report the synthesis and characterization of a kinetically blocked 1,14:11,12-dibenzopentacene, DP-Mes, which represents a rare persistent triplet diradical of a non-Kekulé polycyclic benzenoid hydrocarbon. In contrast to its structural isomer 1,14:7,8-dibenzopentacene (heptazethrene) with a singlet biradical ground state, DP-Mes is a triplet diradical as confirmed by ESR and ESTN measurements and density functional theory calculations. DP-Mes also displays intermolecular antiferromagnetic spin interactions in solution at low temperature. © 2014 the Partner Organisations.

  11. Photorelease of triplet and singlet oxygen from dioxygen complexes

    Czech Academy of Sciences Publication Activity Database

    Wagnerová, Dana Marie; Lang, Kamil

    2011-01-01

    Roč. 255, 23-24 (2011), s. 2904-2911 ISSN 0010-8545 R&D Projects: GA ČR GAP207/10/1447; GA ČR GAP208/10/1678 Institutional research plan: CEZ:AV0Z40320502 Keywords : singlet oxygen * triplet oxygen * photochemical elimination * photorelease * Dioxygen complex Subject RIV: CA - Inorganic Chemistry Impact factor: 12.110, year: 2011

  12. Transient photocurrent in molecular junctions: singlet switching on and triplet blocking.

    Science.gov (United States)

    Petrov, E G; Leonov, V O; Snitsarev, V

    2013-05-14

    The kinetic approach adapted to describe charge transmission in molecular junctions, is used for the analysis of the photocurrent under conditions of moderate light intensity of the photochromic molecule. In the framework of the HOMO-LUMO model for the single electron molecular states, the analytic expressions describing the temporary behavior of the transient and steady state sequential (hopping) as well as direct (tunnel) current components have been derived. The conditions at which the current components achieve their maximal values are indicated. It is shown that if the rates of charge transmission in the unbiased molecular diode are much lower than the intramolecular singlet-singlet excitation/de-excitation rate, and the threefold degenerated triplet excited state of the molecule behaves like a trap blocking the charge transmission, a possibility of a large peak-like transient switch-on photocurrent arises.

  13. Statistical equilibrium in cometary C2. IV. A 10 level model including singlet-triplet transitions

    International Nuclear Information System (INIS)

    Krishna Swamy, K.S.; O'dell, C.R.; Rice Univ., Houston, TX)

    1987-01-01

    Resonance fluorescence theory was used to calculate the population distribution in the energy states of the C2 molecule in comets. Ten electronic states, each with 14 vibrational states, were used in the calculations. These new calculations differ from earlier work in terms of additional electronic levels and the role of singlet-triplet transitions between the b and X levels. Since transition moments are not known, calculations are made of observable flux ratios for an array of possible values. Comparison with existing observations indicates that the a-X transition is very important, and there is marginal indication that the b-X transition is present. Swan band sequence flux ratios at large heliocentric distance are needed, as are accurate Mulliken/Swan and Phillips/Ballik-Ramsay (1963) observations. 29 references

  14. Triplet formation in the ion recombination in irradiated liquids

    International Nuclear Information System (INIS)

    Bartczak, W.M.; Tachiya, M.; Hummel, A.

    1990-01-01

    The formation of singlet and triplet excited stages in the ion recombination in groups of oppositely charged ions (or positive ions and electrons) in nonpolar liquids, as occurs in the tracks of high energy electrons, is considered. Theoretical studies on triplet formation in groups of ion pairs have thus far concentrated on the case where recombination of the negative ions with any of the positive ions in the group is equally probable (random recombination). In this paper the probability for geminate recombination (electron and parent positive ion) vs cross-recombination (an electron with a positive ion other than its parent ion) in multiple ion pair groups is calculated by computer simulation and the effect of the initial spatial configuration of the charged species is investigated. It is also shown explicitly that the probability for singlet formation as a result of cross recombination is equal to 1/4, when spin relaxation by magnetic interaction with the medium and by exchange interaction can be neglected. The effect of the preferential recombination on the singlet formation probability is illustrated and recent experimental results on singlet to triplet ratios are discussed. (author)

  15. Minimum triplet covers of binary phylogenetic X-trees.

    Science.gov (United States)

    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.

  16. Sirenomelia in a Nigerian triplet: a case report

    Science.gov (United States)

    2011-01-01

    Introduction Sirenomelia, also known as mermaid syndrome, is a very rare fatal congenital abnormality in which the legs are fused together, giving them the appearance of a mermaid's tail. It is commonly associated with abnormal kidney development, genital and rectal abnormalities. A handful of cases have been reported in other parts of the world, however, no cases have previously been reported in a Nigerian neonate. To the best of our knowledge, we believe that this is the first case reported from West Africa and in a triplet. Case presentation A 16-hour-old baby boy, the second of a set of Nigerian triplets, presented to our facility with fusion of the entire lower limbs, imperforate anus, indiscernible genital structures, single umbilical artery and a neural tube defect. His parents were from the Hausa ethnic group and not related. Conclusion Sirenomelia has not been previously described in a set of triplets, and it is hoped that this report from West Africa will give information about the non-racial predilection of this condition. PMID:21888626

  17. Sirenomelia in a Nigerian triplet: a case report

    Directory of Open Access Journals (Sweden)

    Wonodi Woroma

    2011-09-01

    Full Text Available Abstract Introduction Sirenomelia, also known as mermaid syndrome, is a very rare fatal congenital abnormality in which the legs are fused together, giving them the appearance of a mermaid's tail. It is commonly associated with abnormal kidney development, genital and rectal abnormalities. A handful of cases have been reported in other parts of the world, however, no cases have previously been reported in a Nigerian neonate. To the best of our knowledge, we believe that this is the first case reported from West Africa and in a triplet. Case presentation A 16-hour-old baby boy, the second of a set of Nigerian triplets, presented to our facility with fusion of the entire lower limbs, imperforate anus, indiscernible genital structures, single umbilical artery and a neural tube defect. His parents were from the Hausa ethnic group and not related. Conclusion Sirenomelia has not been previously described in a set of triplets, and it is hoped that this report from West Africa will give information about the non-racial predilection of this condition.

  18. Sirenomelia in a Nigerian triplet: a case report.

    Science.gov (United States)

    Ugwu, Rosemary O; Eneh, Augusta U; Wonodi, Woroma

    2011-09-02

    Sirenomelia, also known as mermaid syndrome, is a very rare fatal congenital abnormality in which the legs are fused together, giving them the appearance of a mermaid's tail. It is commonly associated with abnormal kidney development, genital and rectal abnormalities. A handful of cases have been reported in other parts of the world, however, no cases have previously been reported in a Nigerian neonate. To the best of our knowledge, we believe that this is the first case reported from West Africa and in a triplet. A 16-hour-old baby boy, the second of a set of Nigerian triplets, presented to our facility with fusion of the entire lower limbs, imperforate anus, indiscernible genital structures, single umbilical artery and a neural tube defect. His parents were from the Hausa ethnic group and not related. Sirenomelia has not been previously described in a set of triplets, and it is hoped that this report from West Africa will give information about the non-racial predilection of this condition.

  19. Dynamics of photoexcited carrier relaxation and recombination in CdTe/CdS thin films

    Energy Technology Data Exchange (ETDEWEB)

    Levi, D.H.; Fluegel, B.D.; Ahrenkiel, R.K. [National Renewable Energy Lab., Golden, CO (United States)] [and others

    1996-05-01

    Efficiency-limiting defects in photovoltaic devices are readily probed by time-resolved spectroscopy. This paper presents the first direct optical measurements of the relaxation and recombination pathways of photoexcited carriers in the CdS window layer of CdTe/CdS polycrystalline thin films. Femtosecond time-resolved pump/probe measurements indicate the possible existence of a two-phase CdS/CdSTe layer, rather than a continuously graded alloy layer at the CdTe/CdS interface. Complementary time-resolved photoluminescence (PL) measurements show that the photoexcited carriers are rapidly captured by deep-level defects. The temporal and density-dependent properties of the photoluminescence prove that the large Stokes shift of the PL relative to the band edge is due to strong phonon coupling to deep-level defects in CdS. The authors suggest that modifications in the CdS processing may enhance carrier collection efficiency in the blue spectral region.

  20. DNA partitions into triplets under tension in the presence of organic cations, with sequence evolutionary age predicting the stability of the triplet phase

    NARCIS (Netherlands)

    Taghavi, Amirhossein; van der Schoot, Paul; Berryman, Joshua T

    2017-01-01

    Using atomistic simulations, we show the formation of stable triplet structure when particular GC-rich DNA duplexes are extended in solution over a timescale of hundreds of nanoseconds, in the presence of organic salt. We present planar-stacked triplet disproportionated DNA (Σ DNA) as a possible

  1. Probing odd-triplet contributions to the long-ranged proximity effect by scanning tunneling spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Diesch, Simon; Machon, Peter; Belzig, Wolfgang; Scheer, Elke [Universitaet Konstanz, Konstanz (Germany); Suergers, Christoph; Beckmann, Detlef [Karlsruhe Institute of Technology, Karlsruhe (Germany)

    2015-07-01

    In conventional superconductors, electrons are bound in singlet Cooper pairs, i.e. with opposite spin. More recently, experiments on superconductor-ferromagnet-systems have shown Cooper pairs tunneling through ferromagnetic layers, indicating Cooper pairs of equal spin, thus corresponding to a long-range triplet proximity effect. Most experimental evidence for triplet superconductivity comes from observations of the thickness dependence of the Josephson current through a ferromagnetic barrier, but there is an increasing interest in obtaining direct spectroscopic evidence. This project aims at analyzing the electronic density of states of a thin diffusive normal metal layer (Ag) coupled to a superconductor (Al) across a ferromagnetic insulator (EuS) using a scanning tunneling microscope in spectroscopy mode at 280 mK. For this purpose, we fabricated EuS films of different thicknesses and acquired spectroscopic data at different magnetic fields. We observe significant broadening of the superconductive energy gap and a variety of sub-gap structures including zero-bias conductance peaks induced by the presence of the ferromagnet.

  2. Pyridine-2,6-diyl dinitroxides as room-temperature triplet ligands

    Energy Technology Data Exchange (ETDEWEB)

    Kawakami, Hinako; Tonegawa, Asato; Ishida, Takayuki, E-mail: takayuki.ishida@uec.ac.jp [Department of Engineering Science, The University of Electro-Communications, Tokyo (Japan)

    2016-02-01

    We have proposed tert-butyl 2-pyridyl nitroxide radicals as a promising paramagnetic chelating ligand, where the direct radical-metal bond leads to strong magnetic interaction. We successfully synthesized and isolated PyBN derivatives (pyridine-2,6-diyl bis(tert-butyl nitroxides)). The molecular and crystal structures of the target biradicals, MesPyBN, AntPyBN and tBuOPyBN were determined from the X-ray crystal structure analysis, which possess mesityl, 9-anthryl and tert-butoxy groups at the 5-position of the pyridine ring, respectively. The ground triplet state was characterized by means of SQUID susceptometry for each compound. On heating, the χ{sub m}T values of all the PyBN derivatives increased and reached a plateau at ca. 1.0 cm{sup 3} K mol{sup −1} at 300 K. It implies that biradicals behaved as triplet molecules even at room temperature, or 2J/k{sub B} >> 300 K. From the decay monitored in solution electron-spin resonance spectroscopy, MesPyBN was the most persistent, while tBuOPyBN was the most reactive, of the three.

  3. Resolution limit of probe-forming systems with magnetic quadrupole lens triplets and quadruplets

    International Nuclear Information System (INIS)

    Ponomarev, A.G.; Melnik, K.I.; Miroshnichenko, V.I.; Storizhko, V.E.; Sulkio-Cleff, B.

    2003-01-01

    Over the past decade, in MeV ion beam microanalysis efforts to achieve a spatial resolution better than 0.1 μm with a beam current of ∼100 pA have been connected with microprobes of new generation where the probe is formed by means of separated magnetic quadrupole lens structures . However, as was pointed out in , no dramatic improvements in spatial resolution have been produced so far. For better understanding of the situation the authors carried out theoretical studies of multiparameter sets of probe-forming systems based on separated triplets and quadruplets of magnetic quadrupole lenses. Comparisons were made between the highest current values attained at different systems for a given beam spot size. The maximum parasitic sextupole and octupole field components were found whose contributions to spot broadening are tolerable. It is shown that the use of modern electrostatic accelerators and precision magnetic quadrupole lenses makes it possible to eliminate the effect of chromatic aberrations and second- and third-order parasitic aberrations resulting from distortions of the quadrupole lens symmetry. Therefore probe-forming systems with triplets and quadruplets of magnetic quadrupole lenses have a lower theoretical spatial resolution limit which is restricted mainly by intrinsic spherical third-order aberrations in state-of-the-art microprobes

  4. α decay of the T=1, 2+ state in B10 and isospin symmetry breaking in the A=10 triplet

    Energy Technology Data Exchange (ETDEWEB)

    Kuvin, S. A.; Wuosmaa, A. H.; Lister, C. J.; Avila, M. L.; Hoffman, C. R.; Kay, B. P.; McNeel, D. G.; Morse, C.; McCutchan, E. A.; Santiago-Gonzalez, D.; Winkelbauer, J. R.

    2017-10-01

    The rate of the T = 1, 2(+) to T = 1, 0(+) transition in B-10 (T = 1, T-z = 0) is compared to the analog transitions in Be-10 (T = 1, T-z = -1) and C-10 (T = 1, T-z = +1) to provide constraints on ab initio calculations using realistic nuclear forces. The relevant state in B-10, at E-x = 5.164 MeV, is particle unbound. Therefore, a determination of the B(E2) electromagnetic transition rate requires a precise and accurate determination of the width of the state, as well as the alpha-particle and gamma-ray branching ratios. Previous measurements of the a-particle branching ratio are just barely in agreement. We report on a new study of the alpha-particle branch by studying the B-10(p, p') B-10* reaction in inverse kinematics with the HELIOS spectrometer. The alpha-particle branching ratio that we observe, 0.144 +/- 0.027, is in good agreement with the evaluated value and improves the associated uncertainty. The resulting experimental B(E2) value is 7.0 +/- 2.2 e(2)fm(4) and is more consistent with a flat trend across the A = 10 triplet than previously reported. This is inconsistent with Green's functionMonte Carlo predictions using realistic three-nucleon Hamiltonians, which overpredict the B(E2) value in C-10 and B-10.

  5. On the pathway of photoexcited electrons: probing photon-to-electron and photon-to-phonon conversions in silicon by ATR-IR

    DEFF Research Database (Denmark)

    Karabudak, Engin; Yüce, Emre; Schlautmann, Stefan

    2012-01-01

    Photoexcitation and charge carrier thermalization inside semiconductor photocatalysts are two important steps in solar fuel production. Here, photoexcitation and charge carrier thermalization in a silicon wafer are for the first time probed by a novel, yet simple and user-friendly Attenuated Tota...

  6. Negligible Electronic Interaction between Photoexcited Electron-Hole Pairs and Free Electrons in Phosphorus-Boron Co-Doped Silicon Nanocrystals

    Energy Technology Data Exchange (ETDEWEB)

    Limpens, Rens [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Neale, Nathan R [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Fujii, Minoru [Kobe University; Gregorkiewicz, Tom [University of Amsterdam

    2018-03-05

    Phosphorus (P) and boron (B) co-doped Si nanocrystals (NCs) have raised interest in the optoelectronic industry due to their electronic tunability, optimal carrier multiplication properties, and straightforward dispersibility in polar solvents. Yet a basic understanding of the interaction of photoexcited electron-hole (e-h) pairs with new physical features that are introduced by the co-doping process (free carriers, defect states, and surface chemistry) is missing. Here, we present the first study of the ultrafast carrier dynamics in SiO2-embedded P-B co-doped Si NC ensembles using induced absorption spectroscopy through a two-step approach. First, the induced absorption data show that the large fraction of the dopants residing on the NC surface slows down carrier relaxation dynamics within the first 20 ps relative to intrinsic (undoped) Si NCs, which we interpret as enhanced surface passivation. On longer time-scales (picosecond to nanosecond regime), we observe a speeding up of the carrier relaxation dynamics and ascribe it to doping-induced trap states. This argument is deduced from the second part of the study, where we investigate multiexciton interactions. From a stochastic modeling approach we show that localized carriers, which are introduced by the P or B dopants, have minor electronic interactions with the photoexcited e-h pairs. This is understood in light of the strong localization of the introduced carriers on their original P- or B-dopant atoms, due to the strong quantum confinement regime in these relatively small NCs (<6 nm).

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

    Science.gov (United States)

    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.

  8. Reproduction performance of cows with single, twin and triplet calves

    Directory of Open Access Journals (Sweden)

    Anna Sawa

    2012-01-01

    Full Text Available The aim of this study was to analyse data on 74,081 calvings, subsequent lactation performance and culling of 23,588 Black-and-White cows improved with Holstein-Friesians. The animals represented the active population in Pomerania and Kujavia, first calved in 2000 and 2001, and were culled before the end of 2008. Frequency of calvings, which averaged 1.5% for twin births and just 0.02% for triplet births, increased with age of cow and also with increasing milk yield in the preceding lactation. Performance results showed that mothers of twins were superior to mothers of single calves in terms of milk yield (1.3 kg milk/day milking. Despite the greater perinatal mortality of twins and triplets, multiple pregnancies gave rise to a greater number of calves compared to single pregnancies. However, multiple pregnancies were accompanied by adverse effects such as increased proportion of complications requiring human assistance, mechanical assistance and veterinary intervention (1.2 × more. Fertility of the cows deteriorated after multiple pregnancies, with particularly unfavourable indicators of fertility found for triplet births, decreased chance of survival to the next calving, and increased culling rates in cows, especially due to udder diseases, infertility, reproductive diseases, old age, metabolic and gastrointestinal diseases, and locomotor system diseases. It was found that the increasing milk yield was paralleled by the increasing proportion of multiple pregnancies. This has highlighted the need for early and reliable diagnosis and management of twin pregnancies, which is supposed to facilitate parturition and ensure survival of calves.

  9. Three-Nucleon Forces and Triplet Pairing in Neutron Matter

    Science.gov (United States)

    Papakonstantinou, P.; Clark, J. W.

    2017-12-01

    The existence of superfluidity of the neutron component in the core of a neutron star, associated specifically with triplet P-wave pairing, is currently an open question that is central to interpretation of the observed cooling curves and other neutron-star observables. Ab initio theoretical calculations aimed at resolving this issue face unique challenges in the relevant high-density domain, which reaches beyond the saturation density of symmetrical nuclear matter. These issues include uncertainties in the three-nucleon (3N) interaction and in the effects of strong short-range correlations—and more generally of in-medium modification of nucleonic self-energies and interactions. A survey of existing solutions of the gap equations in the triplet channel demonstrates that the net impact on the gap magnitude of 3N forces, coupled channels, and mass renormalization shows extreme variation dependent on specific theoretical inputs, in some cases even pointing to the absence of a triplet gap, thus motivating a detailed analysis of competing effects within a well-controlled model. In the present study, we track the effects of the 3N force and in-medium modifications in the representative case of the ^3P_2 channel, based on the Argonne v_{18} two-nucleon (2N) interaction supplemented by 3N interactions of the Urbana IX family. Sensitivity of the results to the input interaction is clearly demonstrated. We point out consistency issues with respect to the simultaneous treatment of 3N forces and in-medium effects, which warrant further investigation. We consider this pilot study as the first step toward a systematic and comprehensive exploration of coupled-channel ^3P F_2 pairing using a broad range of 2N and 3N interactions from the current generation of refined semi-phenomenological models and models derived from chiral effective field theory.

  10. Role of photoexcited nitrogen dioxide chemistry on ozone formation and emission control strategy over the Pearl River Delta, China

    Science.gov (United States)

    A new hydroxyl radical formation pathway via photo-excited nitrogen dioxide chemistry is incorporated into a chemistry-only box model as well as a 3D air quality model to examine its potential role on ozone formation and emission control strategy over the Pearl River Delta region...

  11. Controllable behaviours of rogue wave triplets in the nonautonomous nonlinear and dispersive system

    International Nuclear Information System (INIS)

    Dai Chaoqing; Tian Qing; Zhu Shiqun

    2012-01-01

    A similarity transformation connecting the variable coefficient nonlinear Schrödinger equation with the standard nonlinear Schrödinger equation is constructed. The self-similar rogue wave triplet solutions (rational solutions) are analytically obtained for the nonautonomous nonlinear and dispersive system. The controllable behaviours of rogue wave triplets in two typical soliton management systems are discussed. In the exponential dispersion decreasing fibre, three kinds of rogue wave triplets with controllable behaviours are analysed. In the periodic distributed system, the rogue wave triplets recur periodically in the form of a cluster. (paper)

  12. Exploring the triplet parameters space to optimise the final focus of the FCC-hh

    CERN Document Server

    AUTHOR|(CDS)2141109; Abelleira, Jose; Seryi, Andrei; Cruz Alaniz, Emilia

    2017-01-01

    One of the main challenges when designing final focus systems of particle accelerators is maximising the beam stay clear in the strong quadrupole magnets of the inner triplet. Moreover it is desirable to keep the quadrupoles in the triplet as short as possible for space and costs reasons but also to reduce chromaticity and simplify corrections schemes. An algorithm that explores the triplet parameter space to optimise both these aspects was written. It uses thin lenses as a first approximation and MADX for more precise calculations. In cooperation with radiation studies, this algorithm was then applied to design an alternative triplet for the final focus of the Future Circular Collider (FCC-hh).

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

    Science.gov (United States)

    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.

  14. Mother-daughter in vitro fertilization triplet surrogate pregnancy.

    Science.gov (United States)

    Michelow, M C; Bernstein, J; Jacobson, M J; McLoughlin, J L; Rubenstein, D; Hacking, A I; Preddy, S; Van der Wat, I J

    1988-02-01

    A successful triplet pregnancy has been established in a surrogate gestational mother following the transfer of five embryos fertilized in vitro. The oocytes were donated by her biological daughter, and the sperm obtained from the daughter's husband. The daughter's infertility followed a total abdominal hysterectomy performed for a postpartum hemorrhage as a result of a placenta accreta. Synchronization of both their menstrual cycles was obtained using oral contraceptive suppression for 2 months, followed by stimulation of both the surrogate gestational mother and her daughter such that embryo transfer would occur at least 48 hr after the surrogate gestational mother's own ovulation. This case raises a number of medical, social, psychological, and ethical issues.

  15. The role of triplet correlation function in dense fluids

    International Nuclear Information System (INIS)

    Rashid, R.I.M.A.

    1993-09-01

    In the theory of dense liquids, one usually introduces various correlation functions for describing properties of such systems. It has proved impossible to solve these correlation functions exactly and as such one often resorts to some meaningful approximations for their solutions. It is well known that unless proper precautions are taken, the approximate solutions will violate some useful sum rules and thermodynamic consistency conditions. Here the general rules for generating thermodynamically consistent approximate correlation functions are discussed. The role of triplet correlation is elucidated further by calculating a residual correction to the vacancy formation energy via three-particle correlation in rare gas solids. (author). 16 refs, 4 figs, 1 tab

  16. Tsallis q-triplet and Stock Market Indices: The cases of S & P 500 and TVIX

    Directory of Open Access Journals (Sweden)

    A. C. Iliopoulos

    2015-01-01

    Full Text Available In this study we present results of the evaluation of q − triplet of Tsallis non-extensive statistics concerning two time stock market time series, Standart & Poor’s 500 (S & P 500 and TVIX. The analysis of the results, support the hypothesis in which economic dynamics from physical point of view correspond to far from equilibrium spatial distributed non-linear dynamics. In particular, the analysis of the stock market time series revealed underlying complex dynamics, indicating clearly that the statistics of the dynamics in the multifractal phase space can be described by Tsallis distribution functions of power law and heavy tails forms. The non-extensive character of the underlying dynamics is related to the existence of long range interactions in space and time, as well as the interaction in many scales. In addition, the detailed analysis of S & P index unraveled the existence of non-equilibrium phase transitions depicted clearly in the variations of Tsallis q-triplet values. These phase transitions are connected with non-equilibrium stationary states of economical dynamics derived from processes of strong self organization which correspond to local maxima of Tsallis entropy, while the changes in the control parameters can induce new phase transitions and shifts to new metaequilibrium steady states of maximizing Tsallis entropy. These phase transitions lead to changes in Tsallis qtriplet values which correspond to multi-fractal changes in the formation of the phase state and an alteration in the phenomenology of the economical system. Finally, these characteristics also indicate the existence of fractional dynamics in the phase space which can be described through fractional Fokker-Planck equations and anomalous diffusion equations. The solutions of these equations are fractional spatiotemporal functions and non-Gaussian distributions functions which fall into the category of Levy distributions and Tsallis distributions.

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

    Science.gov (United States)

    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.

  18. Kinetic and mechanisms of methanimine reactions with singlet and triplet molecular oxygen: Substituent and catalyst effects

    Science.gov (United States)

    Asgharzadeh, Somaie; Vahedpour, Morteza

    2018-06-01

    Methanimine reaction with O2 on singlet and triplet potential energy surfaces are investigated using B3PW91, M06-2X, MP2 and CCSD(T) methods. Thermodynamic and kinetic parameters are calculated at M06-2X method. The most favorable channel involves H-abstraction of CH2NH+O2 to the formation of HCN + H2O2 products via low level energy barrier. The catalytic effect of water molecule on HCN + H2O2 products pathway are investigated. Result shows that contribution of water molecule using complex formation with methanimine can decreases barrier energy of transition state and the reaction rate increases. Also, substituent effect of fluorine atom as deactivating group are investigated on the main reaction pathway.

  19. Shortest triplet clustering: reconstructing large phylogenies using representative sets

    Directory of Open Access Journals (Sweden)

    Sy Vinh Le

    2005-04-01

    Full Text Available Abstract Background Understanding the evolutionary relationships among species based on their genetic information is one of the primary objectives in phylogenetic analysis. Reconstructing phylogenies for large data sets is still a challenging task in Bioinformatics. Results We propose a new distance-based clustering method, the shortest triplet clustering algorithm (STC, to reconstruct phylogenies. The main idea is the introduction of a natural definition of so-called k-representative sets. Based on k-representative sets, shortest triplets are reconstructed and serve as building blocks for the STC algorithm to agglomerate sequences for tree reconstruction in O(n2 time for n sequences. Simulations show that STC gives better topological accuracy than other tested methods that also build a first starting tree. STC appears as a very good method to start the tree reconstruction. However, all tested methods give similar results if balanced nearest neighbor interchange (BNNI is applied as a post-processing step. BNNI leads to an improvement in all instances. The program is available at http://www.bi.uni-duesseldorf.de/software/stc/. Conclusion The results demonstrate that the new approach efficiently reconstructs phylogenies for large data sets. We found that BNNI boosts the topological accuracy of all methods including STC, therefore, one should use BNNI as a post-processing step to get better topological accuracy.

  20. Assessment of immunological properties of neurofilament triplet proteins.

    Science.gov (United States)

    Schlaepfer, W W; Lee, V; Wu, H L

    1981-12-07

    The relationship between mammalian neurofilament triplet proteins was studied immunologically using rabbit and guinea pig antibodies to bovine neurofilament triplet proteins. Neurofilament proteins were separated by preparative electrophoresis, each protein being isolated and re-electrophoresed to enhance purification. Antisera to 68,000 (P68), 150,000 (P150) and 200,000 (P200) dalton neurofilament proteins showed greatest activity with the corresponding protein immunogen but also revealed cross-reactivity with the other two neurofilament proteins when assessed by the ELISA method. The same antigenic inoculum elicited variable cross-reactivity, more in the guinea pig than in the rabbit. Rabbit antisera to P68 was specific in that it did not cross-react with P150 or P200. Rabbit antisera to P150 and to P200 were rendered specific by absorption with P200 and P150, respectively. By electron microscopy, isolated neurofilaments became decorated with an uniform coat of antibodies when exposed to specific antisera for each of the neurofilament proteins. By indirect immunofluorescence, each antisera showed identical patterns of tissue localization, corresponding to the distribution of neurofilaments in peripheral nerve, spinal ganglia, spinal cord, cerebellum and cerebrum. Neurofilament antigens were not detected in liver, kidney, spleen, lung, bladder, intestine, aorta, heart or tongue.

  1. Fractional vortex lattice structures in spin-triplet superconductors

    International Nuclear Information System (INIS)

    Chung, Suk Bum; Agterberg, Daniel F; Kim, Eun-A

    2009-01-01

    Motivated by recent interest in spin-triplet superconductors, we investigate the vortex lattice structures for this class of unconventional superconductors. We discuss how the order parameter symmetry can give rise to U(1)xU(1) symmetry in the same sense as in spinor condensates, making half-quantum vortices (HQVs) topologically stable. We then calculate the vortex lattice structure of HQVs, with particular attention on the roles of the crystalline lattice, the Zeeman coupling and Meissner screening, all absent in spinor condensates. Finally, we consider how spin-orbit coupling leads to a breakdown of the U(1)xU(1) symmetry in free energy and whether the HQV lattice survives this symmetry breaking. As examples, we examine simpler spin-triplet models proposed in the context of Na x CoO 2 ·yH 2 O and Bechgaard salts, as well as the better known and more complex model for Sr 2 RuO 4 .

  2. Mode of conception of triplets and high order multiple pregnancies.

    LENUS (Irish Health Repository)

    Basit, I

    2012-03-01

    A retrospective audit was performed of all high order multiple pregnancies (HOMPs) delivered in three maternity hospitals in Dublin between 1999 and 2008. The mode of conception for each pregnancy was established with a view to determining means of reducing their incidence. A total of 101 HOMPs occurred, 93 triplet, 7 quadruplet and 1 quintuplet. Information regarding the mode of conception was available for 78 (81%) pregnancies. Twenty eight (27.7%) were spontaneous, 34 (33.7%) followedlVF\\/ICSI\\/FET treatment (in-vitro fertilisation, intracytoplasmic sperm injection, frozen embryo transfer), 16 (15.8%) resulted from Clomiphene Citrate treatment and 6 (6%) followed ovulation induction with gonadotrophins. Triplet and HOMPs are a major cause of maternal, feta land neonatal morbidity. Many are iatrogenic, arising from fertility treatments including Clomiphene. Reducing the numbers of embryos transferred will address IVF\\/ICSI\\/FET-related multiple pregnancy rates and this is currently happening in Ireland. Clomiphene and gonadotrophins should only be prescribed when appropriate resources are available to monitor patients adequately.

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

    Science.gov (United States)

    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.

  4. Dynamical mechanism of charge separation by photoexcited generation of proton–electron pairs in organic molecular systems. A nonadiabatic electron wavepacket dynamics study

    Energy Technology Data Exchange (ETDEWEB)

    Yamamoto, Kentaro, E-mail: kyamamoto@fukui.kyoto-u.ac.jp; Takatsuka, Kazuo, E-mail: kaztak@fukui.kyoto-u.ac.jp

    2016-08-22

    Graphical abstract: Asymptotic biradical state produced by the excited-state coupled proton–electron transfer (CPET), resulting in charge separation (proton–electron pair creation) on a proton–electron acceptor A, in a series of photochemical systems generally denoted as X–Mn–OH{sub 2}⋯A, where X = (OH, Ca(OH){sub 3}) and A = (N-methylformamidine, guanidine, imidazole, or ammonia clusters). - Abstract: In this perspective article, we review, along with presenting new results, a series of our theoretical analyses on the excited-state mechanism of charge separation (proton–electron pair creation) relevant to the photoinduced water-splitting reaction (2H{sub 2}O → 4H{sup +} + 4e{sup −} + O{sub 2}) in organic and biological systems, which quite often includes Mn clusters in various molecular configurations. The present mechanism is conceived to be universal in the triggering process of the photoexcited water splitting dynamics. In other words, any Mn-based catalytic charge separation is quite likely to be initiated according to this mechanism. As computationally tractable yet realistic models, we examine a series of systems generally expressed as X–Mn–OH{sub 2}⋯A, where X = (OH, Ca(OH){sub 3}) and A = (N-methylformamidine, guanidine, imidazole or ammonia cluster) in terms of the theory of nonadiabatic electron wavepacket dynamics. We first find both an electron and a proton are simultaneously transferred to the acceptors through conical intersections upon photoexcitation. In this mechanism, the electron takes different pathways from that of the proton and reaches the densely lying Rydberg-like states of the acceptors in the end, thereby inducing charge separation. Therefore the presence of the Rydberg-like diffused unoccupied states as an electron acceptor is critical for this reaction to proceed. We also have found another crucial nonadiabatic process that deteriorates the efficiency of charge separation by rendering the created pair of proton

  5. Suppressing Energy Loss due to Triplet Exciton Formation in Organic Solar Cells: The Role of Chemical Structures and Molecular Packing

    KAUST Repository

    Chen, Xiankai; Wang, Tonghui; Bredas, Jean-Luc

    2017-01-01

    In the most efficient solar cells based on blends of a conjugated polymer (electron donor) and a fullerene derivative (electron acceptor),ultrafast formation of charge-transfer (CT) electronic states at the donor-acceptor interfaces and efficient separation of these CT states into free charges, lead to internal quantum efficiencies near 100%. However, there occur substantial energy losses due to the non-radiative recombinations of the charges, mediated by the loweset-energy (singlet and triplet) CT states; for example, such recombinations can lead to the formation of triplet excited electronic states on the polymer chains, which do not generate free charges. This issue remains a major factor limiting the power conversion efficiencies (PCE) of these devices. The recombination rates are, however, difficult to quantify experimentally. To shed light on these issues, here, an integrated multi-scale theoretical approach that combines molecular dynamics simulations with quantum chemistry calculations is employed in order to establish the relationships among chemical structures, molecular packing, and non-radiative recombination losses mediated by the lowest-energy charge-transfer states.

  6. Suppressing Energy Loss due to Triplet Exciton Formation in Organic Solar Cells: The Role of Chemical Structures and Molecular Packing

    KAUST Repository

    Chen, Xiankai

    2017-04-21

    In the most efficient solar cells based on blends of a conjugated polymer (electron donor) and a fullerene derivative (electron acceptor),ultrafast formation of charge-transfer (CT) electronic states at the donor-acceptor interfaces and efficient separation of these CT states into free charges, lead to internal quantum efficiencies near 100%. However, there occur substantial energy losses due to the non-radiative recombinations of the charges, mediated by the loweset-energy (singlet and triplet) CT states; for example, such recombinations can lead to the formation of triplet excited electronic states on the polymer chains, which do not generate free charges. This issue remains a major factor limiting the power conversion efficiencies (PCE) of these devices. The recombination rates are, however, difficult to quantify experimentally. To shed light on these issues, here, an integrated multi-scale theoretical approach that combines molecular dynamics simulations with quantum chemistry calculations is employed in order to establish the relationships among chemical structures, molecular packing, and non-radiative recombination losses mediated by the lowest-energy charge-transfer states.

  7. Mixed Inert scalar triplet dark matter, radiative neutrino masses and leptogenesis

    Directory of Open Access Journals (Sweden)

    Wen-Bin Lu

    2017-11-01

    Full Text Available The neutral component of an inert scalar multiplet with hypercharge can provide a stable dark matter particle when its real and imaginary parts have a splitting mass spectrum. Otherwise, a tree-level dark-matter-nucleon scattering mediated by the Z boson will be much above the experimental limit. In this paper we focus on a mixed inert scalar triplet dark matter scenario where a complex scalar triplet with hypercharge can mix with another real scalar triplet without hypercharge through their renormalizable coupling to the standard model Higgs doublet. We consider three specified cases that carry most of the relevant features of the full parameter space: (i the neutral component of the real triplet dominates the dark matter particle, (ii the neutral component of the complex triplet dominates the dark matter particle; and (iii the neutral components of the real and complex triplets equally constitute the dark matter particle. Subject to the dark matter relic abundance and direct detection constraint, we perform a systematic study on the allowed parameter space with particular emphasis on the interplay among triplet-doublet terms and gauge interactions. In the presence of these mixed inert scalar triplets, some heavy Dirac fermions composed of inert fermion doublets can be utilized to generate a tiny Majorana neutrino mass term at one-loop level and realize a successful leptogenesis for explaining the cosmic baryon asymmetry.

  8. Codon-triplet context unveils unique features of the Candida albicans protein coding genome

    Directory of Open Access Journals (Sweden)

    Oliveira José L

    2007-11-01

    Full Text Available Abstract Background The evolutionary forces that determine the arrangement of synonymous codons within open reading frames and fine tune mRNA translation efficiency are not yet understood. In order to tackle this question we have carried out a large scale study of codon-triplet contexts in 11 fungal species to unravel associations or relationships between codons present at the ribosome A-, P- and E-sites during each decoding cycle. Results Our analysis unveiled high bias within the context of codon-triplets, in particular strong preference for triplets of identical codons. We have also identified a surprisingly large number of codon-triplet combinations that vanished from fungal ORFeomes. Candida albicans exacerbated these features, showed an unbalanced tRNA population for decoding its pool of codons and used near-cognate decoding for a large set of codons, suggesting that unique evolutionary forces shaped the evolution of its ORFeome. Conclusion We have developed bioinformatics tools for large-scale analysis of codon-triplet contexts. These algorithms identified codon-triplets context biases, allowed for large scale comparative codon-triplet analysis, and identified rules governing codon-triplet context. They could also detect alterations to the standard genetic code.

  9. Epidemiological and birth weight characteristics of triplets: a study from the Dutch twin register

    NARCIS (Netherlands)

    Orlebeke, J.F.; Boomsma, D.I.; Eriksson, A.W.

    1993-01-01

    From 112 triplet sets, born in The Netherlands from the end of 1986 to the beginning of 1991 and registered in the Dutch Twin Register, several details such as birth weight, gestational age, zygosity, and etiology were assessed by questionnaire, which was filled out by the mother. For 33 triplet

  10. Maternal and neonatal outcomes in twin and triplet gestations in Western Saudi Arabia

    Directory of Open Access Journals (Sweden)

    Samera F. AlBasri

    2017-06-01

    Full Text Available Objectives: Tocompare maternal and neonatal complications in twin and triplet gestations at King Abdulaziz University Hospital, Jeddah, Saudi Arabia. Methods: Retrospective medical records of 165 women with 144 twin and 21 triplet pregnancies from 2004 to 2011 were analyzed. Comparisons were carried out for maternal complications, gestational age at birth, neonatal birth weight, and neonatal intensive care admission. Results: Most common complications were preterm birth (49%, gestational diabetes mellitus (13.3%, and premature rupture of membrane (4.8%. All triplet pregnancies and 42% twin pregnancies terminated in preterm birth. Gestational length was longer (p less than 0.001 in twin births (36.0 ± 3.05 weeks than for triplet births (32 ± 3.81 weeks. Rates for in vitro fertilization, ovulation induction, and cesareans were higher in women with triplets than in those with twins. Neonatal intensive care unit (NICU admission was higher (p less than 0.001 for triplets (76.2% than for twins (23.6%. The mean weight of twins was 2333.83 ± 558.69 grams and triplets was 1553.41 ± 569.73 grams. Hyaline membrane disease, neonatal jaundice, and neonatal sepsis were most common neonatal complications. Conclusion: Neonates from triplet pregnancies were preterm, had low birth weight and needed more often NICU admission in comparison to those from twin pregnancies.

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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.

  13. Ultrafast lattice dynamics in photoexcited nanostructures. Femtosecond X-ray diffraction with optimized evaluation schemes

    International Nuclear Information System (INIS)

    Schick, Daniel

    2013-01-01

    Within the course of this thesis, I have investigated the complex interplay between electron and lattice dynamics in nanostructures of perovskite oxides. Femtosecond hard X-ray pulses were utilized to probe the evolution of atomic rearrangement directly, which is driven by ultrafast optical excitation of electrons. The physics of complex materials with a large number of degrees of freedom can be interpreted once the exact fingerprint of ultrafast lattice dynamics in time-resolved X-ray diffraction experiments for a simple model system is well known. The motion of atoms in a crystal can be probed directly and in real-time by femtosecond pulses of hard X-ray radiation in a pump-probe scheme. In order to provide such ultrashort X-ray pulses, I have built up a laser-driven plasma X-ray source. The setup was extended by a stable goniometer, a two-dimensional X-ray detector and a cryogen-free cryostat. The data acquisition routines of the diffractometer for these ultrafast X-ray diffraction experiments were further improved in terms of signal-to-noise ratio and angular resolution. The implementation of a high-speed reciprocal-space mapping technique allowed for a two-dimensional structural analysis with femtosecond temporal resolution. I have studied the ultrafast lattice dynamics, namely the excitation and propagation of coherent phonons, in photoexcited thin films and superlattice structures of the metallic perovskite SrRuO 3 . Due to the quasi-instantaneous coupling of the lattice to the optically excited electrons in this material a spatially and temporally well-defined thermal stress profile is generated in SrRuO 3 . This enables understanding the effect of the resulting coherent lattice dynamics in time-resolved X-ray diffraction data in great detail, e.g. the appearance of a transient Bragg peak splitting in both thin films and superlattice structures of SrRuO 3 . In addition, a comprehensive simulation toolbox to calculate the ultrafast lattice dynamics and the

  14. Highly efficient greenish-blue platinum-based phosphorescent organic light-emitting diodes on a high triplet energy platform

    Energy Technology Data Exchange (ETDEWEB)

    Chang, Y. L., E-mail: yilu.chang@mail.utoronto.ca; Gong, S., E-mail: sgong@chem.utoronto.ca; White, R.; Lu, Z. H., E-mail: zhenghong.lu@utoronto.ca [Department of Materials Science and Engineering, University of Toronto, 184 College St., Toronto, Ontario M5S 3E4 (Canada); Wang, X.; Wang, S., E-mail: wangs@chem.queensu.ca [Department of Chemistry, Queen' s University, 90 Bader Lane, Kingston, Ontario K7L 3N6 (Canada); Yang, C. [Department of Chemistry, Wuhan University, Wuhan 430072 (China)

    2014-04-28

    We have demonstrated high-efficiency greenish-blue phosphorescent organic light-emitting diodes (PHOLEDs) based on a dimesitylboryl-functionalized C^N chelate Pt(II) phosphor, Pt(m-Bptrz)(t-Bu-pytrz-Me). Using a high triplet energy platform and optimized double emissive zone device architecture results in greenish-blue PHOLEDs that exhibit an external quantum efficiency of 24.0% and a power efficiency of 55.8 lm/W. This record high performance is comparable with that of the state-of-the-art Ir-based sky-blue organic light-emitting diodes.

  15. Manufacturing experience for the LHC inner triplet quadrupole cables

    CERN Document Server

    Scanlan, R M; Bossert, R; Kerby, J S; Ghosh, A K; Boivin, M; Roy, T

    2002-01-01

    The design for the U.S. LHC Inner Triplet Quadrupole magnet requires a 37 strand (inner layer) and a 46 strand (outer layer) cable. This represents the largest number of strands attempted to date for a production quantity of Rutherford-type cable. The cable parameters were optimized during the production of a series of short prototype magnets produced at FNAL. These optimization studies focused on critical current degradation, dimensional control, coil winding, and interstrand resistance. After the R&D phase was complete, the technology was transferred to NEEW and a new cabling machine was installed to produce these cables. At present, about 60 unit lengths, out of 90 required for the entire production series of magnets, have been completed for each type of cable. The manufacturing experience with these challenging cables will be reported. Finally, the implications for even larger cables, with more strands, will be discussed. (8 refs).

  16. Learning deep features with adaptive triplet loss for person reidentification

    Science.gov (United States)

    Li, Zhiqiang; Sang, Nong; Chen, Kezhou; Gao, Changxin; Wang, Ruolin

    2018-03-01

    Person reidentification (re-id) aims to match a specified person across non-overlapping cameras, which remains a very challenging problem. While previous methods mostly focus on feature extraction or metric learning, this paper makes the attempt in jointly learning both the global full-body and local body-parts features of the input persons with a multichannel convolutional neural network (CNN) model, which is trained by an adaptive triplet loss function that serves to minimize the distance between the same person and maximize the distance between different persons. The experimental results show that our approach achieves very promising results on the large-scale Market-1501 and DukeMTMC-reID datasets.

  17. HE I triplet line emission in class 1 Seyfert galaxies

    International Nuclear Information System (INIS)

    Feldman, F.R.

    1979-01-01

    The equation of statistical equilibrium were solved for an 11-level helium atom, including all important radiative and collisional transitions and allowing for self-absorption from any level. Gas physical conditions considered are 5 x 10 8 cm -3 less than or equal to N less than or equal to 5 x 10 10 cm -3 , 5000 K less than or equal to T less than or equal to 20,000 K and a range of optical depth in the lambda 10830 line (10 less than or equal to tau(lambda 10830) less than or equal to 500) as a free parameter. For a photoionized, optically thick cloud, tau(lambda 10830) is shown to be nearly proportional to a measure of the ratio of photoionizing flux to cloud density (U 1 ), provided that photoionization from excited He 0 levels can be neglected. Calculated triplet line intensities as a function of tau(lambda 10830) are presented in graphical form, illustrating the significance of collisional excitation from 2 3 S and 2 3 P as well as self-absorption in lines terminating on 2 3 P. The possible importance of photoionization from the n = 2 levels by continuum and resonance-line radiation was investigated. This process may significantly influence triplet line strengths for small photoionizing-source/cloud separations (high U 1 ), unless most scattered hydrogen Lα and C IV lambda 1549 photons are destroyed by dust grains (or by some other mechanism). New spectrophotometric observations of 3C 120, Mrk 618, NGC 7469, and Mrk 335 are compared to the theoretical results. It appears that class 1 Seyfert galaxies with strong helium lines may be characterized by N approx. = 5 x 10 9 cm -3 , T approx. = 15,000 K and tau(lambda 10830) approx. = 100, assuming no photoionization from n = 2

  18. InGaN compositional patterning by ultraviolet photoexcitation during NH3-based MOMBE - A pathway to 3D epitaxy

    International Nuclear Information System (INIS)

    Pritchett, D.; Henderson, W.; Billingsley, D.; Doolittle, W.A.

    2008-01-01

    Lateral compositional patterning of InGaN during NH 3 -based MOMBE by digital micromirror patterning of UV photoexcitation is demonstrated. Preferential desorption of In/In-methyl species during InGaN surface exposure to an elliptically focused 5 kW Hg-Xe arc lamp (λ=365 nm) limits the incorporation of indium during growth. Localized photoexcitation results in the preferential In/In-methyl desorption, resulting in indium mole fractions of 0.10 in unexposed regions to as low as 0 in fully exposed regions. The technique demonstrates promise for integration of micromirrors for dynamic and maskless selective epitaxy towards the realization of complex, 3D device structures. (copyright 2008 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  19. Characteristics of terahertz wave modulation using wavelength-selective photoexcitation in pentacene/Si and TIPS pentacene/Si bilayers

    Directory of Open Access Journals (Sweden)

    Hyung Keun Yoo

    2016-11-01

    Full Text Available We demonstrate the characteristics of the optical control of terahertz (THz wave transmission in photoexcited bilayers of pentacene/Si and 6,13-bis(triisopropylsilylethynyl pentacene (TIPS pentacene/Si. The modulation efficiency is influenced significantly by the photoexcitation wavelength of the optical beams. Lower optical absorption of organic materials leads to higher modulation efficiency because the photocarriers excited on Si with a higher diffusion rate and mobility are far more instrumental in increasing the modulation than the excitons generated on the organic layers. Securing a sufficient depth for carrier diffusion on organic layers is also important for increasing the THz modulation efficiency. These findings may be useful for designing highly efficient and spectrally controllable THz wave modulators.

  20. An instant photo-excited electrons relaxation on the photo-degradation properties of TiO2-x films

    CSIR Research Space (South Africa)

    Nkosi, SS

    2014-11-01

    Full Text Available of Photochemistry and Photobiology A: Chemistry 293 (2014) 72–80 An instant photo-excited electrons relaxation on the photo- degradation properties of TiO2−x films S.S. Nkosi a,b,∗, I. Kortidis d, D.E. Motaungc,∗, P.R. Makgwanec, O.M. Ndwandwe b, S.S. Rayc, G...

  1. Transient Spectroscopy of Photoexcitations and Morphology Control of Organometal Trihalide Perovskites

    Science.gov (United States)

    Zhai, Yaxin; Lafalce, Evan; Sheng, Chuan-Xiang; Zhang, Chuang; Sun, Dali; Vardeny, Zeev Valy

    We studied the photoexcitation dynamics in various hybrid perovskites by using broadband ps transient photomodulation (PM) spectroscopy and variable stripe length (VSL) technique. We observed both excitonic and free carriers spectral features in MAPbI3 but mainly excitonic transition in MAPbI1.1Br1.9 and MAPbI3-xClx films. We also fabricated MAPbBr3 films with nano-crystal pinning (NCP) treatment, which allows for smaller crystalline grain size. The transient spectra show a narrower and longer-lived photobleaching band in NCP treated films consistent with the increase in the photoluminescence efficiency. In addition the net optical gain measured by VSL is markedly increased up to 300 cm-1, and the lasing threshold is concurrently reduced. Measurement of the waveguide losses in the NCP films shows that the improvement in lasing properties can partly be attributed to the reduced optical scattering. Work supported by the AFOSR through a MURI Grant RA 9550-14-1-0037.

  2. A photo-excited broadband to dual-band tunable terahertz prefect metamaterial polarization converter

    Science.gov (United States)

    Zhu, Jianfeng; Yang, Yang; Li, Shufang

    2018-04-01

    A new and simple design of photo-excited broadband to dual-band tunable terahertz (THz) metamaterial cross polarization converter is proposed in this paper. The tunable converter is a sandwich structure with the center-cut cross-shaped metallic patterned structure as a resonator, the middle dielectric layer as a spacer and the bottom metallic film as the ground. The conductivity of the photoconductive semiconductor (Silicon) filled in the gap of the cross-shaped metallic resonator can be tuned by the incident pump power, leading to an easy modulation of the electromagnetic response of the proposed converter. The results show that the proposed cross-polarization converter can be tuned from a broadband with polarization conversion ratio (PCR) beyond 95% (1.86-2.94 THz) to dual frequency bands (fl = 1 . 46 THz &fh = 2 . 9 THz). The conversion peaks can reach 99.9% for the broadband and, 99.5% (fl) and 99.7% (fh) for the dual-band, respectively. Most importantly, numerical simulations demonstrate that the broadband/dual-band polarization conversion mechanism of the converter originates from the localized surface plasmon modes, which make the design simple and different from previous designs. With these good features, the proposed broadband to dual-band tunable polarization converter is expected to be used in widespread applications.

  3. Photoexcitation and Photochemical Stability of Organic Photovoltaic Materials from First Principles

    Science.gov (United States)

    Sai, Na; Leung, Kevin

    2013-03-01

    The development of high efficiency organic photovoltaics (OPV) has recently become enabled by the synthesis of new conjugated polymers with low band gap that allow light absorption over a broader range of the spectrum. Stability of these new polymers, a key requirement for commercialization, has not yet received sufficient attention. Here, we report first-principles theoretical modeling of photo-induced degradation of OPV polymers carried out using ab-initio density functional theory (DFT). We report photooxidation routes and reaction products for reactive species including superoxide oxygen anions and hydroxyl groups interacting with the standard workhorse OPV polymer, poly(3-hexyl-thiophene) (P3HT). We discuss theoretical issues and challenges affecting the modeling such reactions in OPV polymers. We also discuss the application of theoretical methods to low-band-gap polymers, and in particular, the effect of the chemical substitution on the photoexcitation properties of these new polymers. Sandia National Laboratories is a multiprogram laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Deparment of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000. This work is supported by the Energy Frontier Research Center funded by the U.S. DOE Office of Basic Energy Sciences under Award number DE-SC0001091.

  4. Photoexcitations in fully organic nanocomposites of poly(3-hexylthiophene) and multiwalled carbon nanotubes

    International Nuclear Information System (INIS)

    Bakour, Anass; Geschier, Fredéric; Baitoul, Mimouna; Wéry, Jany; Massuyeau, Florian; Faulques, Eric

    2016-01-01

    Insertion effects of multiwalled carbon nanotubes (MWNTs) at different loads in the regioregular poly(3-hexylthiophene) (RR-P3HT) electroactive polymer are investigated with transmission electron microscopy (TEM), X-ray diffraction, infrared and optical absorption, photoluminescence (PL) and photoconductivity techniques. MWNTs in composites quench the deep red emission of P3HT. They also act as inhibitors of polymer aggregates favoring shorter conjugated segments during composite synthesis and the formation of a charge-transfer complex at the P3HT/MWNT interface through delocalization of π electrons along the conjugated segments. Under photoexcitation, a significant fraction of excitons dissociates non radiatively with charge hopping towards the MWNTs network and triggers an augmentation of photoconductivity. - Highlights: • Composites of multiwalled carbon nanotubes (MWNTs) and poly(3- hexylthiophene) (P3HT). • Thin nanocomposite films with various MWNTs concentrations x. • Full study with synthesis, structural, optical and vibrational experiments. • Drastic and ultrafast photoluminescence quenching with increasing x. • Augmentation of photoconductivity in composite.

  5. Photoexcitations in fully organic nanocomposites of poly(3-hexylthiophene) and multiwalled carbon nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Bakour, Anass [Laboratory of Solid State Physics, Research Group Polymers and Nanomaterials, University Sidi Mohammed Ben Abdellah, Faculty of Sciences Dhar El Mahraz, P.O. Box 1796 Atlas, 30000 Fes (Morocco); Geschier, Fredéric [Institut des Matériaux Jean Rouxel, Université de Nantes, CNRS, UMR 6502, 2 Rue de la Houssinière, 44322 Nantes (France); Baitoul, Mimouna [Laboratory of Solid State Physics, Research Group Polymers and Nanomaterials, University Sidi Mohammed Ben Abdellah, Faculty of Sciences Dhar El Mahraz, P.O. Box 1796 Atlas, 30000 Fes (Morocco); Wéry, Jany; Massuyeau, Florian [Institut des Matériaux Jean Rouxel, Université de Nantes, CNRS, UMR 6502, 2 Rue de la Houssinière, 44322 Nantes (France); Faulques, Eric, E-mail: eric.faulques@cnrs-imn.fr [Institut des Matériaux Jean Rouxel, Université de Nantes, CNRS, UMR 6502, 2 Rue de la Houssinière, 44322 Nantes (France)

    2016-03-01

    Insertion effects of multiwalled carbon nanotubes (MWNTs) at different loads in the regioregular poly(3-hexylthiophene) (RR-P3HT) electroactive polymer are investigated with transmission electron microscopy (TEM), X-ray diffraction, infrared and optical absorption, photoluminescence (PL) and photoconductivity techniques. MWNTs in composites quench the deep red emission of P3HT. They also act as inhibitors of polymer aggregates favoring shorter conjugated segments during composite synthesis and the formation of a charge-transfer complex at the P3HT/MWNT interface through delocalization of π electrons along the conjugated segments. Under photoexcitation, a significant fraction of excitons dissociates non radiatively with charge hopping towards the MWNTs network and triggers an augmentation of photoconductivity. - Highlights: • Composites of multiwalled carbon nanotubes (MWNTs) and poly(3- hexylthiophene) (P3HT). • Thin nanocomposite films with various MWNTs concentrations x. • Full study with synthesis, structural, optical and vibrational experiments. • Drastic and ultrafast photoluminescence quenching with increasing x. • Augmentation of photoconductivity in composite.

  6. Study of the Contributions of Donor and Acceptor Photoexcitations to Open Circuit Voltage in Bulk Heterojunction Organic Solar Cells

    Directory of Open Access Journals (Sweden)

    Douglas Yeboah

    2017-10-01

    Full Text Available One of the key parameters in determining the power conversion efficiency (PCE of bulk heterojunction (BHJ organic solar cells (OSCs is the open circuit voltage . The processes of exciting the donor and acceptor materials individually in a BHJ OSC are investigated and are found to produce two different expressions for . Using the contributions of electron and hole quasi-Fermi levels and charge carrier concentrations, the two different expressions are derived as functions of the energetics of the donor and acceptor materials and the photo-generated charge carrier concentrations, and calculated for a set of donor-acceptor blends. The simultaneous excitation of both the donor and acceptor materials is also considered and the corresponding , which is different from the above two, is derived. The calculated from the photoexcitation of the donor is found to be somewhat comparable with that obtained from the photoexcitation of the acceptor in most combinations of the donor and acceptor materials considered here. It is also found that the calculated from the simultaneous excitations of donor and acceptor in BHJ OSCs is also comparable with the other two . All three thus derived produce similar results and agree reasonably well with the measured values. All three depend linearly on the concentration of the photoexcited charge carriers and hence incident light intensity, which agrees with experimental results. The outcomes of this study are expected to help in finding materials that may produce higher and hence enhanced PCE in BHJ OSCs.

  7. Bandgap modulation in photoexcited topological insulator Bi{sub 2}Te{sub 3} via atomic displacements

    Energy Technology Data Exchange (ETDEWEB)

    Hada, Masaki, E-mail: hadamasaki@okayama-u.ac.jp [Graduate School of Natural Science and Technology, Okayama University, Okayama 700-8530 (Japan); Materials and Structures Laboratory, Tokyo Institute of Technology, Yokohama 226-8503 (Japan); PRESTO, Japan Science and Technology Agency, Kawaguchi 332-0012 (Japan); Norimatsu, Katsura; Tsuruta, Tetsuya; Igarashi, Kyushiro; Kayanuma, Yosuke; Sasagawa, Takao; Nakamura, Kazutaka G. [Materials and Structures Laboratory, Tokyo Institute of Technology, Yokohama 226-8503 (Japan); Tanaka, Sei' ichi; Ishikawa, Tadahiko; Koshihara, Shin-ya [Department of Chemistry and Materials Science, Tokyo Institute of Technology, Tokyo 152-8551 (Japan); Keskin, Sercan [The Max Planck Institute for the Structure and Dynamics of Matter, The Hamburg Centre for Ultrafast Imaging, University of Hamburg, Hamburg 22761 (Germany); Miller, R. J. Dwayne [The Max Planck Institute for the Structure and Dynamics of Matter, The Hamburg Centre for Ultrafast Imaging, University of Hamburg, Hamburg 22761 (Germany); Departments of Chemistry and Physics, University of Toronto, Toronto M5S 3H6 (Canada); Onda, Ken [PRESTO, Japan Science and Technology Agency, Kawaguchi 332-0012 (Japan); Graduate School of Science and Engineering, Tokyo Institute of Technology, Yokohama 226-8502 (Japan)

    2016-07-14

    The atomic and electronic dynamics in the topological insulator (TI) Bi{sub 2}Te{sub 3} under strong photoexcitation were characterized with time-resolved electron diffraction and time-resolved mid-infrared spectroscopy. Three-dimensional TIs characterized as bulk insulators with an electronic conduction surface band have shown a variety of exotic responses in terms of electronic transport when observed under conditions of applied pressure, magnetic field, or circularly polarized light. However, the atomic motions and their correlation between electronic systems in TIs under strong photoexcitation have not been explored. The artificial and transient modification of the electronic structures in TIs via photoinduced atomic motions represents a novel mechanism for providing a comparable level of bandgap control. The results of time-domain crystallography indicate that photoexcitation induces two-step atomic motions: first bismuth and then tellurium center-symmetric displacements. These atomic motions in Bi{sub 2}Te{sub 3} trigger 10% bulk bandgap narrowing, which is consistent with the time-resolved mid-infrared spectroscopy results.

  8. Deep blue exciplex organic light-emitting diodes with enhanced efficiency; P-type or E-type triplet conversion to singlet excitons?

    Science.gov (United States)

    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.

  9. Exploring Higgs triplet models via vector boson scattering at the LHC

    International Nuclear Information System (INIS)

    Godfrey, Stephen; Moats, Ken

    2010-01-01

    We present the results of a study of Higgs triplet boson production arising in the littlest Higgs, left-right symmetric, and Georgi-Machacek models in the W ± W ± , W ± Z, W + W - , and ZZ channels at the LHC. We focus on the ''gold-plated'' purely leptonic decay modes and consider the irreducible electroweak, QCD, and t-quark backgrounds, applying a combination of forward-jet tagging, central-jet vetoing, and stringent leptonic cuts to suppress the backgrounds. We find that, given the constraints on the triplet vacuum expectation value (vev), considerable luminosity is required to observe Higgs triplet bosons in vector boson scattering. Observing a Higgs triplet at the LHC is most promising in the Georgi-Machacek model due to a weaker constraint on the triplet vev. In this model, we find that a Higgs triplet boson with a mass of 1.0(1.5) TeV can be observed at the LHC with an integrated luminosity as low as 41(119) fb -1 in the W ± W ± channel and as low as 171(474) fb -1 in the W ± Z channel. Observation of Higgs triplet bosons in these channels would help identify the underlying theory.

  10. Excited states

    CERN Document Server

    Lim, Edward C

    1974-01-01

    Excited States, Volume I reviews radiationless transitions, phosphorescence microwave double resonance through optical spectra in molecular solids, dipole moments in excited states, luminescence of polar molecules, and the problem of interstate interaction in aromatic carbonyl compounds. The book discusses the molecular electronic radiationless transitions; the double resonance techniques and the relaxation mechanisms involving the lowest triplet state of aromatic compounds; as well as the optical spectra and relaxation in molecular solids. The text also describes dipole moments and polarizab

  11. Running with triplets: How slepton masses change with doubly-charged Higgs bosons

    International Nuclear Information System (INIS)

    Setzer, N.; Spinner, S.

    2007-01-01

    We examine the slepton masses of SUSYLR models and how they change due to the presence of light doubly-charged Higgs bosons. We discover that the measurement of the slepton masses could bound and even predict the value of the third generation Yukawa coupling of leptons to the SU(2) R triplets. We also consider the unification prospects for this model with the addition of left-handed, B-L=0 triplets--a model we call the triplet extended supersymmetric standard model (TESSM)

  12. Distinctive Spectral Features of Exciton and Excimer States in the Ultrafast Electronic Deactivation of the Adenine Dinucleotide

    Science.gov (United States)

    Stuhldreier, Mayra C.; Röttger, Katharina; Temps, Friedrich

    We report the observation by transient absorption spectroscopy of distinctive spectro-temporal signatures of delocalized exciton versus relaxed, weakly bound excimer states in the ultrafast electronic deactivation after UV photoexcitation of the adenine dinucleotide.

  13. Dynamics of multidissociation paths of acetaldehyde photoexcited at 157 nm: Branching ratios, distributions of kinetic energy, and angular anisotropies of products

    Science.gov (United States)

    Lee, Shih-Huang

    2009-11-01

    After the photolysis of acetaldehyde (CH3CHO) at 157.6 nm in a molecular-beam apparatus using photofragment translational spectroscopy and vacuum-ultraviolet photoionization to detect products, we observed 13 photofragments associated with six primary dissociation channels and secondary dissociation of products CH3CO and HCO. We measured time-of-flight spectra and spatial angular anisotropies of products and evaluated the branching ratios of products. All photoproducts have nearly isotropic angular distributions with an average |β| value less than 0.05. Primary dissociations to CH3CO+H and CH3+HCO are two major paths; most CH3CO subsequently decomposes spontaneously to CH3+CO and CH2CO+H and most HCO decomposes to H+CO. The ternary dissociation to CH3+CO+H thus accounts for approximately half of the total branching. Dissociations to CH2CO+H2 and CH2+CH2O are observable, but the production of CH4+CO is ambiguous. The productions of C2H3+OH and C2H2+H2O indicate that isomerization from acetaldehyde to ethenol occurs before fragmentation. After photoexcitation to the n-3p state, most acetaldehyde converts into states T1 and S0 but a little isomerizes to ethenol followed by multichannel decomposition.

  14. Glass-like recovery of antiferromagnetic spin ordering in a photo-excited manganite Pr0.7Ca0.3MnO3

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, S. Y.; Langner, M. C.; Zhu, Y.; Chuang, Y. -D.; Rini, M.; Glover, T. E.; Hertlein, M. P.; Gonzalez, A.G. Cruz; Tahir, N.; Tomioka, Y.; Tokura, Y.; Hussain, Z.; Schoenlein, R. W.

    2014-01-16

    Electronic orderings of charges, orbitals and spins are observed in many strongly correlated electron materials, and revealing their dynamics is a critical step toward understanding the underlying physics of important emergent phenomena. Here we use time-resolved resonant soft x-ray scattering spectroscopy to probe the dynamics of antiferromagnetic spin ordering in the manganite Pr0:7Ca0:3MnO3 following ultrafast photo-exitation. Our studies reveal a glass-like recovery of the spin ordering and a crossover in the dimensionality of the restoring interaction from quasi-1D at low pump fluence to 3D at high pump fluence. This behavior arises from the metastable state created by photo-excitation, a state characterized by spin disordered metallic droplets within the larger charge- and spin-ordered insulating domains. Comparison with time-resolved resistivity measurements suggests that the collapse of spin ordering is correlated with the insulator-to-metal transition, but the recovery of the insulating phase does not depend on the re-establishment of the spin ordering.

  15. Pair and triplet approximation of a spatial lattice population model with multiscale dispersal using Markov chains for estimating spatial autocorrelation.

    Science.gov (United States)

    Hiebeler, David E; Millett, Nicholas E

    2011-06-21

    We investigate a spatial lattice model of a population employing dispersal to nearest and second-nearest neighbors, as well as long-distance dispersal across the landscape. The model is studied via stochastic spatial simulations, ordinary pair approximation, and triplet approximation. The latter method, which uses the probabilities of state configurations of contiguous blocks of three sites as its state variables, is demonstrated to be greatly superior to pair approximations for estimating spatial correlation information at various scales. Correlations between pairs of sites separated by arbitrary distances are estimated by constructing spatial Markov processes using the information from both approximations. These correlations demonstrate why pair approximation misses basic qualitative features of the model, such as decreasing population density as a large proportion of offspring are dropped on second-nearest neighbors, and why triplet approximation is able to include them. Analytical and numerical results show that, excluding long-distance dispersal, the initial growth rate of an invading population is maximized and the equilibrium population density is also roughly maximized when the population spreads its offspring evenly over nearest and second-nearest neighboring sites. Copyright © 2011 Elsevier Ltd. All rights reserved.

  16. Possible evidence for spin-transfer torque induced by spin-triplet supercurrent

    KAUST Repository

    Li, Lailai; Zhao, Yuelei; Zhang, Xixiang; Sun, Young

    2017-01-01

    Cooper pairs in superconductors are normally spin singlet. Nevertheless, recent studies suggest that spin-triplet Cooper pairs can be created at carefully engineered superconductor-ferromagnet interfaces. If Cooper pairs are spin

  17. Understanding triplet formation pathways in bulk heterojunction polymer : fullerene photovoltaic devices

    NARCIS (Netherlands)

    Tedla, B.; Zhu, F.; Cox, M.; Drijkoningen, J.; Manca, J.V.; Koopmans, B.; Goovaerts, E.

    2015-01-01

    Triplet exciton (TE) formation pathways are systematically investigated in prototype bulk heterojunction (BHJ) "super yellow" poly(p-phenylene vinylene) (SY-PPV) solar cell devices with varying fullerene compositions using complementary optoelectrical and electrically detected magnetic resonance

  18. Reconstructing neutrino properties from collider experiments in a Higgs triplet neutrino mass model

    International Nuclear Information System (INIS)

    Aristizabal Sierra, D.; Hirsch, M.; Valle, J. W. F.; Villanova del Moral, A.

    2003-01-01

    We extend the minimal supersymmetric standard model with bilinear R-parity violation to include a pair of Higgs triplet superfields. The neutral components of the Higgs triplets develop small vacuum expectation values (VEVs) quadratic in the bilinear R-parity breaking parameters. In this scheme the atmospheric neutrino mass scale arises from bilinear R-parity breaking while for reasonable values of parameters the solar neutrino mass scale is generated from the small Higgs triplet VEVs. We calculate neutrino masses and mixing angles in this model and show how the model can be tested at future colliders. The branching ratios of the doubly charged triplet decays are related to the solar neutrino angle via a simple formula

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

    Science.gov (United States)

    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.

  20. ESR-spin trapping studies on the interaction between anthraquinone triplets and aromatic compounds

    International Nuclear Information System (INIS)

    Moger, G.; Rockenbauer, A.; Simon, P.

    1980-01-01

    The ESR spin trapping technique was used for the detection of transient C-centered radicals in the photochemical interaction between triplet anthraquinone and aromatic hydroperoxide and alcohol. (author)

  1. IceBridge Riegl Laser Altimeter L2 Geolocated Surface Elevation Triplets

    Data.gov (United States)

    National Aeronautics and Space Administration — The IceBridge Riegl Laser Altimeter L2 Geolocated Surface Elevation Triplets (ILUTP2) data set contains surface range values for Antarctica and Greenland derived...

  2. Efficient Algorithms for Computing the Triplet and Quartet Distance Between Trees of Arbitrary Degree

    DEFF Research Database (Denmark)

    Brodal, Gerth Stølting; Fagerberg, Rolf; Mailund, Thomas

    2013-01-01

    ), respectively, and counting how often the induced topologies in the two input trees are different. In this paper we present efficient algorithms for computing these distances. We show how to compute the triplet distance in time O(n log n) and the quartet distance in time O(d n log n), where d is the maximal......The triplet and quartet distances are distance measures to compare two rooted and two unrooted trees, respectively. The leaves of the two trees should have the same set of n labels. The distances are defined by enumerating all subsets of three labels (triplets) and four labels (quartets...... degree of any node in the two trees. Within the same time bounds, our framework also allows us to compute the parameterized triplet and quartet distances, where a parameter is introduced to weight resolved (binary) topologies against unresolved (non-binary) topologies. The previous best algorithm...

  3. Radiative corrections to the Higgs couplings in the triplet model

    International Nuclear Information System (INIS)

    KIKUCHI, M.

    2014-01-01

    The feature of extended Higgs models can appear in the pattern of deviations from the Standard Model (SM) predictions in coupling constants of the SM-like Higgs boson (h). We can thus discriminate extended Higgs models by precisely measuring the pattern of deviations in the coupling constants of h, even when extra bosons are not found directly. In order to compare the theoretical predictions to the future precision data at the ILC, we must evaluate the theoretical predictions with radiative corrections in various extended Higgs models. In this paper, we give our comprehensive study for radiative corrections to various Higgs boson couplings of h in the minimal Higgs triplet model (HTM). First, we define renormalization conditions in the model, and we calculate the Higgs coupling; gγγ, hWW, hZZ and hhh at the one loop level. We then evaluate deviations in coupling constants of the SM-like Higgs boson from the predictions in the SM. We find that one-loop contributions to these couplings are substantial as compared to their expected measurement accuracies at the ILC. Therefore the HTM has a possibility to be distinguished from the other models by comparing the pattern of deviations in the Higgs boson couplings.

  4. An atlas of Calcium triplet spectra of active galaxies

    CERN Document Server

    Garcia-Rissmann, A; Asari, N V; Fernandes, R C; Schmitt, H; González-Delgado, R M; Storchi-Bergmann, T

    2005-01-01

    We present a spectroscopic atlas of active galactic nuclei covering the region around the 8498, 8542, 8662 Calcium triplet (CaT) lines. The sample comprises 78 objects, divided into 43 Seyfert 2s, 26 Seyfert 1s, 3 Starburst and 6 normal galaxies. The spectra pertain to the inner ~300 pc in radius, and thus sample the central kinematics and stellar populations of active galaxies. The data are used to measure stellar velocity dispersions (sigma_star) both with cross-correlation and direct fitting methods. These measurements are found to be in good agreement with each-other and with those in previous studies for objects in common. The CaT equivalent width is also measured. We find average values and sample dispersions of W_CaT of 4.6+/-2.0, 7.0 and 7.7+/-1.0 angstrons for Seyfert 1s, Seyfert 2s and normal galaxies, respectively. We further present an atlas of [SIII]\\lambda 9069 emission line profiles for a subset of 40 galaxies. These data are analyzed in a companion paper which addresses the connection between ...

  5. Singlet-to-triplet ratio in the deuteron breakup reaction pd → pnp at 585 MeV

    International Nuclear Information System (INIS)

    Uzikov, Yu.N.; Komarov, V.I.; Rathmann, F.; Seyfarth, H.

    2001-01-01

    Available experimental data on the exclusive pd → pnp reaction at 585 MeV show a narrow peak in the proton-neutron final-state interaction region. It was supposed previously, on the basis of a phenomenological analysis of the shape of this peak, that the final spin-singlet pn state provided about one third of the observed cross section. By comparing the absolute value of the measured cross section with that of pd elastic scattering using the Faeldt-Wilkin extrapolation theorem, it is shown here that the pd → pnp data can be explained mainly by the spin-triplet final state with a singlet admixture of a few percent. The smallness of the singlet contribution is compatible with existing pN → pNπ data and the one-pion exchange mechanism of the pd → pnp reaction

  6. Walking Down the Chalcogenic Group of the Periodic Table: From Singlet to Triplet Organic Emitters.

    Science.gov (United States)

    Kremer, Adrian; Aurisicchio, Claudia; De Leo, Federica; Ventura, Barbara; Wouters, Johan; Armaroli, Nicola; Barbieri, Andrea; Bonifazi, Davide

    2015-10-19

    The synthesis, X-ray crystal structures, ground- and excited-state UV/Vis absorption spectra, and luminescence properties of chalcogen-doped organic emitters equipped on both extremities with benzoxa-, benzothia-, benzoselena- and benzotellurazole (1X and 2X ) moieties have been reported for the first time. The insertion of the four different chalcogen atoms within the same molecular skeleton enables the investigation of only the chalcogenic effect on the organisation and photophysical properties of the material. Detailed crystal-structure analyses provide evidence of similar packing for 2O -2Se , in which the benzoazoles are engaged in π-π stacking and, for the heavier atoms, in secondary X⋅⋅⋅X and X⋅⋅⋅N bonding interactions. Detailed computational analysis shows that the arrangement is essentially governed by the interplay of van der Waals and secondary bonding interactions. Progressive quenching of the fluorescence and concomitant onset of phosphorescence features with gradually shorter lifetimes are detected as the atomic weight of the chalcogen heteroatom increases, with the tellurium-doped derivatives exhibiting only emission from the lowest triplet excited state. Notably, the phosphorescence spectra of the selenium and tellurium derivatives can be recorded even at room temperature; this is a very rare finding for fully organic emitters. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Full-switching FSF-type superconducting spin-triplet magnetic random access memory element

    Science.gov (United States)

    Lenk, D.; Morari, R.; Zdravkov, V. I.; Ullrich, A.; Khaydukov, Yu.; Obermeier, G.; Müller, C.; Sidorenko, A. S.; von Nidda, H.-A. Krug; Horn, S.; Tagirov, L. R.; Tidecks, R.

    2017-11-01

    In the present work a superconducting Co/CoOx/Cu41Ni59 /Nb/Cu41Ni59 nanoscale thin film heterostructure is investigated, which exhibits a superconducting transition temperature, Tc, depending on the history of magnetic field applied parallel to the film plane. In more detail, around zero applied field, Tc is lower when the field is changed from negative to positive polarity (with respect to the cooling field), compared to the opposite case. We interpret this finding as the result of the generation of the odd-in-frequency triplet component of superconductivity arising at noncollinear orientation of the magnetizations in the Cu41Ni59 layer adjacent to the CoOx layer. This interpretation is supported by superconducting quantum interference device magnetometry, which revealed a correlation between details of the magnetic structure and the observed superconducting spin-valve effects. Readout of information is possible at zero applied field and, thus, no permanent field is required to stabilize both states. Consequently, this system represents a superconducting magnetic random access memory element for superconducting electronics. By applying increased transport currents, the system can be driven to the full switching mode between the completely superconducting and the normal state.

  8. Tsallis q-triplet, intermittent turbulence and Portevin-Le Chatelier effect

    Science.gov (United States)

    Iliopoulos, A. C.; Aifantis, E. C.

    2018-05-01

    In this paper, we extend a previous study concerning Portevin-LeChatelier (PLC) effect and Tsallis statistics (Iliopoulos et al., 2015). In particular, we estimate Tsallis' q-triplet, namely {qstat, qsens, qrel} for two sets of stress serration time series concerning the deformation of Cu-15%Al alloy corresponding to different deformation temperatures and thus types (A and B) of PLC bands. The results concerning the stress serrations analysis reveal that Tsallis q- triplet attains values different from unity ({qstat, qsens, qrel} ≠ {1,1,1}). In particular, PLC type A bands' serrations were found to follow Tsallis super-q-Gaussian, non-extensive, sub-additive, multifractal statistics indicating that the underlying dynamics are at the edge of chaos, characterized by global long range correlations and power law scaling. For PLC type B bands' serrations, the results revealed a Tsallis sub-q-Gaussian, non-extensive, super-additive, multifractal statistical profile. In addition, our results reveal also significant differences in statistical and dynamical features, indicating important variations of the stress field dynamics in terms of rate of entropy production, relaxation dynamics and non-equilibrium meta-stable stationary states. We also estimate parameters commonly used for characterizing fully developed turbulence, such as structure functions and flatness coefficient (F), in order to provide further information about jerky flow underlying dynamics. Finally, we use two multifractal models developed to describe turbulence, namely Arimitsu and Arimitsu (A&A) [2000, 2001] theoretical model which is based on Tsallis statistics and p-model to estimate theoretical multifractal spectrums f(a). Furthermore, we estimate flatness coefficient (F) using a theoretical formula based on Tsallis statistics. The theoretical results are compared with the experimental ones showing a remarkable agreement between modeling and experiment. Finally, the results of this study verify, as

  9. Damages induced in lambda phage DNA by enzyme-generated triplet acetone

    International Nuclear Information System (INIS)

    Menck, C.F.; Cabral Neto, J.B.; Gomes, R.A.; Faljoni-Alario, A.

    1985-01-01

    Exposure of lambda phage to triplet acetone, generated during the aerobic oxidation of isobutanal by peroxidase, leads to genome lesions. The majority of these lesions are detected as DNA single-strand breaks only in alkaline conditions, so true breaks were not observed. Also, no sites sensitive to UV-endonuclease from Micrococcus luteus were found in DNA from treated phage. The participation of triplet acetone in the generation of such DNA damage is discussed. (Author) [pt

  10. Possible evidence for spin-transfer torque induced by spin-triplet supercurrent

    KAUST Repository

    Li, Lailai

    2017-10-04

    Cooper pairs in superconductors are normally spin singlet. Nevertheless, recent studies suggest that spin-triplet Cooper pairs can be created at carefully engineered superconductor-ferromagnet interfaces. If Cooper pairs are spin-polarized they would transport not only charge but also a net spin component, but without dissipation, and therefore minimize the heating effects associated with spintronic devices. Although it is now established that triplet supercurrents exist, their most interesting property - spin - is only inferred indirectly from transport measurements. In conventional spintronics, it is well known that spin currents generate spin-transfer torques that alter magnetization dynamics and switch magnetic moments. The observation of similar effects due to spin-triplet supercurrents would not only confirm the net spin of triplet pairs but also pave the way for applications of superconducting spintronics. Here, we present a possible evidence for spin-transfer torques induced by triplet supercurrents in superconductor/ferromagnet/superconductor (S/F/S) Josephson junctions. Below the superconducting transition temperature T_c, the ferromagnetic resonance (FMR) field at X-band (~ 9.0 GHz) shifts rapidly to a lower field with decreasing temperature due to the spin-transfer torques induced by triplet supercurrents. In contrast, this phenomenon is absent in ferromagnet/superconductor (F/S) bilayers and superconductor/insulator/ferromagnet/superconductor (S/I/F/S) multilayers where no supercurrents pass through the ferromagnetic layer. These experimental observations are discussed with theoretical predictions for ferromagnetic Josephson junctions with precessing magnetization.

  11. Accurate simulation of geometry, singlet-singlet and triplet-singlet excitation of cyclometalated iridium(III) complex.

    Science.gov (United States)

    Wang, Jian; Bai, Fu-Quan; Xia, Bao-Hui; Zhang, Hong-Xing; Cui, Tian

    2014-03-01

    In the current contribution, we present a critical study of the theoretical protocol used for the determination of the electronic spectra properties of luminescent cyclometalated iridium(III) complex, [Ir(III)(ppy)₂H₂dcbpy]⁺ (where, ppy = 2-phenylpyridine, H₂dcbpy = 2,2'-bipyridine-4,4'-dicarboxylic acid), considered as a representative example of the various problems related to the prediction of electronic spectra of transition metal complex. The choice of the exchange-correlation functional is crucial for the validity of the conclusions that would be drawn from the numerical results. The influence of the exchange-correlation on geometry parameter and absorption/emission band, the role of solvent effects on time-dependent density function theory (TD-DFT) calculations, as well as the importance of the chosen proper procedure to optimize triplet excited geometry, have been thus examined in detail. From the obtained results, some general conclusions and guidelines are presented: i) PBE0 functional is the most accurate in prediction of ground state geometry; ii) the well-established B3LYP, B3P86, PBE0, and X3LYP have similar accuracy in calculation of absorption spectrum; and iii) the hybrid approach TD-DFT//CIS gives out excellent agreement in the evaluation of triplet excitation energy.

  12. SO2 photoexcitation mechanism links mass-independent sulfur isotopic fractionation in cryospheric sulfate to climate impacting volcanism

    Science.gov (United States)

    Hattori, Shohei; Schmidt, Johan A.; Johnson, Matthew S.; Danielache, Sebastian O.; Yamada, Akinori; Ueno, Yuichiro; Yoshida, Naohiro

    2013-01-01

    Natural climate variation, such as that caused by volcanoes, is the basis for identifying anthropogenic climate change. However, knowledge of the history of volcanic activity is inadequate, particularly concerning the explosivity of specific events. Some material is deposited in ice cores, but the concentration of glacial sulfate does not distinguish between tropospheric and stratospheric eruptions. Stable sulfur isotope abundances contain additional information, and recent studies show a correlation between volcanic plumes that reach the stratosphere and mass-independent anomalies in sulfur isotopes in glacial sulfate. We describe a mechanism, photoexcitation of SO2, that links the two, yielding a useful metric of the explosivity of historic volcanic events. A plume model of S(IV) to S(VI) conversion was constructed including photochemistry, entrainment of background air, and sulfate deposition. Isotopologue-specific photoexcitation rates were calculated based on the UV absorption cross-sections of 32SO2, 33SO2, 34SO2, and 36SO2 from 250 to 320 nm. The model shows that UV photoexcitation is enhanced with altitude, whereas mass-dependent oxidation, such as SO2 + OH, is suppressed by in situ plume chemistry, allowing the production and preservation of a mass-independent sulfur isotope anomaly in the sulfate product. The model accounts for the amplitude, phases, and time development of Δ33S/δ34S and Δ36S/Δ33S found in glacial samples. We are able to identify the process controlling mass-independent sulfur isotope anomalies in the modern atmosphere. This mechanism is the basis of identifying the magnitude of historic volcanic events. PMID:23417298

  13. Katanin localization requires triplet microtubules in Chlamydomonas reinhardtii.

    Directory of Open Access Journals (Sweden)

    Jessica M Esparza

    Full Text Available Centrioles and basal bodies are essential for a variety of cellular processes that include the recruitment of proteins to these structures for both centrosomal and ciliary function. This recruitment is compromised when centriole/basal body assembly is defective. Mutations that cause basal body assembly defects confer supersensitivity to Taxol. These include bld2, bld10, bld12, uni3, vfl1, vfl2, and vfl3. Flagellar motility mutants do not confer sensitivity with the exception of mutations in the p60 (pf19 and p80 (pf15 subunits of the microtubule severing protein katanin. We have identified additional pf15 and bld2 (ε-tubulin alleles in screens for Taxol sensitivity. Null pf15 and bld2 alleles are viable and are not essential genes in Chlamydomonas. Analysis of double mutant strains with the pf15-3 and bld2-6 null alleles suggests that basal bodies in Chlamydomonas may recruit additional proteins beyond katanin that affect spindle microtubule stability. The bld2-5 allele is a hypomorphic allele and its phenotype is modulated by nutritional cues. Basal bodies in bld2-5 cells are missing proximal ends. The basal body mutants show aberrant localization of an epitope-tagged p80 subunit of katanin. Unlike IFT proteins, katanin p80 does not localize to the transition fibers of the basal bodies based on an analysis of the uni1 mutant as well as the lack of colocalization of katanin p80 with IFT74. We suggest that the triplet microtubules are likely to play a key role in katanin p80 recruitment to the basal body of Chlamydomonas rather than the transition fibers that are needed for IFT localization.

  14. Ordinary and triplet superconducting spin valve effect in Fe/Pb based systems

    Energy Technology Data Exchange (ETDEWEB)

    Leksin, Pavel; Schumann, Joachim; Krupskaya, Yulia; Kataev, Vladislav; Hess, Christian; Schmidt, Oliver; Buechner, Bernd [Leibniz Institute for Solid State and Materials Research IFW Dresden (Germany); Garifyanov, Nadir; Garifullin, Ilgiz [Zavoisky Physical-Technical Institute of RAS, Kazan (Russian Federation); Fominov, Yakov [L. D. Landau Institute for Theoretical Physics of RAS, Moscow (Russian Federation)

    2015-07-01

    We report on experimental evidence for the occurrence of the long range triplet correlations (LRTC) of the superconducting (SC) condensate in the spin-valve heterostructures CoO{sub x}/Fe1/Cu/Fe2/Pb. The LRTC generation in this layer sequence is accompanied by a T{sub c} suppression near the orthogonal mutual orientation of the Fe1 and Fe2 layers' magnetization. This T{sub c} drop reaches its maximum of 60mK at the Fe2 layer thickness d{sub Fe2} = 0.6 nm and falls down when d{sub Fe2} is increased. The modification of the Fe/Pb interface by using a thin Cu layer between Fe and Pb layers reduces the SC transition width without preventing the interaction between Pb and Fe2 layers. The dependence of the SSVE magnitude on Fe1 layer thickness d{sub Fe1} reveals maximum of the effect when d{sub Fe1} and d{sub Fe2} are equal and the d{sub Fe2} value is minimal. Using the optimal d{sub Fe1}, d{sub Fe2} and the intermediate Cu layer we realized almost full switching from normal to SC state due to SSVE.

  15. Three-dimensional triplet tracking for LHC and future high rate experiments

    International Nuclear Information System (INIS)

    Schöning, A

    2014-01-01

    The hit combinatorial problem is a main challenge for track reconstruction and triggering at high rate experiments. At hadron colliders the dominant fraction of hits is due to low momentum tracks for which multiple scattering (MS) effects dominate the hit resolution. MS is also the dominating source for hit confusion and track uncertainties in low energy precision experiments. In all such environments, where MS dominates, track reconstruction and fitting can be largely simplified by using three-dimensional (3D) hit-triplets as provided by pixel detectors. This simplification is possible since track uncertainties are solely determined by MS if high precision spatial information is provided. Fitting of hit-triplets is especially simple for tracking detectors in solenoidal magnetic fields. The over-constrained 3D-triplet method provides a complete set of track parameters and is robust against fake hit combinations. Full tracks can be reconstructed step-wise by connecting hit triplet combinations from different layers, thus heavily reducing the combinatorial problem and accelerating track linking. The triplet method is ideally suited for pixel detectors where hits can be treated as 3D-space points. With the advent of relatively cheap and industrially available CMOS-sensors the construction of highly granular full scale pixel tracking detectors seems to be possible also for experiments at LHC or future high energy (hadron) colliders. In this paper tracking performance studies for full-scale pixel detectors, including their optimisation for 3D-triplet tracking, are presented. The results obtained for different types of tracker geometries and different reconstruction methods are compared. The potential of reducing the number of tracking layers and - along with that - the material budget using this new tracking concept is discussed. The possibility of using 3D-triplet tracking for triggering and fast online reconstruction is highlighted

  16. Monte Carlo study of efficiency roll-off of phosphorescent organic light-emitting diodes: Evidence for dominant role of triplet-polaron quenching

    Energy Technology Data Exchange (ETDEWEB)

    Eersel, H. van, E-mail: h.v.eersel@tue.nl; Coehoorn, R. [Department of Applied Physics, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven (Netherlands); Philips Research Laboratories, High Tech Campus 4, 5656 AE Eindhoven (Netherlands); Bobbert, P. A.; Janssen, R. A. J. [Department of Applied Physics, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven (Netherlands)

    2014-10-06

    We present an advanced molecular-scale organic light-emitting diode (OLED) model, integrating both electronic and excitonic processes. Using this model, we can reproduce the measured efficiency roll-off for prototypical phosphorescent OLED stacks based on the green dye tris[2-phenylpyridine]iridium (Ir(ppy){sub 3}) and the red dye octaethylporphine platinum (PtOEP) and study the cause of the roll-off as function of the current density. Both the voltage versus current density characteristics and roll-off agree well with experimental data. Surprisingly, the results of the simulations lead us to conclude that, contrary to what is often assumed, not triplet-triplet annihilation but triplet-polaron quenching is the dominant mechanism causing the roll-off under realistic operating conditions. Simulations for devices with an optimized recombination profile, achieved by carefully tuning the dye trap depth, show that it will be possible to fabricate OLEDs with a drastically reduced roll-off. It is envisaged that J{sub 90}, the current density at which the efficiency is reduced to 90%, can be increased by almost one order of magnitude as compared to the experimental state-of-the-art.

  17. Monte Carlo study of efficiency roll-off of phosphorescent organic light-emitting diodes: Evidence for dominant role of triplet-polaron quenching

    International Nuclear Information System (INIS)

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

    2014-01-01

    We present an advanced molecular-scale organic light-emitting diode (OLED) model, integrating both electronic and excitonic processes. Using this model, we can reproduce the measured efficiency roll-off for prototypical phosphorescent OLED stacks based on the green dye tris[2-phenylpyridine]iridium (Ir(ppy) 3 ) and the red dye octaethylporphine platinum (PtOEP) and study the cause of the roll-off as function of the current density. Both the voltage versus current density characteristics and roll-off agree well with experimental data. Surprisingly, the results of the simulations lead us to conclude that, contrary to what is often assumed, not triplet-triplet annihilation but triplet-polaron quenching is the dominant mechanism causing the roll-off under realistic operating conditions. Simulations for devices with an optimized recombination profile, achieved by carefully tuning the dye trap depth, show that it will be possible to fabricate OLEDs with a drastically reduced roll-off. It is envisaged that J 90 , the current density at which the efficiency is reduced to 90%, can be increased by almost one order of magnitude as compared to the experimental state-of-the-art.

  18. Heavy Atom Substituents as Molecular Probes for Solvent Effects on the Dynamics of Short-lived Triplet Exciplexes

    OpenAIRE

    Winter, Gerhard; Steiner, Ulrich

    1980-01-01

    The influence of heavy atom substituents (Br, I) in the electron donor aniline on the electron transfer reaction with thiopyronine triplet is investigated by flash spectroscopy in solvents of different viscosity and polarity. Triplet quenching constants and radical yields are determined. The results are analysed in terms of decay constants of an intermediate triplet exciplex where the heavy atom substituents significantly enhance the intersystem crossing process leading to singlet ground stat...

  19. Equilibration kinetics in isolated and membrane-bound photosynthetic reaction centers upon illumination: a method to determine the photoexcitation rate.

    Science.gov (United States)

    Manzo, Anthony J; Goushcha, Alexander O; Barabash, Yuri M; Kharkyanen, Valery N; Scott, Gary W

    2009-07-01

    Kinetics of electron transfer, following variation of actinic light intensity, for photosynthetic reaction centers (RCs) of purple bacteria (isolated and membrane-bound) were analyzed by measuring absorbance changes in the primary photoelectron donor absorption band at 865 nm. The bleaching of the primary photoelectron donor absorption band in RCs, following a sudden increase of illumination from the dark to an actinic light intensity of I(exp), obeys a simple exponential law with the rate constant alphaI(exp) + k(rec), in which alpha is a parameter relating the light intensity, measured in mW/cm(2), to a corresponding theoretical rate in units of reciprocal seconds, and k(rec) is the effective rate constant of the charge recombination in the photosynthetic RCs. In this work, a method for determining the alpha parameter value is developed and experimentally verified for isolated and membrane-bound RCs, allowing for rigorous modeling of RC macromolecule dynamics under varied photoexcitation conditions. Such modeling is necessary for RCs due to alterations of the forward photoexcitation rates and relaxation rates caused by illumination history and intramolecular structural dynamics effects. It is demonstrated that the classical Bouguer-Lambert-Beer formalism can be applied for the samples with relatively low scattering, which is not necessarily the case with strongly scattering media or high light intensity excitation.

  20. LETTER TO THE EDITOR: Quantum manifestations of closed orbits in the photoexcitation scaled spectrum of the hydrogen atom in crossed fields

    Science.gov (United States)

    Rao, Jianguo; Delande, D.; Taylor, K. T.

    2001-06-01

    The scaled photoexcitation spectrum of the hydrogen atom in crossed electric and magnetic fields has been obtained by means of accurate quantum mechanical calculation using a new algorithm. Closed orbits in the corresponding classical system have also been obtained, using a new, efficient and practical searching procedure. Two new classes of closed orbit have been identified. Fourier transforming each photoexcitation quantum spectrum to yield a plot against scaled action has allowed direct comparison between peaks in such plots and the scaled action values of closed orbits. Excellent agreement has been found with all peaks assigned.

  1. Control the length of beam trajectory with a quadruple triplet for heavy ion accelerator

    International Nuclear Information System (INIS)

    Zhang, Zhan; Wei, Shaoqing; Lee, Sang Jin; Kim, Do Gyun; Kim, Jang Youl

    2016-01-01

    Beam trajectory is needed to be controlled in heavy ion accelerator system. Quadruple magnets are widely used in heavy ion accelerator for focusing the transporting particles. A quadruple triplet system which consists of three consecutive quadrupoles, Q1, Q2 and Q3, is used to control beam trajectory at a focused position. Q1 and Q3 have symmetry with respect to Q2. The beam trajectory in magnet system is affected by higher order fields existed in real fields. For quadrupoles, the representation simulation of beam trajectory was carried out to study the beam trajectory and to estimate an effect of higher order field in triplet system. SCALA program was used to simulate the beam trajectory in OperaTM. SCALA can analyze a large number of beam trajectories at the same time by adjusting the size of finite element of the emitter. With OperaTM and MatlabTM programs, the position of focused beam spot in quadruple triplet system can be increased or decreased using evolution strategy (ES) method, therefore the length of triplet system can be controlled. Finally, the quadruple triplet system with the appropriate length and expected beam spot range was suggested in this paper

  2. Control the length of beam trajectory with a quadruple triplet for heavy ion accelerator

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Zhan; Wei, Shaoqing; Lee, Sang Jin [Uiduk University, Gyeongju (Korea, Republic of); Kim, Do Gyun; Kim, Jang Youl [Rare Isotope Science Project, Institute for Basic Science, Daejeon (Korea, Republic of)

    2016-12-15

    Beam trajectory is needed to be controlled in heavy ion accelerator system. Quadruple magnets are widely used in heavy ion accelerator for focusing the transporting particles. A quadruple triplet system which consists of three consecutive quadrupoles, Q1, Q2 and Q3, is used to control beam trajectory at a focused position. Q1 and Q3 have symmetry with respect to Q2. The beam trajectory in magnet system is affected by higher order fields existed in real fields. For quadrupoles, the representation simulation of beam trajectory was carried out to study the beam trajectory and to estimate an effect of higher order field in triplet system. SCALA program was used to simulate the beam trajectory in OperaTM. SCALA can analyze a large number of beam trajectories at the same time by adjusting the size of finite element of the emitter. With OperaTM and MatlabTM programs, the position of focused beam spot in quadruple triplet system can be increased or decreased using evolution strategy (ES) method, therefore the length of triplet system can be controlled. Finally, the quadruple triplet system with the appropriate length and expected beam spot range was suggested in this paper.

  3. Energy-donor phosphorescence quenching study of triplet–triplet energy transfer between UV absorbers

    International Nuclear Information System (INIS)

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

    2015-01-01

    The intermolecular triplet–triplet energy transfer from a photounstable UV-A absorber, 4-tert-butyl-4′-methoxydibenzoylmethane (BMDBM), to UV-B absorbers, 2-ethylhexyl 4-methoxycinnamate (octyl methoxycinnamate, OMC), octocrylene (OCR) and dioctyl 4-methoxybenzylidenemalonate (DOMBM) has been observed using a 355 nm laser excitation in rigid solutions at 77 K. The decay curves of the energy-donor phosphorescence in the presence of the UV-B absorbers deviate from the exponential decay at the initial stage of the decay. The Stern–Volmer formulation is not valid in rigid solutions because molecular diffusion is impossible. The experimental results indicate that the rate constant of triplet–triplet energy transfer from BMDBM to the UV-B absorbers, k T–T , decreases in the following order: k T–T (BMDBM–DOMBM)>k T–T (BMDBM–OMC)≥k T–T (BMDBM–OCR). The presence of DOMBM enhances the photostability of the widely used combination of UV-A and UV-B absorbers, BMDBM and OCR. The effects of the triplet–triplet energy transfer on the photostability of BMDBM are discussed. - Highlights: • The intermolecular triplet–triplet energy transfer between UV absorbers was observed. • The phosphorescence decay deviates from exponential at the initial stage of decay. • The effects of triplet–triplet energy transfer on the photostability are discussed

  4. The alignment of the LHC low beta triplets. Review of instrumentation and methods

    International Nuclear Information System (INIS)

    Coosemans, W.; Mainaud Durand, H.; Marin, A.; Quesnel, J-P.

    2003-01-01

    Alignment tolerances for the LHC insertions are particularly stringent regarding the low beta quadrupoles, which induce strict positioning tolerances, in a severe environment (high radiation fluxes and magnetic fields): positioning of one inner triplet with respect to the other (left/right side): ±0.5 mm (3σ), stability of the positioning of one quadrupole inside its triplet: a few microns. We propose to continuously monitor the relative position of the quadrupoles of one inner triplet with respect to a reference frame materialized by a wire and a water surface, and to use common references to link a triplet on one side to the triplet on the other side of the experiment. When the offset between real and reference position becomes too great, the quadrupole will be moved using remote motorized jacks. Instrumentation (HLS, WPS, radial measuring system, etc.) and methods will be detailed as well as the first results obtained on a cryo-magnet prototype named TAP used as test facility. The TAP is equipped with HLS linked by two types of hydraulic networks (two pipes with air and water separated, one pipe half filled), WPS and one inclinometer. It is installed on three polyurethane motorized jacks in order to study and compare servo positioning using the different sensors. (author)

  5. Direct determination of triplet phases and enantiomorphs of non-centrosymmetric structures. Pt. 2

    International Nuclear Information System (INIS)

    Huemmer, K.; Weckert, E.; Bondza, H.

    1989-01-01

    Direct measurements of triplet phase relationships for non-centrosymmetric light-atom organic structures with medium-size unit cells are reported. The phase information can be extracted from the three-beam profiles of a Renninger ψ-scan experiment. The measurements were carried out with a special ψ-circle diffractometer installed on a rotating Cu-anode generator. The incident-beam divergence is reduced to 0.02 0 . The experimental results confirm the theoretical considerations of paper I of this work. As triplet phases of ±90 0 can be distinguished, the absolute structure can be determined unambiguously. The measurements show that the triplet-phase-dependent interference effects may be superposed on phase-independent Umweganregung or Aufhellung effects. By a comparison of the ψ-scan profiles of two centrosymmetrically related three-beam cases, the triplet phases of which have opposite signs, it is possible to evaluate the phase-independent effects and to determine the value of the triplet phase with an accuracy of at least 90 0 . (orig.)

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

    Science.gov (United States)

    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.

  7. 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).

    Science.gov (United States)

    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.

  8. Observation of resonance fluorescence and the Mollow triplet from a coherently driven site-controlled quantum dot

    DEFF Research Database (Denmark)

    Unsleber, Sebastian; Maier, Sebastian; McCutcheon, Dara

    2015-01-01

    -controlled semiconductor quantum dot to an external resonant laser field. For strong continuous-wave driving we observe the characteristic Mollow triplet and analyze the Rabi splitting and sideband widths as a function of driving strength and temperature. The sideband widths increase linearly with temperature...... and the square of the driving strength, which we explain via coupling of the exciton to longitudinal acoustic phonons. We also find an increase of the Rabi splitting with temperature, which indicates a temperature induced delocalization of the excitonic wave function resulting in an increase of the oscillator...... strength. Finally, we demonstrate coherent control of the exciton excited state population via pulsed resonant excitation and observe a damping of the Rabi oscillations with increasing pulse area, which is consistent with our exciton-photon coupling model. We believe that our work outlines the possibility...

  9. Unusual behavior of nuclear relaxation in CeCu2Si2 'possible evidence for triplet superconductivity'

    International Nuclear Information System (INIS)

    Kitaoka, Y.; Asayama, K.; Ueda, K.; Kohara, T.

    1984-01-01

    Nuclear relaxation of 63 Cu in the superconducting state of the Kondo-lattice system CeCu 2 Si 2 has been studied with the use of the 63 Cu nuclear quadrupole resonance technique under zero field and down to 65mK. The nuclear spin-lattice relaxation rate (1/T 1 ) decreases drastically just below Tsub(c)=0.67 K down to 0.5Tsub(c) without the apparent enhanced behavior and then is found to be almost temperature independent below 0.3Tsub(c). These results suggest that the superconductivity in CeCu 2 Si 2 is not in the usual BCS regime. The analysis based upon the existing triplet pairing model with an anisotropic energy gap describes well the behavior from Tsub(c) down to 0.5Tsub(c), while the temperature independence below 0.3Tsub(c) remains unexplained. (author)

  10. A New Track Reconstruction Algorithm suitable for Parallel Processing based on Hit Triplets and Broken Lines

    Directory of Open Access Journals (Sweden)

    Schöning André

    2016-01-01

    Full Text Available Track reconstruction in high track multiplicity environments at current and future high rate particle physics experiments is a big challenge and very time consuming. The search for track seeds and the fitting of track candidates are usually the most time consuming steps in the track reconstruction. Here, a new and fast track reconstruction method based on hit triplets is proposed which exploits a three-dimensional fit model including multiple scattering and hit uncertainties from the very start, including the search for track seeds. The hit triplet based reconstruction method assumes a homogeneous magnetic field which allows to give an analytical solutions for the triplet fit result. This method is highly parallelizable, needs fewer operations than other standard track reconstruction methods and is therefore ideal for the implementation on parallel computing architectures. The proposed track reconstruction algorithm has been studied in the context of the Mu3e-experiment and a typical LHC experiment.

  11. Codon size reduction as the origin of the triplet genetic code.

    Directory of Open Access Journals (Sweden)

    Pavel V Baranov

    Full Text Available The genetic code appears to be optimized in its robustness to missense errors and frameshift errors. In addition, the genetic code is near-optimal in terms of its ability to carry information in addition to the sequences of encoded proteins. As evolution has no foresight, optimality of the modern genetic code suggests that it evolved from less optimal code variants. The length of codons in the genetic code is also optimal, as three is the minimal nucleotide combination that can encode the twenty standard amino acids. The apparent impossibility of transitions between codon sizes in a discontinuous manner during evolution has resulted in an unbending view that the genetic code was always triplet. Yet, recent experimental evidence on quadruplet decoding, as well as the discovery of organisms with ambiguous and dual decoding, suggest that the possibility of the evolution of triplet decoding from living systems with non-triplet decoding merits reconsideration and further exploration. To explore this possibility we designed a mathematical model of the evolution of primitive digital coding systems which can decode nucleotide sequences into protein sequences. These coding systems can evolve their nucleotide sequences via genetic events of Darwinian evolution, such as point-mutations. The replication rates of such coding systems depend on the accuracy of the generated protein sequences. Computer simulations based on our model show that decoding systems with codons of length greater than three spontaneously evolve into predominantly triplet decoding systems. Our findings suggest a plausible scenario for the evolution of the triplet genetic code in a continuous manner. This scenario suggests an explanation of how protein synthesis could be accomplished by means of long RNA-RNA interactions prior to the emergence of the complex decoding machinery, such as the ribosome, that is required for stabilization and discrimination of otherwise weak triplet codon

  12. On measurement of photon polarization by triplet production differential cross sections

    International Nuclear Information System (INIS)

    Vinokurov, E.A.; Boldyshev, V.F.

    1984-01-01

    Dependence of triplet production by linearly polarized photon (the recoil electron momenta being p 1 >=p 10 ) upon the electron pair invariant mass Δ (in the ranges of 0.1 mc 10 2 2 ) is studied aiming to analyze possible use of triplet photoproduction to measure polarization of high-energy photon beams. It is shown that the regions 2m 2 and 2m 200 mc 2 are optimum and provide a 17-35% accuracy improvement for the photon beam polarization measurement, the number of events decreasing by a factor of 2.4-4.4

  13. Antimicrobial photodynamic activity and cytocompatibility of Au25(Capt18 clusters photoexcited by blue LED light irradiation

    Directory of Open Access Journals (Sweden)

    Miyata S

    2017-04-01

    Full Text Available Saori Miyata,1 Hirofumi Miyaji,1 Hideya Kawasaki,2 Masaki Yamamoto,2 Erika Nishida,1 Hiroko Takita,3 Tsukasa Akasaka,4 Natsumi Ushijima,3 Toshihiko Iwanaga,5 Tsutomu Sugaya1 1Department of Periodontology and Endodontology, Hokkaido University Graduate School of Dental Medicine, Kita-ku, Sapporo, 2Department of Chemistry and Materials Engineering, Faculty of Chemistry, Materials and Bioengineering, Kansai University, Suita-shi, Osaka, 3Support Section for Education and Research, Hokkaido University Graduate School of Dental Medicine, 4Department of Biomedical, Dental Materials and Engineering, Graduate School of Dental Medicine, Hokkaido University, 5Department of Anatomy, Laboratory of Histology and Cytology, Hokkaido University Graduate School of Medicine, Kita-ku, Sapporo, Japan Abstract: Antimicrobial photodynamic therapy (aPDT has beneficial effects in dental treatment. We applied captopril-protected gold (Au25(Capt18 clusters as a novel photosensitizer for aPDT. Photoexcited Au clusters under light irradiation generated singlet oxygen (1O2. Accordingly, the antimicrobial and cytotoxic effects of Au25(Capt18 clusters under dental blue light-emitting diode (LED irradiation were evaluated. 1O2 generation of Au25(Capt18 clusters under blue LED irradiation (420–460 nm was detected by a methotrexate (MTX probe. The antimicrobial effects of photoexcited Au clusters (0, 5, 50, and 500 µg/mL on oral bacterial cells, such as Streptococcus mutans, Aggregatibacter actinomycetemcomitans, and Porphyromonas gingivalis, were assessed by morphological observations and bacterial growth experiments. Cytotoxicity testing of Au clusters and blue LED irradiation was then performed against NIH3T3 and MC3T3-E1 cells. In addition, the biological performance of Au clusters (500 µg/mL was compared to an organic dye photosensitizer, methylene blue (MB; 10 and 100 µg/mL. We confirmed the 1O2 generation ability of Au25(Capt18 clusters through the fluorescence

  14. Study of the photoexcited carrier dynamics in InP:Fe using time-resolved reflection and photoluminescence spectra

    International Nuclear Information System (INIS)

    Huang Shihua; Li Xi; Lu Fang

    2004-01-01

    The photoexcited carrier dynamics and photoluminescence of the undoped InP and Fe implanted InP was studied by time-resolved reflection and photoluminescence spectra. The decay times of reflection recovery and the radiative recombination for Fe implanted InP are shorter than those of undoped InP. Considering the surface recombination, a model was developed to simulate the reflection recovery dynamics, it agrees with the experimental results very well. Moreover, we obtained the ambipolar diffusion coefficient and the surface recombination velocity by using the model. For Fe-doped InP, the surface recombination velocity is much larger than that for the undoped InP, which is probably due to Fe 2+/3+ trapping centers and the large surface band bending. The PL decay time for Fe implanted InP is shorter than that for undoped InP, which is ascribed to the capture centers introduced by metallic precipitates

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

    Science.gov (United States)

    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.

  16. Activation of store – operated Ca(2+ entry in cisplatin resistant leukemic cells after treatment with photoexcited fullerene C(60 and cisplatin

    Directory of Open Access Journals (Sweden)

    D. V. Franskevych

    2018-04-01

    Full Text Available Ca2+-regulating system in cancer cells is suggested to be remodulated particularly by reduced store-operated Ca2+ entry (SOCE through plasma membrane in order to maintain moderately reduced cytosolic Ca2+ concentration and to avoid apoptosis. The endoplasmic reticulum (ER Ca2+ pool content and the size of SOCE in leukemic wild type (L1210 and resistant to cisplatin (L1210R cells in control, after treatment with either cisplatin (1 µg/ml or photoexcited fulleren C60 (10-5 M alone, or their combination were estimated with the use of Indo-1 AM. The SOCE in resistant to cisplatin L1210R cells was found to be lower than in the wild-type cells. After treatment with cisplatin the decrease of thapsigargin (TG-sensitive ER Ca2+ pool with no significant increase of SOCE was observed in L1210 cells, while no changes were detected in L1210R cells. Photoexcitation of intracellular accumulated fullerene C60 in the visible range of spectrum (410-700 nm was accompanied by increase of SOCE not only in sensitive, but in resistant cells as well. In resistant L1210R cells treated with photoexcited C60 essential effect of cisplatin on Ca2+ homeostasis became obvious: the size of SOCE proved to be higher than after treatment with photoexcited C60 alone. The data obtained allow suggesting­ the influence of photoexcited C60 not only on Ca2+-regulating system, but on those involved in controlling cisplatin entry into drug resistant cancer cells.

  17. Possibilities of introducing different functional circuits on top of a structural neuron triplet: Where do the gains lie?

    International Nuclear Information System (INIS)

    Franović, Igor; Miljković, Vladimir

    2012-01-01

    Highlights: ► We identify different types of functional circuits in structural triplets. ► The approach utilizes the properties of synapses with fast-threshold modulation. ► We observe correspondence between sequences in the time series and the triads. ► Triads are assigned roles with respect to synchronization. ► Regularization of bursting series is explained by classifying all the bursts. - Abstract: Instigated by the research on clusterization phenomena in complex neural networks, we study a triplet of bursting Rulkov map neurons connected via inhibitory synapses with delay. It is demonstrated how on a background of structural motif one can build different types of functional circuits. The approach is based on utilizing the properties of the chemical synapses, whose gating is modeled by the fast threshold modulation, in conjunction with the phase plane analysis, allowing the system state to be represented in terms of maps the neurons reside on. For both the dynamical configurations, monitoring the layout of active neurons, and the functional motifs, following the maps where the synchronized neurons lie, we establish a one-on-one correspondence between sequences in the time series and the triads, making up the subgraphs of the original graph. By introducing the appropriate sets of quantities, one obtains not only the distributions of triads as a function of synaptic parameters, but is also able to identify a distinct triad whose presence may be viewed as a signature of the burst synchronization process. In another setup, the regularization of burst cycles for an arbitrary neuron is explained by classifying all the bursts as long or short, with their fractions linked to the abundances of triads under variation of synaptic parameters.

  18. Assessing the occurrence of the dibromide radical (Br2−·) in natural waters: Measures of triplet-sensitised formation, reactivity, and modelling

    International Nuclear Information System (INIS)

    De Laurentiis, Elisa; Minella, Marco; Maurino, Valter; Minero, Claudio; Mailhot, Gilles; Sarakha, Mohamed; Brigante, Marcello; Vione, Davide

    2012-01-01

    The triplet state of anthraquinone-2-sulphonate (AQ2S) is able to oxidise bromide to Br · /Br 2 −· , with rate constant (2–4) ⋅ 10 9 M −1 s −1 that depends on the pH. Similar processes are expected to take place between bromide and the triplet states of naturally occurring chromophoric dissolved organic matter ( 3 CDOM*). The brominating agent Br 2 −· could thus be formed in natural waters upon oxidation of bromide by both · OH and 3 CDOM*. Br 2 −· would be consumed by disproportionation into bromide and bromine, as well as upon reaction with nitrite and most notably with dissolved organic matter (DOM). By using the laser flash photolysis technique, and phenol as model organic molecule, a second-order reaction rate constant of ∼ 3 ⋅ 10 2 L (mg C) −1 s −1 was measured between Br 2 −· and DOM. It was thus possible to model the formation and reactivity of Br 2 −· in natural waters, assessing the steady-state [Br 2 −· ] ≈ 10 −13 –10 −12 M. It is concluded that bromide oxidation by 3 CDOM* would be significant compared to oxidation by · OH. The 3 CDOM*-mediated process would prevail in DOM-rich and bromide-rich environments, the latter because elevated bromide would completely scavenge · OH. Under such conditions, · OH-assisted formation of Br 2 −· would be limited by the formation rate of the hydroxyl radical. In contrast, the formation rate of 3 CDOM* is much higher compared to that of · OH in most surface waters and would provide a large 3 CDOM* reservoir for bromide to react with. A further issue is that nitrite oxidation by Br 2 −· could be an important source of the nitrating agent · NO 2 in bromide-rich, nitrite-rich and DOM-poor environments. Such a process could possibly account for significant aromatic photonitration observed in irradiated seawater and in sunlit brackish lagoons. Highlights: ► The triplet state of anthraquinone-2-sulphonate oxidises bromide to Br 2 −· . ► Dissolved organic matter is

  19. Magnetoanisotropic spin-triplet Andreev reflection in ferromagnet-Ising superconductor junctions

    Science.gov (United States)

    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.

  20. Efficient Generation of Long-Lived Triplet Excitons in 2D Hybrid Perovskite.

    Science.gov (United States)

    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.

  1. Maternal and Fetal Outcomes of Triplet Gestation in a Tertiary Hospital in Oman

    Directory of Open Access Journals (Sweden)

    Maryam Al-Shukri

    2014-05-01

    Full Text Available Objectives: The aim of this study was to describe the fetal and maternal outcomes of triplet gestation and to report on the maternal characteristics of those pregnancies in a tertiary care centre in Oman. Methods: A retrospective study was undertaken of all triplet pregnancies delivered at Sultan Qaboos University Hospital, Muscat, Oman, between January 2009 and December 2011. Results: Over the three-year study period, there were 9,140 deliveries. Of these, there were 18 triplet pregnancies, giving a frequency of 0.2%. The mean gestational age at delivery was 31.0 ± 3.0 weeks, and the mean birth weight was 1,594 ± 460 g. The most common maternal complications were preterm labour in 13 pregnancies (72.2%, gestational diabetes in 7 (39% and gestational hypertension in 5 (28%. Of the total deliveries, there were 54 neonates. Neonatal complications among these included hyaline membrane disease in 25 neonates (46%, hyperbilirubinaemia in 24 (43%, sepsis in 18 (33% and anaemia in 8 (15%. The perinatal mortality rate was 55 per 1,000 births. Conclusion: The maternal and neonatal outcomes of triplet pregnancies were similar to those reported in other studies.

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

    Science.gov (United States)

    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.

  3. Tri-P-LETS: Changing the Face of High School Computer Science

    Science.gov (United States)

    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,…

  4. Macro, Submicro, and Symbolic: The Many Faces of the Chemistry "Triplet"

    Science.gov (United States)

    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…

  5. Triplets of galaxies: Their dynamics, evolution, and the origin of chaos in them

    Science.gov (United States)

    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.

  6. Triplet superconductivity in PrOs{sub 4}Sb{sub 12}

    Energy Technology Data Exchange (ETDEWEB)

    Maki, K. [Department of Physics and Astronomy, University of Southern California, Los Angeles, CA 90089-0484 (United States); Won, H. [Department of Physics, Hallym University Chuncheon 200-702 (Korea, Republic of) ]. E-mail: hkwon@hallym.ac.kr; Parker, David [Department of Physics and Astronomy, University of Southern California, Los Angeles, CA 90089-0484 (United States); Haas, Stephan [Department of Physics and Astronomy, University of Southern California, Los Angeles, CA 90089-0484 (United States); Izawa, K. [Institute for Solid State Physics, University of Tokyo, Kashiwanoha, Kashiwa, Chiba 277-8581 (Japan); Matsuda, Y. [Institute for Solid State Physics, University of Tokyo, Kashiwanoha, Kashiwa, Chiba 277-8581 (Japan)

    2005-04-30

    Here we propose spin triplet superconductors for the A- and B-phase in PrOs{sub 4}Sb{sub 12}. The present model describes consistently the thermal conductivity {kappa}{sub zz} data obtained by Izawa et al. for T>=150mK.

  7. Photoprotection in the antenna complexes of photosystem II : Role of individual xanthophylls in chlorophyll triplet quenching

    NARCIS (Netherlands)

    Mozzo, Milena; Dall'Osto, Luca; Hienerwadel, Rainer; Bassi, Roberto; Croce, Roberta

    2008-01-01

    In this work the photoprotective role of all xanthophylls in LHCII, Lhcb4, and Lhcb5 is investigated by laser-induced Triplet-minus-Singlet (TmS) spectroscopy. The comparison of native LHCII trimeric complexes with different carotenoid composition shows that the xanthophylls in sites V1 and N1 do

  8. λ7774 Oxygen Triplet in Open Cluster Dwarfs: Pleiades and M34

    International Nuclear Information System (INIS)

    Schuler, S.C.; King, J.R.; Hobbs, L.M.; Pinsonneault, M.H.

    2005-01-01

    We have undertaken a LTE analysis of the high-excitation 7774 A O I triplet in high-resolution, moderate signal-to-noise spectra of 15 Pleiades (HET/HRS) and 8 M34 (Keck/HIRES) open cluster dwarfs. Effective temperatures range from 5048 - 6172 K for the Pleiades sample and from 5290 - 6130 K for the M34 sample. Relative O abundances have been derived using model atmospheres interpolated from four different sets of ATLAS9 grids: with convective overshoot, without convective overshoot, with the mixing length parameter set to 0.5, and with the convective treatment of Canuto, Goldman, and Mazzitelli. In contrast to existing NLTE predictions, a dramatic increase in O I triplet abundance with decreasing temperature is seen for both clusters, regardless of atmospheric model. S I abundances of three Pleiads derived from the high-excitation λ6052.67 feature mimic the O I abundance behavior. O abundances have also been derived from the 6300 A [OI] feature in three Pleiads; the abundances exhibit a much lower mean value than the cool dwarf triplet results. These data suggest LTE abundances derived from the O I triplet for cool dwarfs (T eff =<5800 K) should be viewed with caution

  9. Photoprotection in the antenna complexes of photosystem II - Role of individual xanthophylls in chlorophyll triplet quenching

    NARCIS (Netherlands)

    Mozzo, Milena; Dall'Osto, Luca; Hienerwadel, Rainer; Bassi, Roberto; Croce, Roberta; Osto, Luca Dall’

    2008-01-01

    In this work the photoprotective role of all xanthophylls in LHCII, Lhcb4, and Lhcb5 is investigated by laser-induced Triplet-minus-Singlet (TmS) spectroscopy. The comparison of native LHCII trimeric complexes with different carotenoid composition shows that the xanthophylls in sites V1 and N1 do

  10. The xanthophylls in light-harvesting complex II of higher plants: light harvesting and triplet quenching.

    NARCIS (Netherlands)

    Peterman, E.J.G.; Gradinaru, C.C.; Calkoen, F.; Borst, J.C.; van Grondelle, R.; van Amerongen, H.

    1997-01-01

    A spectral and functional assignment of the xanthophylls in monomeric and trimeric light-harvesting complex II of green plants has been obtained using HPLC analysis of the pigment composition, laser-flash induced triplet- minus-singlet, fluorescence excitation, and absorption spectra. It is shown

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  13. On the rate of triplet excitation transfer in the diffuse limit

    International Nuclear Information System (INIS)

    Davidovich, M.A.; Knox, R.S.

    1979-11-01

    The usefulness of spectral data in estimating intermolecular triplet excitation transfer rates in found to be rather limited and to depend explicitly on the mechaisms which allow the optical transitions. Necessary conditions for the validity of such use of spectra are given, and the otherwise required correction factors are discussed and estimated. (Author) [pt

  14. Three-Dimensional Triplet Tracking for LHC and Future High Rate Experiments

    CERN Document Server

    Schöning, Andre

    2014-10-20

    The hit combinatorial problem is a main challenge for track reconstruction and triggering at high rate experiments. At hadron colliders the dominant fraction of hits is due to low momentum tracks for which multiple scattering (MS) effects dominate the hit resolution. MS is also the dominating source for hit confusion and track uncertainties in low energy precision experiments. In all such environments, where MS dominates, track reconstruction and fitting can be largely simplified by using three-dimensional (3D) hit-triplets as provided by pixel detectors. This simplification is possible since track uncertainties are solely determined by MS if high precision spatial information is provided. Fitting of hit-triplets is especially simple for tracking detectors in solenoidal magnetic fields. The over-constrained 3D-triplet method provides a complete set of track parameters and is robust against fake hit combinations. The triplet method is ideally suited for pixel detectors where hits can be treated as 3D-space poi...

  15. Neurodevelopmental outcomes of triplets or higher-order extremely low birth weight infants.

    Science.gov (United States)

    Wadhawan, Rajan; Oh, William; Vohr, Betty R; Wrage, Lisa; Das, Abhik; Bell, Edward F; Laptook, Abbot R; Shankaran, Seetha; Stoll, Barbara J; Walsh, Michele C; Higgins, Rosemary D

    2011-03-01

    Extremely low birth weight twins have a higher rate of death or neurodevelopmental impairment than singletons. Higher-order extremely low birth weight multiple births may have an even higher rate of death or neurodevelopmental impairment. Extremely low birth weight (birth weight 401-1000 g) multiple births born in participating centers of the Neonatal Research Network between 1996 and 2005 were assessed for death or neurodevelopmental impairment at 18 to 22 months' corrected age. Neurodevelopmental impairment was defined by the presence of 1 or more of the following: moderate to severe cerebral palsy; mental developmental index score or psychomotor developmental index score less than 70; severe bilateral deafness; or blindness. Infants who died within 12 hours of birth were excluded. Maternal and infant demographic and clinical variables were compared among singleton, twin, and triplet or higher-order infants. Logistic regression analysis was performed to establish the association between singletons, twins, and triplet or higher-order multiples and death or neurodevelopmental impairment, controlling for confounding variables that may affect death or neurodevelopmental impairment. Our cohort consisted of 8296 singleton, 2164 twin, and 521 triplet or higher-order infants. The risk of death or neurodevelopmental impairment was increased in triplets or higher-order multiples when compared with singletons (adjusted odds ratio: 1.7 [95% confidence interval: 1.29-2.24]), and there was a trend toward an increased risk when compared with twins (adjusted odds ratio: 1.27 [95% confidence: 0.95-1.71]). Triplet or higher-order births are associated with an increased risk of death or neurodevelopmental impairment at 18 to 22 months' corrected age when compared with extremely low birth weight singleton infants, and there was a trend toward an increased risk when compared with twins.

  16. Coexistence of spin-triplet superconductivity with magnetism within a single mechanism for orbitally degenerate correlated electrons: statistically consistent Gutzwiller approximation

    International Nuclear Information System (INIS)

    Zegrodnik, M; Spałek, J; Bünemann, J

    2013-01-01

    An orbitally degenerate two-band Hubbard model is analyzed with the inclusion of the Hund's rule-induced spin-triplet even-parity paired states and their coexistence with magnetic ordering. The so-called statistically consistent Gutzwiller approximation (SGA) has been applied to the case of a square lattice. The superconducting gaps, the magnetic moment and the free energy are analyzed as a function of the Hund's rule coupling strength and the band filling. Also, the influence of the intersite hybridization on the stability of paired phases is discussed. In order to examine the effect of correlations the results are compared with those calculated earlier within the Hartree–Fock (HF) approximation combined with the Bardeen–Cooper–Schrieffer (BCS) approach. Significant differences between the two methods used (HF + BCS versus SGA + real-space pairing) appear in the stability regions of the considered phases. Our results supplement the analysis of this canonical model used widely in the discussions of pure magnetic phases with the detailed elaboration of the stability of the spin-triplet superconducting states and the coexistent magnetic-superconducting states. At the end, we briefly discuss qualitatively the factors that need to be included for a detailed quantitative comparison with the corresponding experimental results. (paper)

  17. 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)

    Science.gov (United States)

    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.

  18. Reaction pathways of photoexcited retinal in proteorhodopsin studied by pump-dump-probe spectroscopy.

    Science.gov (United States)

    Rupenyan, Alisa; van Stokkum, Ivo H M; Arents, Jos C; van Grondelle, Rienk; Hellingwerf, Klaas J; Groot, Marie Louise

    2009-12-17

    Proteorhodopsin (pR) is a membrane-embedded proton pump from the microbial rhodopsin family. Light absorption by its retinal chromophore initiates a photocycle, driven by trans/cis isomerization on the femtosecond to picosecond time scales. Here, we report a study on the photoisomerization dynamics of the retinal chromophore of pR, using dispersed ultrafast pump-dump-probe spectroscopy. The application of a pump pulse initiates the photocycle, and with an appropriately tuned dump pulse applied at a time delay after the dump, the molecules in the initial stages of the photochemical process can be de-excited and driven back to the ground state. In this way, we were able to resolve an intermediate on the electronic ground state that represents chromophores that are unsuccessful in isomerization. In particular, the fractions of molecules that undergo slow isomerization (20 ps) have a high probability to enter this state rather than the isomerized K-state. On the ground state reaction surface, return to the stable ground state conformation via a structural or vibrational relaxation occurs in 2-3 ps. Inclusion of this intermediate in the kinetic scheme led to more consistent spectra of the retinal-excited state, and to a more accurate estimation of the quantum yield of isomerization (Phi = 0.4 at pH 6).

  19. Programmable Triplet Formation and Decay in Metal-Organic Chromophores

    Science.gov (United States)

    2011-12-13

    CH2Cl2 via the polarizable continuum model, are used to reveal the nature of the excited states in these molecules that are responsible for the...composed of a 50:50 mixture of an ethyleneoxide/epichlorohydrin copolymer, P(EO/EP). Films that were prepared under an argon atmosphere and maintained

  20. Triplet transitions of neutral CO in the spectra of comets and the abundance of CO2 or molecules containing the CO group in comets

    International Nuclear Information System (INIS)

    Biermann, L.

    1976-03-01

    The high-dispersion spectra of comet Mrkos (1957 V) taken at Mt. Palomar by J. L. Greenstein and remeasured by A. Woszczyk contain many unidentified weak lines. The possibility that some of these lines belong to transitions between triplet levels of neutral CO molecules is investigated. Their presence would suggest excitation related to the dissociative recombination of a parent containing the CO group, which is first ionized by solar uv. Of 31 CO lines (of the Asundi and Triplet systems), 14 are masked by known or by questionably identified lines as statistically expected. Of the remaining 17, 13 coincide within a few tenths of an Angstrom with an unidentified line and 4 do not. These results are contrary to statistical expectations. (Some members of the third positive system of CO, which might be present, have not been included in the figures.) Although these figures strongly favor the identification proposed, the numbers are not large enough to support entirely the argument of a small statistical probability (0.2 percent) of the observed state. Also, the rotational structure of the CO bands for the triplet systems needs further investigation. C. F. Lillie's observations of comet Bennett (1970 II) between 1200 and 1800 A, especially of the fourth positive system of CO, seem to favor a cometary atmosphere characterized by a large relative abundance of CO 2 and/or molecules containing the CO group. A model outlined for comet Bennett at 0.8 a.u. seems to be approximately consistent with observations. The chemical aspects, however, especially need further consideration. New observations, particularly of the Cameron bands of CO, are needed to settle the questions raised

  1. InGaN compositional patterning by ultraviolet photoexcitation during NH{sub 3}-based MOMBE - A pathway to 3D epitaxy

    Energy Technology Data Exchange (ETDEWEB)

    Pritchett, D.; Henderson, W.; Billingsley, D.; Doolittle, W.A. [School of Electrical and Computer Engineering, Georgia Institute of Technology, 777 Atlantic Dr., Atlanta, GA 30332 (United States)

    2008-07-01

    Lateral compositional patterning of InGaN during NH{sub 3}-based MOMBE by digital micromirror patterning of UV photoexcitation is demonstrated. Preferential desorption of In/In-methyl species during InGaN surface exposure to an elliptically focused 5 kW Hg-Xe arc lamp ({lambda}=365 nm) limits the incorporation of indium during growth. Localized photoexcitation results in the preferential In/In-methyl desorption, resulting in indium mole fractions of 0.10 in unexposed regions to as low as 0 in fully exposed regions. The technique demonstrates promise for integration of micromirrors for dynamic and maskless selective epitaxy towards the realization of complex, 3D device structures. (copyright 2008 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  2. Effect of the external electric field on the kinetics of recombination of photoexcited carriers in a ZnSe/BeTe type II heterostructure

    Science.gov (United States)

    Filatov, E. V.; Maksimov, A. A.; Tartakovskii, I. I.; Yakovlev, D. R.; Waag, A.

    2012-02-01

    The kinetics of the radiative recombination of photoexcited electrons and holes for a spatially direct transition in a ZnSe/BeTe type II heterostructure in an external electric field has been analyzed. A strong decrease (more than two orders of magnitude) in the photoluminescence intensity, as well as a decrease in the duration of the relaxation of the direct transition, is observed when the electric field is applied. The energy levels and wavefunctions of electrons and holes in the ZnSe/BeTe heterostructure subjected to the electric field have been numerically calculated. It has been shown that the observed decrease in the photoluminescence intensity and duration of the relaxation of the direct transition is due to both an increase in the radiative recombination time and an increase in the rate of escape of photoexcited holes from the above-barrier level in the ZnSe layer to the BeTe layer.

  3. A “Swingable” straight-chain affinity molecule immobilized on a semi-conductor electrode for photo-excited current-based molecular sensing

    International Nuclear Information System (INIS)

    Takatsuji, Yoshiyuki; Wakabayashi, Ryo; Sakakura, Tatsuya; Haruyama, Tetsuya

    2015-01-01

    The molecular affinities of biomolecules have found applications in the areas of clinical diagnostics, drug discovery, as well as allied fields of study. An affinity sensor is a unique in situ assay tool, which is valuable and convenient in practical situations. In this study, we designed a photo-excitable molecular interface with an affinity domain and fabricated with a “swingable” straight-chain affinity molecule immobilized on a semi-conductor electrode (SCE). The straight-chain affinity molecule possessed a photo-excitable dye at one end and was bound to the SCE surface at the other by the EC tag method, which was developed previously. A straight-chain molecule is too long to transfer electrons from the photo-excited dye to the conduction band of the SCE. However, the straight-chain molecule was designed with a “swing” structure, which made the transfer of electrons possible. The central region of the chain molecule has an affinity to the activated estrogen receptor (ER). When the activated ER bound to the affinity region, the molecular lost its swingable function, the electron transfer from the photo-excited dye to the SCE was consequently suppressed. Based on the unique swingable molecular interface, the affinity sensor can be used to determine the in situ concentration of endocrine disrupter ESTROGEN (17β-estradiol) at concentrations ranging from 2 to 10 nM with very good reproducibility. The superior assay reproducibility is responsible for the success of the EC tag method, which is a quantitative method for immobilizing molecules on SCE.

  4. Beam Dynamics Requirements for the Powering Scheme of the HL-LHC Triplet

    CERN Document Server

    AUTHOR|(CDS)2075212; Fartoukh, Stephane; Giovannozzi, Massimo

    2015-01-01

    For the HL-LHC, β ∗ values as small as 15 cm are envisaged as baseline scenario for the high luminosity insertions IR1 and IR5, thus leading to an increase of the maximum β- functions in the inner triplet (IT). The larger beta-functions in the IT result in a higher sensitivity of the beam to any linear or non-linear, static or dynamic, field imperfections in the IT region. In this paper, we summarize accordingly the tolerances of the triplet power supplies in terms of current ripple, stability and reproducibility. Both the baseline IT powering scheme and other alternative schemes will be presented, the later reducing the tune shift caused by a current modulation and thus weakening its possible impact on the long term stability.

  5. Quench protection of the LHC inner triplet quadrupoles built at Fermilab

    CERN Document Server

    Bauer, P; Chiesa, L; Di Marco, J; Fehér, S; Lamm, M J; McInturff, A D; Nobrega, A; Orris, D; Tartaglia, M; Tompkins, J C; Zlobin, A V

    2001-01-01

    High gradient quadrupoles are being developed by the US-LHC Accelerator project for the LHC interaction region inner triplets. These 5.5 m long magnets have a single 70 mm aperture and operate in superfluid helium at a peak gradient of 215 T/m. Through the construction and test of eight 2 meter long model quadrupoles, strip heaters of various geometries and insulation thicknesses have proven to be effective in protecting the magnets from excessively high coil temperatures and coil voltages to ground. This paper reports on the results of the model program to optimize the heater performance within the context of the LHC inner triplet electrical power and quench detection scheme. (6 refs).

  6. Field quality measurements of the LQXB inner triplet quadrupoles for LHC

    CERN Document Server

    Velev, G V; Carcagno, R; Di Marco, J; Fehér, S; Glass, H; Kashikhin, V V; Kerby, J; Lamm, M J; Makulski, A; Nobrega, A; Nogiec, J; Orris, D; Peterson, T; Rabehl, Roger Jon; Schlabach, P; Strait, J; Sylvester, C D; Tartaglia, M; Tompkins, J C; Zlobin, A V

    2005-01-01

    As a part of the USLHC program, Fermilab is building half of the inner triplet quadrupole magnets for the LHC. Two identical quadrupoles (MQXB) with a dipole corrector between them in a single cryogenic unit (LQXB) comprise the Q2 optical element of the final focus triplets in the interaction regions. The 5.5 m long MQXB have a 70 mm aperture and operate in superfluid helium at 1.9 K with a peak field gradient of 215 T/m. Manufacturing of the 18 magnets is in an advanced stage. A program of magnetic field quality measurements of the magnets is performed at room temperature during magnet fabrication as well as at superfluid helium temperature during the cold qualification of each magnet. Results of the measurements are summarized in this paper. (12 refs).

  7. Triplet pregnancy after intracytoplasmic sperm injection of cryopreserved oocytes: case report.

    Science.gov (United States)

    Young, E; Kenny, A; Puigdomenech, E; Van Thillo, G; Tiverón, M; Piazza, A

    1998-08-01

    To report a triplet pregnancy that occurred after intracytoplasmic injection of sperm into cryopreserved oocytes. Case report. Instituto de Ginecología y Fertilidad (IFER), Buenos Aires, Argentina. A 36-year-old infertile patient with premature ovarian failure and a previous term pregnancy with fresh donated oocytes. We administered leuprolide acetate for pituitary down-regulation followed by E2 valerianate in incremental doses until an endometrial lining of >8 mm was observed by ultrasound. Thawing of frozen donated oocytes, intracytoplasmic sperm injection (ICSI), and translaparoscopic fallopian tube ET also were performed. Natural micronized progesterone was administered intravaginally (600 mg/d) before ET. Ultrasound at the 8th week of gestation revealed a triplet pregnancy with active fetal heartbeats. A triple intrauterine gestation was achieved with the use of microinjection into cryopreserved oocytes. This case illustrates the feasibility of oocyte cryopreservation for clinical use in the era of ICSI.

  8. q-triplet for Brazos River discharge: The edge of chaos?

    Science.gov (United States)

    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.

  9. He II Heat Exchanger Test Unit for the LHC Inner Triplet

    CERN Document Server

    Blanco-Viñuela, E; Huang, Y; Nicol, T H; Peterson, T; Van Weelderen, R

    2002-01-01

    The Inner Triplet Heat Exchanger Test Unit (IT-HXTU) is a 30-m long thermal model designed at Fermilab, built in US industry, fully automated and tested at CERN as part of the US LHC program to develop the LHC Interaction Region quadrupole system. The cooling scheme of the IT-HXTU is based on heat exchange between stagnant pressurized He II in the magnet cold mass and saturated He II (two-phase) flowing in a heat exchanger located outside of and parallel to the cold mass. The purposes of this test are, among others, to validate the proposed cooling scheme and to define an optimal control strategy to be implemented in the future LHC accelerator. This paper discusses the results for the heat exchanger test runs and emphasizes the thermal and hydraulic behavior of He II for the inner triplet cooling scheme.

  10. Compact quadrupole triplet for the S-DALINAC polarized electron injector SPIN

    Energy Technology Data Exchange (ETDEWEB)

    Eckardt, C.; Eichhorn, R.; Enders, J.; Hessler, C.; Poltoratska, Y. [Inst. fuer Kernphysik, Technische Univ. Darmstadt (Germany); Ackermann, W.; Mueller, W.F.O.; Steiner, B.; Weiland, T. [Inst. fuer Theorie Elektromagnetischer Felder, Technische Univ. Darmstadt (Germany)

    2007-07-01

    An ultra compact quadrupole triplet for the S-DALINAC Polarized Electron Injector SPIN has been developed. This development is due to limiting spatial restrictions. Each individual quadrupole has a length of 8 mm, affixed by two 2 mm aluminum plates, resulting in a length of only 12 mm per quadrupole. The gaps between each quadrupole are set to 18 mm, therefore the complete triplet has a total length of only 72 mm. The quadrupole design includes a large aperture, suitable for CF 35 beam pipes. As fringe fields reach far info neighboring yokes, the assembly requires simulation by a beam dynamics tool for optimal weighting of the current excitation. Measurement of the magnetic field distribution is compared to numerical values and the quadrupole strength is calculated. (orig.)

  11. Mechanism of deactivation of triplet-excited riboflavin by ascorbate, carotenoids, and tocopherols in homogeneous and heterogeneous aqueous food model systems.

    Science.gov (United States)

    Cardoso, Daniel R; Olsen, Karsten; Skibsted, Leif H

    2007-07-25

    Tocopherols (alpha, beta, gamma, and delta) and Trolox were found to deactivate triplet-excited riboflavin in homogeneous aqueous solution (7:3 v/v tert-butanol/water) with second-order reaction rates close to diffusion control [k2 between 4.8 x 10(8) (delta-tocopherol) and 6.2 x 10(8) L mol(-1) s(-1) (Trolox) at 24.0 +/- 0.2 degrees C] as determined by laser flash photolysis transient absorption spectroscopy. In aqueous buffer (pH 6.4) the rate constant for Trolox was 2.6 x 10(9) L mol(-1) s1 and comparable to the rate constant found for ascorbate (2.0 x 10(9) L mol(-1) s(-1)). The deactivation rate constant was found to be inferior in heterogeneous systems as shown for alpha-tocopherol and Trolox in aqueous Tween-20 emulsion (approximately by a factor of 4 compared to 7:3 v/v tert-butanol/water). Neither beta-carotene (7:3 v/v tert-butanol/water and Tween-20 emulsion), lycopene (7:3 v/v tert-butanol/water), nor crocin (aqueous buffer at pH 6.4, 7:3 v/v tert-butanol/water, and Tween-20 emulsion) showed any quenching on the triplet excited state of riboflavin. Therefore, all carotenoids seem to reduce the formation of triplet-excited riboflavin through an inner-filter effect. Activation parameters were based on the temperature dependence of the triplet-excited deactivation between 15 and 35 degrees C, and the isokinetic behavior, which was found to include purine derivatives previously studied, confirms a common deactivation mechanism with a bimolecular diffusion-controlled encounter with electron (or hydrogen atom) transfer as rate-determining step. DeltaH for deactivation by ascorbic acid, Trolox, and homologue tocopherols (ranging from 18 kJ mol(-1) for Trolox in Tween-20 emulsion to 184 kJ mol(-1) for ascorbic acid in aqueous buffer at pH 6.4) showed a linear dependence on DeltaS (ranging from -19 J mol(-1) K(-1) for Trolox in aqueous buffer at pH 6.4 to +550 J mol(-1) K(-1) for ascorbic acid in aqueous buffer pH 6.4). Among photooxidation products from the

  12. Massive Triplet Excitations in a Magnetized Anisotropic Haldane Spin Chain

    International Nuclear Information System (INIS)

    Zheludev, Andrey I.; Honda, Z.; Broholm, C.L.; Katsumada, K.; Shapiro, S.M.; Kolezhuk, A.; Park, S.; Qiu, Y.

    2003-01-01

    Inelastic neutron scattering experiments on the Haldane-gap quantum antiferromagnet Ni(C 5 D 14 N 2 ) 2 N 3 (PF 6 ) are performed at mK temperatures in magnetic fields of almost twice the critical field H c applied perpendicular to the spin chains. Above H c a reopening of the spin gap is clearly observed. In the high-field Neel-ordered state the spectrum is dominated by three distinct excitation branches. A theoretical model consistently describing the experimental data is proposed.

  13. All-inorganic perovskite nanocrystal assisted extraction of hot electrons and biexcitons from photoexcited CdTe quantum dots.

    Science.gov (United States)

    Mondal, Navendu; De, Apurba; Samanta, Anunay

    2018-01-03

    Excitation of semiconductor quantum dots (QDs) by photons possessing energy higher than the band-gap creates a hot electron-hole pair, which releases its excess energy as waste heat or under certain conditions (when hν > 2E g ) produces multiple excitons. Extraction of these hot carriers and multiple excitons is one of the key strategies for enhancing the efficiency of QD-based photovoltaic devices. However, this is a difficult task as competing carrier cooling and relaxation of multiple excitons (through Auger recombination) are ultrafast processes. Herein, we study the potential of all-inorganic perovskite nanocrystals (NCs) of CsPbX 3 (X = Cl, Br) as harvesters of these short-lived species from photo-excited CdTe QDs. The femtosecond transient absorption measurements show CsPbX 3 mediated extraction of both hot and thermalized electrons of the QDs (under a low pump power) and (under a high pump fluence) extraction of multiple excitons prior to their Auger assisted recombination. A faster timescale of thermalized electron transfer (∼2 ps) and a higher extraction efficiency of hot electrons (∼60%) are observed in the presence of CsPbBr 3 . These observations demonstrate the potential of all-inorganic perovskite NCs in the extraction of these short-lived energy rich species implying that complexes of the QDs and perovskite NCs are better suited for improving the efficiency of QD-sensitized solar cells.

  14. Unified picture of the photoexcitations in phenylene-based conjugated polymers: Universal spectral and dynamical features in subpicosecond transient absorption

    International Nuclear Information System (INIS)

    Kraabel, B.; Klimov, V. I.; Kohlman, R.; Xu, S.; Wang, H-L.; McBranch, D. W.

    2000-01-01

    Using subpicosecond transient absorption spectroscopy, we investigate the primary photoexcitations in thin films and solutions of several phenylene-based conjugated polymers and an oligomer. We identify several features in the transient absorption spectra and dynamics that are common to all of the materials which we studied from this family. The first spectral feature is a photoinduced absorption (PA) band peaking near 1 eV that has intensity-dependent dynamics that match the stimulated emission dynamics exactly over two orders of magnitude in excitation density. This band is associated with singlet intrachain excitons. The second spectral feature (observed only in thin films and aggregated solutions) is a PA band peaking near 1.8 eV, that is longer lived than the 1 eV exciton PA band, and that has dynamics that are independent (or weakly dependent) on excitation density. This feature is attributed to polarons, generated through a mechanism that is sample dependent. In pristine samples, polarons are generated via a mechanism that is quadratic in exciton density, whereas in photodegraded samples or samples doped with electron acceptors, the generation mechanism becomes linear in exciton density. (c) 2000 The American Physical Society

  15. Localized holes and delocalized electrons in photoexcited inorganic perovskites: Watching each atomic actor by picosecond X-ray absorption spectroscopy

    Directory of Open Access Journals (Sweden)

    Fabio G. Santomauro

    2017-07-01

    Full Text Available We report on an element-selective study of the fate of charge carriers in photoexcited inorganic CsPbBr3 and CsPb(ClBr3 perovskite nanocrystals in toluene solutions using time-resolved X-ray absorption spectroscopy with 80 ps time resolution. Probing the Br K-edge, the Pb L3-edge, and the Cs L2-edge, we find that holes in the valence band are localized at Br atoms, forming small polarons, while electrons appear as delocalized in the conduction band. No signature of either electronic or structural changes is observed at the Cs L2-edge. The results at the Br and Pb edges suggest the existence of a weakly localized exciton, while the absence of signatures at the Cs edge indicates that the Cs+ cation plays no role in the charge transport, at least beyond 80 ps. This first, time-resolved element-specific study of perovskites helps understand the rather modest charge carrier mobilities in these materials.

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

    Science.gov (United States)

    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.

  17. Singlet and Triplet Excitation Management in a Bichromophoric Near-Infrared-Phosphorescent BODIPY-Benzoporphyrin Platinum Complex

    KAUST Repository

    Whited, Matthew T.; Djurovich, Peter I.; Roberts, Sean T.; Durrell, Alec C.; Schlenker, Cody W.; Bradforth, Stephen E.; Thompson, Mark E.

    2011-01-01

    efficient near-infrared phosphorescence (λem = 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

  18. Simultaneous monitoring of singlet and triplet exciton variations in solid organic semiconductors driven by an external static magnetic field

    Energy Technology Data Exchange (ETDEWEB)

    Ding, Baofu, E-mail: b.ding@ecu.edu.au; Alameh, Kamal, E-mail: k.alameh@ecu.edu.au [Electron Science Research Institute, Edith Cowan University, 270 Joondalup Drive, Joondalup, WA 6027 (Australia)

    2014-07-07

    The research field of organic spintronics has remarkably and rapidly become a promising research area for delivering a range of high-performance devices, such as magnetic-field sensors, spin valves, and magnetically modulated organic light emitting devices (OLEDs). Plenty of microscopic physical and chemical models based on exciton or charge interactions have been proposed to explain organic magneto-optoelectronic phenomena. However, the simultaneous observation of singlet- and triplet-exciton variations in an external magnetic field is still unfeasible, preventing a thorough theoretical description of the spin dynamics in organic semiconductors. Here, we show that we can simultaneously observe variations of singlet excitons and triplet excitons in an external magnetic field, by designing an OLED structure employing a singlet-exciton filtering and detection layer in conjunction with a separate triplet-exciton detection layer. This OLED structure enables the observation of a Lorentzian and a non-Lorentzian line-shape magnetoresponse for singlet excitons and triplet excitons, respectively.

  19. Simultaneous monitoring of singlet and triplet exciton variations in solid organic semiconductors driven by an external static magnetic field

    International Nuclear Information System (INIS)

    Ding, Baofu; Alameh, Kamal

    2014-01-01

    The research field of organic spintronics has remarkably and rapidly become a promising research area for delivering a range of high-performance devices, such as magnetic-field sensors, spin valves, and magnetically modulated organic light emitting devices (OLEDs). Plenty of microscopic physical and chemical models based on exciton or charge interactions have been proposed to explain organic magneto-optoelectronic phenomena. However, the simultaneous observation of singlet- and triplet-exciton variations in an external magnetic field is still unfeasible, preventing a thorough theoretical description of the spin dynamics in organic semiconductors. Here, we show that we can simultaneously observe variations of singlet excitons and triplet excitons in an external magnetic field, by designing an OLED structure employing a singlet-exciton filtering and detection layer in conjunction with a separate triplet-exciton detection layer. This OLED structure enables the observation of a Lorentzian and a non-Lorentzian line-shape magnetoresponse for singlet excitons and triplet excitons, respectively.

  20. Metallicities for old stellar systems from Ca II triplet strengths in member giants

    International Nuclear Information System (INIS)

    Armandroff, T.E.; Da costa, G.S.

    1991-01-01

    The spectra of giants in six well-studied Galactic globulars spanning a wide range of abundance are used to investigate the utility of the Ca II triplet as an abundance indicator. The calibration resulting from these clusters is used to derive metal abundances from the spectra of giants in Eridanus, Pal 12, and the Carina dwarf spheroidal galaxy. The results obtained are compared with earlier determinations based on giant branch photometry. 37 refs