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Sample records for triplet state spectra

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

    SciTech Connect

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

    2011-01-13

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

  2. Zero-field splitting of the ground and excited triplet states of 2-naphthylphenylcarbene studied by hole-burning on triplet-triplet fluorescence excitation spectra

    NASA Astrophysics Data System (ADS)

    Kozankiewicz, B.; Bernard, J.; Migirdicyan, E.; Orrit, M.; Platz, M. S.

    1995-11-01

    Spectral holes were burned in the two main lines of the triplet-triplet 0-0 fluorescence excitation spectrum of 2-napththylphenylcarbene in n-hexane at 1.8 K. For the line assigned to pseudo-E/trans conformer, the central hole at the frequency of burning light has several narrow components separated by 0.3 ± 0.05 and 1.0 ± 0.1 GHz and a satellite doublet line on the low energy side, 14.5 ± 0.5 and 15.5 ± 0.5 GHz away. For the line assigned to the psuedo-Z/cis conformer, the central hole is accompanied by holes burned on the low energy side, 0.8 ± 0.1, 5.2 ± 0.1, 11.9 ± 0.1 and 16.2 ± 0.1 GHz away. The hole-burning pattern is explained by a model taking into account the zero-field splitting (ZFS) of the ground T 0 and excited T 1 triplet states as well as the selectivity of excitation relaxation by the intersystem crossing channel. Analysis provides information about the ZFS parameters of the T 1 state. For the pseudo-E/trans 2-NPC they are: D0 = 0.47 ± 0.02 cm -1, E0 = 0.017 ± 0.003 cm -1, D1 = 0.038 ± 0.003 cm -1 and E1 = 0.005 ± 0.001 cm -1.

  3. Fullerene triplet states in solution

    NASA Astrophysics Data System (ADS)

    Ausman, Kevin Douglas

    Triplet state pre-equilibration by reversible energy transfer has been observed by transient-absorption spectroscopy in mixed toluene solutions of C70 and C60 and of C70 and C60(CH 3)2. The equilibrium constants governing the asymptotic partitioning of triplet energy in these mixtures were determined as a function of temperature. The enthalpies of these excited states were found from van't Hoff plots of the equilibrium constant data to be -0.1 +/- 0.2 and -3.4 +/- 0.3 kJ mol-1 for C60 and C60 (CH3)2 respectively relative to a C70 triplet energy exchange partner. The corresponding relative entropies are 5.8 +/- 0.5 and -4.0 +/- 1.0 kJ mol-1 K-1 respectively. Transient spectra from high temperature C70/C60(CH3)2 mixed samples revealed evidence of a third, unidentified transient absorber that exhibited different kinetics from the pre-equilibrated triplet pool. Triplet state transient difference spectra and intrinsic decay kinetics were measured and compared for C60 and several derivatives of C 60. These derivatives were C60H2, C60(CH 3)2, ortho-xylyl-C60, N,N'-dimethyl-1,2-ethylenediamine- C 60, C60C(COOCH2CH3)2, and C60O. The spectral locations of the main triplet-triplet absorption peak for these compounds correlates linearly with the observed intrinsic intersystem crossing rate constant. The triplet state persistence of C60 was measured in toluene solution as a function of both ground state concentration and solution temperature. The unimolecular intersystem crossing deactivation channel shows very little thermal activation, whereas the observed bimolecular self-quenching decay channel is found to be highly activated. At room temperature, the deduced exponential lifetime of the solvent-caged encounter complex between triplet and ground state molecules is three orders of magnitude shorter than that of the isolated monomer triplet state. This suggests that the self-quenching process is not a simple perturbation of an isolated molecule's intersystem crossing, but

  4. Triplet (S = 1) Ground State Aminyl Diradical

    SciTech Connect

    Rajca, Andrzej; Shiraishi, Kouichi; Pink, Maren; Rajca, Suchada

    2008-04-02

    Aminyl diradical, which is stable in solution at low temperatures, is prepared. EPR spectra and SQUID magnetometry indicate that the diradical is planar and it possesses triplet ground state, with strong ferromagnetic coupling.

  5. Chlorophyll triplet states associated with photosystem II of thylakoids.

    PubMed

    Santabarbara, Stefano; Bordignon, Enrica; Jennings, Robert C; Carbonera, Donatella

    2002-06-25

    The analysis of FDMR thylakoid spectra, determined at multiple emission wavelengths, by a global decomposition technique, has revealed the presence of three previously undescribed triplet populations at emission wavelengths characteristic of Photosystem II chlorophyll/protein complexes. Their zero-field splitting parameters have been determined in order to compare them with the well-studied PSII recombination triplet state. None of these triplets have the zero-field splitting parameters characteristic of the recombination triplet and are therefore probably not generated directly in the reaction center. On the basis of their microwave-induced emission spectra, it is suggested that two are probably generated in the core complex(es) while the third may be generated in the external antenna. These triplets are formed under nonreducing redox conditions, when the recombination triplet is undetectable. It is suggested that they may be involved in the photoinhibitory damage of Photosystem II. The triplet-minus-singlet spectrum associated with the recombination triplet state has been determined for thylakoids after reduction of the secondary acceptors. Its main peak is at 685 nm, slightly red shifted with respect to earlier reports, with a weak signal, of opposite sign at approximately 675 nm. The 685 nm peak indicates that at cryogenic temperatures, the triplet is located on the long-wavelength chlorophyll state present in the reaction center complex of Photosystem II (D1.D2.Cytb(559) complex). From the absence of a clear structure in the 680 nm absorption region, this long-wavelength absorbing state does not appear to be strongly coupled to P(680), though it must be associated with one of the "inner core" pigments recently identified in the photosystem II crystallographic structure [Zouni et al. (2001) Nature 408, 739-743].

  6. Triplet-state energies and substituent effects of excited aroyl compounds in the gas phase.

    PubMed

    Lin, Z P; Aue, W A

    2000-01-01

    Triplet-state energy values obtained from the gas phase are still scarce. In this study, the triplet-state energies of 58 aroyl compounds, introduced as gas chromatographic peaks at atmospheric pressure and typically 473 K, have been determined from the 0-0 bands of their n --> pi* type phosphorescence spectra in excited nitrogen. Correlations of those gas-phase triplet-state energies with Hammett constants could be observed for substituted acetophenones, benzaldehydes and benzophenones.

  7. Properties of the Triplet State of Coumarin Substituted Compounds

    NASA Astrophysics Data System (ADS)

    Bryantseva, N. G.; Gadirov, R. M.; Nikonov, S. Yu.; Sokolova, I. V.

    2015-03-01

    The absorption spectra of the triplet excited state of coumarin sensitizers are investigated both theoretically and experimentally. The most intense triplet-triplet (TT) absorption bands are determined. The experimental spectra of the T-T absorption are compared with the theoretical T-T transitions. The phosphorescence spectra of five compounds are measured at a temperature of 77 K. The quantum phosphorescence yield is determined by the method of comparison with an etalon (8-methoxypsoralen). The phosphorescence lifetime is determined for the examined molecules at a temperature of 77 K. For 3,4-phenyl-4',5'-cyclohexylpsoralen, 4'-methyl-3,4-cycloheptylpsoralen, and 4'5'-dimethyl-3,4-cyclohexylpsoralen compounds, this time is equal to 1.1, 1.25, and 2.5 s, respectively. The main energy deactivation channel for all examined compounds is the phosphorescence. The positions of the lower excited triplet states, calculated by the quantum-chemical method of intermediate neglect of differential overlap with spectroscopic parameterization (INDO/S), are confirmed by the available experimental data.

  8. A Description of Vibrational Modes in Hexaphyrins: Understanding the Aromaticity Reversal in the Lowest Triplet State.

    PubMed

    Sung, Young Mo; Oh, Juwon; Naoda, Koji; Lee, Taegon; Kim, Woojae; Lim, Manho; Osuka, Atsuhiro; Kim, Dongho

    2016-09-19

    Aromaticity reversal in the lowest triplet state, or Baird's rule, has been postulated for the past few decades. Despite numerous theoretical works on aromaticity reversal, experimental study is still at a rudimentary stage. Herein, we investigate the aromaticity reversal in the lowest excited triplet state using a comparable set of [26]- and [28]hexaphyrins by femtosecond time-resolved infrared (IR) spectroscopy. Compared to the relatively simple IR spectra of [26]bis(rhodium) hexaphyrin (R26H), those of [28]bis(rhodium) hexaphyrin (R28H) show complex IR spectra the region for the stretching modes of conjugated rings. Whereas time-resolved IR spectra of R26H in the excited triplet state are dominated by excited state IR absorption peaks, while those of R28H largely show ground state IR bleaching peaks, reflecting the aromaticity reversal in the lowest triplet state. These contrasting IR spectral features serve as new experimental aromaticity indices for Baird's rule.

  9. Toward Triplet Ground State NaLi Molecules

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  10. Chlorophyll a and carotenoid triplet states in light-harvesting complex II of higher plants.

    PubMed Central

    Peterman, E J; Dukker, F M; van Grondelle, R; van Amerongen, H

    1995-01-01

    Laser-flash-induced transient absorption measurements were performed on trimeric light-harvesting complex II to study carotenoid (Car) and chlorophyll (Chl) triplet states as a function of temperature. In these complexes efficient transfer of triplets from Chl to Car occurs as a protection mechanism against singlet oxygen formation. It appears that at room temperature all triplets are being transferred from Chl to Car; at lower temperatures (77 K and below) the transfer is less efficient and chlorophyll triplets can be observed. In the presence of oxygen at room temperature the Car triplets are partly quenched by oxygen and two different Car triplet spectral species can be distinguished because of a difference in quenching rate. One of these spectral species is replaced by another one upon cooling to 4 Ki demonstrating that at least three carotenoids are in close contact with chlorophylls. The triplet minus singlet absorption (T-S) spectra show maxima at 504-506 nm and 517-523 nm, respectively. In the Chl Qy region absorption changes can be observed that are caused by Car triplets. The T-S spectra in the Chl region show an interesting temperature dependence which indicates that various Car's are in contact with different Chl a molecules. The results are discussed in terms of the crystal structure of light-harvesting complex II. PMID:8599673

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

    PubMed Central

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

    2008-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2008-05-01

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

  13. Ion-Pair States in Triplet Molecular Hydrogen

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  14. Eosin Y triplet state as a probe of spatial heterogeneity in microcrystalline cellulose.

    PubMed

    Rodríguez, Hernán B; San Román, Enrique; Duarte, Paulo; Machado, Isabel Ferreira; Ferreira, Luis F Vieira

    2012-01-01

    The photophysical behavior of eosin Y adsorbed onto microcrystalline cellulose was evaluated by reflectance spectroscopy, steady-state fluorescence spectroscopy and laser induced time-resolved luminescence. On increasing the concentration of the dye, small changes in absorption spectra, fluorescence redshifts and fluorescence quenching are observed. Changes in absorption spectra point to the occurrence of weak exciton interactions among close-lying dye molecules, whereas fluorescence is affected by reabsorption and excitation energy trapping. Phosphorescence decays are concentration independent as a result of the negligible exciton interaction of dye pairs in the triplet state. Lifetime distribution and bilinear regression analyses of time-resolved phosphorescence and delayed fluorescence spectra reveal the existence of two different environments: long-lived, more energetic triplet states arise from dyes tightly entrapped within the cellulose chains, while short-lived, less-energetic states result from dyes in more flexible environments. Stronger hydrogen bond interactions between the dye and cellulose hydroxyl groups lead in the latter case to a lower triplet energy and faster radiationless decay. These effects, observed also at low temperatures, are similar to those encountered in several amorphous systems, but rather than being originated in changes in the environment during the triplet lifetime, they are ascribed in this case to spatial heterogeneity.

  15. Pulse train fluorescence technique for measuring triplet state dynamics.

    PubMed

    De Boni, Leonardo; Franzen, Paulo L; Gonçalves, Pablo J; Borissevitch, Iouri E; Misoguti, Lino; Mendonça, Cleber R; Zilio, Sergio C

    2011-05-23

    We report on a method to study the dynamics of triplet formation based on the fluorescence signal produced by a pulse train. Basically, the pulse train acts as sequential pump-probe pulses that precisely map the excited-state dynamics in the long time scale. This allows characterizing those processes that affect the population evolution of the first excited singlet state, whose decay gives rise to the fluorescence. The technique was proven to be valuable to measure parameters of triplet formation in organic molecules. Additionally, this single beam technique has the advantages of simplicity, low noise and background-free signal detection.

  16. Chlorophyll a triplet-state ESR in frozen phosphatidylcholine vesicles

    SciTech Connect

    Hiromitsu, I.; Kevan, L.

    1988-05-19

    Photoexcited chlorophyll a (Chla) triplet state in rapidly frozen egg phosphatidylcholine (EPC) vesicles is investigated at 77 K by electron spin resonance (ESR) spectroscopy using light intensity modulation. The electron spin polarization (ESP) intensity is stronger for 0.2 mM Chla than for 1.0 mM Chla. The absolute values of the zero field splitting parameter, D, are 283 (+/-1) x 10/sup -4/ and 276 (+/-2) x 10/sup -4/ cm/sup -1/, and the average depopulation rates of the triplet state are 0.671 +/- 0.052 and 1.054 +/- 0.036 ms/sup -1/ for 0.2 mM Chla and 1.0 mM Chla, respectively. This difference can be consistently attributed to faster triplet-state migration between adjacent Chla's at the higher 1.0 mM Chla concentration. A characteristic migration time of 2.6 ms is obtained. The ESP pattern of the Chla triplet state in the frozen EPC vesicles resembles that in polycrystals more than that in glasses. This suggests that the local environment around Chla in the vesicles is more structured than in glasses.

  17. Photoexcited triplet states of UV-B absorbers: ethylhexyl triazone and diethylhexylbutamido triazone.

    PubMed

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

    2015-04-01

    The excited states of UV-B absorbers, ethylhexyl triazone (EHT) and diethylhexylbutamido triazone (DBT), have been studied through measurements of UV absorption, fluorescence, phosphorescence, triplet-triplet absorption and electron paramagnetic resonance spectra in ethanol. The energy levels of the lowest excited singlet (S1) and triplet (T1) states and quantum yields of fluorescence and phosphorescence of EHT and DBT were determined. In ethanol at 77 K, the deactivation process of EHT and DBT is predominantly fluorescence, however, a significant portion of the S1 molecules undergoes intersystem crossing to the T1 state. The observed phosphorescence spectra, T1 lifetimes and zero-field splitting parameters suggest that the T1 state of EHT can be assigned to a locally excited (3)ππ* state within p-(N-methylamino)benzoic acid, while the T1 state of DBT can be assigned to a locally excited (3)ππ* state within p-(N-methylamino)benzoic acid or p-amino-N-methylbenzamide. The quantum yields of singlet oxygen generation by EHT and DBT were determined by time-resolved near-IR phosphorescence measurements in ethanol at room temperature. EHT and DBT did not exhibit significantly antioxidative properties by quenching singlet oxygen, in contrast to the study by Lhiaubet-Vallet et al.

  18. Rhenium(I) tricarbonyl polypyridine complexes showing strong absorption of visible light and long-lived triplet excited states as a triplet photosensitizer for triplet-triplet annihilation upconversion.

    PubMed

    Yi, Xiuyu; Zhao, Jianzhang; Wu, Wanhua; Huang, Dandan; Ji, Shaomin; Sun, Jifu

    2012-08-07

    The preparation of rhenium(I) tricarbonyl polypyridine complexes that show a strong absorption of visible light and long-lived triplet excited state and the application of these complexes as triplet photosensitizers for triplet-triplet annihilation (TTA) based upconversion are reported. Imidazole-fused phenanthroline was used as the N^N coordination ligand, on which different aryl groups were attached (Phenyl, Re-0; Coumarin, Re-1 and naphthyl, Re-2). Re-1 shows strong absorption of visible light (ε = 60,800 M(-1) cm(-1) at 473 nm). Both Re-1 and Re-2 show long-lived T(1) states (lifetime, τ(T), is up to 86.0 μs and 64.0 μs, respectively). These properties are in contrast to the weak absorption of visible light and short-lived triplet excited states of the normal rhenium(I) tricarbonyl polypyridine complexes, such as Re-0 (ε = 5100 M(-1) cm(-1) at 439 nm, τ(T) = 2.2 μs). The photophysical properties of the complexes were fully studied with steady state and time-resolved absorption and emission spectroscopes, as well as DFT calculations. The intra-ligand triplet excited state is proposed to be responsible for the exceptionally long-lived T(1) states of Re-1 and Re-2. The Re(I) complexes were used as triplet photosensitizers for TTA based upconversion and an upconversion quantum yield up to 17.0% was observed.

  19. Reaction mechanisms of riboflavin triplet state with nucleic acid bases.

    PubMed

    Lin, Weizhen; Lu, Changyuan; Du, Fuqiang; Shao, Zhiyong; Han, Zhenhui; Tu, Tiecheng; Yao, Side; Lin, Nianyun

    2006-04-01

    ESR and laser flash photolysis studies have determined a reasonable order of reactivity of nucleotides with triplet riboflavin (3Rb*) for the first time. ESR detection of triplet state reactivity of Rb with nucleoside, polynucleotide and DNA has been obtained simultaneously. In addition, ESR spin elimination measurement of the reactivity of 3Rb* with nucleotides in good accord with laser flash photolysis determination of the corresponding rate constants offers a simple and reliable method to detect the reactivities of nucleic acids and its components with photoexcited flavins. Kinetic, ESR and thermodynamic studies have demonstrated that Rb should be a strong endogenous photosensitizer capable of oxidizing all nucleic acid bases, and preferentially two purine nucleotides with high rate constants.

  20. Triplet exciton state and related phenomena in the β -phase of poly(9,9-dioctyl)fluorene

    NASA Astrophysics Data System (ADS)

    Rothe, C.; King, S. M.; Dias, F.; Monkman, A. P.

    2004-11-01

    Using both time-resolved emission and cw photoinduced absorption spectroscopy as a function of temperature, the aggregation phenomena ( β -phase formation) observed in poly(9,9-dioctyl)fluorene is studied. All spectra of the β phase, including absorption, prompt and delayed fluorescence, phosphorescence, and photoinduced triplet absorption feature very narrow linewidths, which are unique within the class of conjugated polymers. From the comparison of the latter data with amorphous polyfluorene, poly(9,9-diethylhexyl)fluorene, as well as with the fully planar ladder-type poly(paraphenylene), we conclude that the origin of the β phase cannot simply be an extended intrachain conjugation, but interchain interactions are involved. Furthermore, the β phase acts as an energetic trap for both singlet and triplet excitons initially created on amorphous chain segments. The delayed fluorescence kinetics of the β phase were measured at different temperatures. From the analysis of these decays within the framework of dispersive triplet migration in a Gaussian density of states distribution, further evidence is provided that the delayed fluorescence originates from triplet-triplet annihilation. At room temperature, it is clear that triplet excitons migrate over large distances, exceeding that of singlet excitons. Also, the segregation time between dispersive triplet migration and classical thermally activated hopping, is in the case of β -phase containing samples, dependent on the separation of the β -phase domains.

  1. Characterization of the singlet and triplet excited states of 3-chloro-4-methylumbelliferone.

    PubMed

    Seixas de Melo, J Sérgio; Cabral, Catarina; Lima, João C; Maçanita, António L

    2011-08-04

    An extensive photophysical characterization of 3-chloro-4-methylumbelliferone (3Cl4MU) in the ground-state, S(0), first excited singlet state, S(1), and lowest triplet state, T(1), was undertaken in water, neutral ethanol, acidified ethanol, and basified ethanol. Quantitative measurements of quantum yields (fluorescence, phosphorescence, intersystem crossing, internal conversion, and singlet oxygen formation) together with lifetimes were obtained at room and low temperature in water, dioxane/water mixtures, and alcohols. The different transient species were assigned and a general kinetic scheme is presented, summarizing the excited-state multiequilibria of 3Cl4MU. In water, the equilibrium is restricted to neutral (N*) and anionic (A*) species, both in the ground (pK(a) = 7.2) and first excited singlet states (pK(a)* = 0.5). In dioxane/water mixtures (pH ca. 6), substantial changes of the kinetics of the S(1) state were observed with the appearance of an additional tautomeric T* species. In low water content mixtures (mixture 9:1 v:v), only the neutral (N*) and tautomeric (T*) forms of 3Cl4MU are observed, whereas at higher water content mixtures (water mole fraction superior to 0.45), all three species N*, T*, and A* coexist in the excited state. In the triplet state, in the nonprotic and nonpolar solvent dioxane, the observed transient signals were assigned as the triplet-triplet transition of the neutral form, N*(T(1)) → N*(T(n)). In water, two transient species were observed and are assigned as the triplets of the neutral N*(T(1)) and the anionic form, A*(T(1)) (also obtained in basified ethanol). The phosphorescence spectra and decays of 3Cl4MU, in neutral, acidified, and basified solutions, demonstrate that only these two species N*(T(1)) and A*(T(1)) exist in the lowest lying triplet state, T(1). The radiative channel was found dominant for the deactivation of the anionic species, whereas with the neutral the S(1) ⇝ S(0) internal conversion competes with

  2. Room temperature triplet state spectroscopy of organic semiconductors.

    PubMed

    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.

  3. Excited triplet states as photooxidants in surface waters

    NASA Astrophysics Data System (ADS)

    Canonica, S.

    2012-12-01

    The chromophoric components of dissolved organic matter (DOM) are generally the main absorbers of sunlight in surface waters and therefore a source of transient reactants under irradiation. Such short-lived species can be relevant for the fate of various classes of chemical contaminants in the aquatic environment. The present contribution focuses on the role of excited triplet states of chromophoric DOM, 3CDOM*, as transient photooxidants initiating the transformation and degradation of organic chemical contaminants. An early study [1] indicated that 3CDOM* may play a dominant role in the photo-induced transformation of electron-rich phenols, a conclusion which was later fortified by the results of transient absorption investigations using aromatic ketones as model photosensitizers [2] and by a recent careful analysis of the effect of oxygen concentration on transformation rates [3]. The variety of aquatic contaminants shown to be affected by triplet-induced oxidation has kept increasing, phenylurea herbicides [4], sulfonamide antibiotics [5] and some phytoestrogens [6] being prominent examples. Recent research has shown that the triplet-induced transformation of specific contaminants, especially aromatic nitrogen compounds, could be inhibited by the presence of DOM, very probably due to its antioxidant moieties [7]. While such moieties are not relevant for the quenching of 3CDOM*, they are expected to react with it in a similar way as the studied contaminants. Analogous reactions can be postulated to occur in liquid or solid phases of the atmospheric environment, as demonstrated in the case of HONO formation [8]. References 1. Canonica, S.; Jans, U.; Stemmler, K.; Hoigné, J. Transformation kinetics of phenols in water: Photosensitization by dissolved natural organic material and aromatic ketones. Environ. Sci. Technol. 1995, 29 (7), 1822-1831. 2. Canonica, S.; Hellrung, B.; Wirz, J. Oxidation of phenols by triplet aromatic ketones in aqueous solution. J. Phys

  4. Triplet excited states of cyclic disulfides and related compounds: electronic structures, geometries, energies, and decay.

    PubMed

    Ginagunta, Saroja; Bucher, Götz

    2011-02-03

    We have performed a computational study on the properties of a series of heterocycles bearing two adjacent heteroatoms, focusing on the structures and electronic properties of their first excited triplet states. If the heteroatoms are both heavy chalcogens (S, Se, or Te) or isoelectronic species, then the lowest excited triplet state usually has (π*, σ*) character. The triplet energies are fairly low (30-50 kcal mol(-1)). The (π*, σ*) triplet states are characterized by a significantly lengthened bond between the two heteroatoms. Thus, in 1,2-dithiolane (1b), the S-S bond length is calculated to be 2.088 Å in the singlet ground state and 2.568 Å in the first triplet excited state. The spin density is predicted to be localized almost exclusively on the sulfur atoms. Replacing one heavy chalcogen atom by an oxygen atom or an NR group results in a significant destabilization of the (π*, σ*) triplet excited state, which then no longer is lower in energy than an open-chain biradical. The size of the heterocyclic ring also contributes to the stability of the (π*, σ*) triplet state, with five-membered rings being more favorable than six-membered rings. Benzoannulation, finally, usually lowers the energy of the (π*, σ*) triplet excited states. If one of the heteroatoms is an oxygen or nitrogen atom, however, the corresponding lowest triplet states are better described as σ,π-biradicals.

  5. Triplet states of bacteriochlorophyll and carotenoids in chromatophores of photosynthetic bacteria.

    PubMed

    Monger, T G; Cogdell, R J; Parson, W W

    1976-10-13

    Chromatophores from photosynthetic bacteria were excited with flashes lasting approx. 15 ns. Transient optical absorbance changes not associated with the photochemical electron-transfer reactions were interpreted as reflecting the conversion of bacteriochlorophyll or carotenoids into triplet states. Triplet states of various carotenoids were detected in five strains of bacteria; triplet states of bacteriochlorophyll, in two strains that lack carotenoids. Triplet states of antenna pigments could be distinguished from those of pigments specifically associated with the photochemical reaction centers. Antenna pigments were converted into their triplet states if the photochemical apparatus was oversaturated with light, if the primary photochemical reaction was blocked by prior chemical oxidation of P-870 or reduction of the primary electron acceptor, or if the bacteria were genetically devoid of reaction centers. Only the reduction of the electron acceptor appeared to lead to the formation of triplet states in the reaction centers. In the antenna bacteriochlorophyll, triplet states probably arise from excited singlet states by intersystem crossing. The antenna carotenoid triplets probably are formed by energy transfer from triplet antenna bacteriochlorophyll. The energy transfer process has a half time of approx. 20 ns, and is about 1 X 10(3) times more rapid than the reaction of the bacteriochlorophyll triplet states with O2. This is consistent with a role of carotenoids in preventing the formation of singlet O2 in vivo. In the absence of carotenoids and O2, they decay half times of the triplet states are 70 mus for the antenna bacteriochlorophyll and 6-10 mus for the reaction center bacteriochlorophyll. The carotenoid triplets decay with half times of 2-8 mus. With eak flashes, the quantum yields of the antenna triplet states are in the order of 0.02. The quantum yields decline severely after approximately one triplet state is formed per photosynthetic unit, so that

  6. Synthesis of Aza-m-Xylylene diradicals with large singlet-triplet energy gap and statistical analyses of their EPR spectra

    SciTech Connect

    Olankitwanit, Arnon; Pink, Maren; Rajca, Suchada; Rajca, Andrzej

    2014-10-08

    We describe synthesis and characterization of a derivative of aza-m-xylylene, diradical 2, that is persistent in solution at room temperature with the half-life measured in minutes (~80–250 s) and in which the triplet ground state is below the lowest singlet state by >10 kcal mol⁻¹. The triplet ground states and ΔEST of 2 in glassy solvent matrix are determined by a new approach based on statistical analyses of their EPR spectra. Characterization and analysis of the analogous diradical 1 are carried out for comparison. Statistical analyses of their EPR spectra reliably provide improved lower bounds for ΔEST (from >0.4 to >0.6 kcal mol⁻¹) and are compatible with a wide range of relative contents of diradical vs monoradical, including samples in which the diradical and monoradical are minor and major components, respectively. This demonstrates a new powerful method for the determination of the triplet ground states and ΔEST applicable to moderately pure diradicals in matrices.

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

    SciTech Connect

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

    2010-06-15

    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.

  8. Quantum chemical study on the population of the lowest triplet state of psoralen

    NASA Astrophysics Data System (ADS)

    Serrano-Pérez, Juan José; Merchán, Manuela; Serrano-Andrés, Luis

    2007-01-01

    The efficient population of the low-lying triplet ππ * state of psoralen is studied with the quantum chemical CASPT2 method. Minima, singlet-triplet crossings, conical intersections, and reaction paths on the low-lying singlet and triplet states hypersurfaces of the system have been computed together with electronic energy gaps and spin-orbit coupling terms. A mechanism is proposed, favorable in the gas phase, for efficient deactivation of the initially populated singlet excited ππ * state, starting with an intersystem crossing with an nπ * triplet state and evolving via a conical intersection toward the final lowest-lying ππ * triplet state, protagonist of the reactivity of psoralen.

  9. Excited triplet state photophysics of the sulphonated aluminium phthalocyanines bound to human serum albumin.

    PubMed

    Foley, M S; Beeby, A; Parker, A W; Bishop, S M; Phillips, D

    1997-03-01

    The binding of the sulphonated aluminum phthalocyanines to human serum albumin (HSA) in aqueous phosphate buffer solution at 25 degrees C has been studied by measuring the properties of the triplet excited states of these dyes. The triplet lifetimes were measured by triplet-triplet absorption flash photolysis. The triplet lifetime of the disulphonated AlS2Pc (2.5 microM) varies from 500 +/- 30 microseconds in the absence of protein to 1.100 microseconds and longer with HSA concentrations above 100 microM. Under identical conditions, the maximum triplet lifetimes of the mono-, tri- and tetrasulphonated compounds bound to HSA are shorter than those for the disulphonated species. The increase in the triplet state lifetimes is attributed to the ability of the bulk aqueous phase to interact with the sensitizer at the site of binding; the site of binding being dependent on the degree of sulphonation. For AlS2Pc and AlS3Pc at all HSA concentrations, and regardless of the degree of sulphonation, all the triplet state decay profiles follow simple pseudo-first-order kinetics. The exponential decay of the triplet phthalocyanine at all HSA concentrations is ascribed to the rapid association and dissociation of the phthalocyanine-HSA complex on the time-scales of the triplet state lifetimes. A simplified one-step binding model is utilized to describe the results. The association of AlS1Pc with HSA results in substantial quenching of the triplet state quantum yield, and a more complex model is required to analyze the results. The tetrasulphonated compound (AlS4Pc) binds to the protein at a site where it experiences some protection from the aqueous phase.

  10. Triplet States of Thioflavin T in Fluorescent Molecular Rotor Model

    NASA Astrophysics Data System (ADS)

    Kuz‧mitskii, V. A.; Stepuro, V. I.

    2017-01-01

    Quantum-chemical INDO/S calculations of Thiofl avin T have been carried out taking account of variation of the angle φ between the planes of the benzothiazole (BTZ) and dimethylaniline (DMA) rings. It was found that when the angle φ changes from 40° to 90° the energy of the triplet state increases by 4000 cm-1, whereas the energy of the singlet state S 1 decreases by 1900 cm-1 and reaches a minimum. The function {E}_{T_1}(φ) has a minimum at φ = 30°, which is 300 cm-1 less than at φ = 40°. The calculated T 1 S 0 interval at φ = 30-40° amounts to 15,600-16,000 cm-1, which agrees well with the phosphorescence data (17,100-17,400 cm-1). For φ = 80-90° the T 1, T 2 , and T 3 levels ( T 1 and T 2 are lower than S 1 ) are close to the S 1 level. The S 1 and T 3 levels intersect at φ 85°, and at φ = 90° the interval Δ {E}_{S_1{T}_3} amounts to only 100 cm-1 due to the small value of the exchange integral corresponding to electron transfer DMA → BTZ.

  11. Bright and dark triplet states of the negatively charged magnetoexcitons revealed in photoluminescence and time-resolved measurements

    NASA Astrophysics Data System (ADS)

    Munteanu, F. M.; Rickel, D. G.; Perry, C. H.; Kim, Yongmin; Simmons, J. A.; Reno, J. L.

    2000-12-01

    Continuous and time-resolved magnetophotoluminescence measurements of three GaAs/AlxGa1-xAs heterostructures have been made in high magnetic fields. The spectra revealed the presence of a singlet and two triplet states (the so-called ``bright'' and ``dark'' states) of the negatively charged magnetoexciton, in addition to the neutral exciton. For an asymmetrically doped single quantum well sample, the singlet and the dark triplet states converge (and possibly cross) at a field of about 40 T. The two single heterojunction samples on the other hand show no such convergence, and the singlet remains the fundamental state at least in fields to 60 T. The lifetimes of the charged magnetoexcitons increased linearly with field, whereas the neutral exciton was essentially field independent. The results clarify earlier experimental studies, and provide a confirmation of a recent theory of the behavior of charged magnetoexcitons in magnetic fields by Wojs et al. [Phys Rev. B 62, 4630 (2000)].

  12. Dynamics of the binding of acridine dyes to DNA investigated by triplet excited state probe techniques

    SciTech Connect

    Geacintov, N.E.; Waldmeyer, J.; Kuzmin, V.A.; Kolubayev, T.

    1981-11-26

    The binding of the polynuclear aromatic dyes acridine orange (AO) and proflavin (PF) to DNA in aqueous phosphate buffer solution at 25 +- 1/sup 0/C has been studied by measuring the properties of the triplet excited states of these dyes. The triplet lifetimes can be measured either by triplet-triplet absorption flash photolysis techniques or by delayed fluorescence methods. The triplet lifetimes of AO vary from about 0.5 ms with no DNA present to 20 to 35 ms at DNA concentration above 10/sup -3/M expressed in concentration of DNA phosphate (P), or at (P)/(D) ratios above 1000 ((D) is the dye concentration). At all DNA concentrations the decay profiles are exponential, except at high excitation intensities where nonexponentialities, attributed to triplet-triplet annihilation, become apparent. Similar results are observed with PF-DNA solutions. The exponentiality of the triplet decay at all DNA concentrations is attributed to rapid association and dissociation of the dye-DNA complexes on the time scales of the triplet lifetimes. A simplified one-step binding model is utilized to describe this effect. A dissociation rate of AO-DNA complexes greater than or equal to 10/sup 3/s/sup -1/ has been estimated from these results. It is shown that a detailed study of the triplet lifetime vs. DNA concentration provides a novel method for the estimation of the apparent equilibrium association constant K* for dye molecules in the triplet excited state and DNA. For AO, K* approx. = 10/sup 5/ M/sup -1/, while for PF it is approx. = 3 x 10/sup 4/ M/sup -1/. These values are of the same order of magnitude as the ground-state dye-DNA equilibrium association constants measured by others.

  13. Direct Observation of Thermal Equilibrium of Excited Triplet States of 9,10-Phenanthrenequinone. A Time-Resolved Resonance Raman Study.

    PubMed

    Kumar, Venkatraman Ravi; Rajkumar, Nagappan; Ariese, Freek; Umapathy, Siva

    2015-10-08

    The photochemistry of aromatic ketones plays a key role in various physicochemical and biological processes, and solvent polarity can be used to tune their triplet state properties. Therefore, a comprehensive analysis of the conformational structure and the solvent polarity induced energy level reordering of the two lowest triplet states of 9,10-phenanthrenequinone (PQ) was carried out using nanosecond-time-resolved absorption (ns-TRA), time-resolved resonance Raman (TR(3)) spectroscopy, and time dependent-density functional theory (TD-DFT) studies. The ns-TRA of PQ in acetonitrile displays two bands in the visible range, and these two bands decay with similar lifetime at least at longer time scales (μs). Interestingly, TR(3) spectra of these two bands indicate that the kinetics are different at shorter time scales (ns), while at longer time scales they followed the kinetics of ns-TRA spectra. Therefore, we report a real-time observation of the thermal equilibrium between the two lowest triplet excited states of PQ, assigned to nπ* and ππ* of which the ππ* triplet state is formed first through intersystem crossing. Despite the fact that these two states are energetically close and have a similar conformational structure supported by TD-DFT studies, the slow internal conversion (∼2 ns) between the T(2)(1(3)nπ*) and T(1)(1(3)ππ*) triplet states indicates a barrier. Insights from the singlet excited states of PQ in protic solvents [ J. Chem. Phys. 2015 , 142 , 24305 ] suggest that the lowest nπ* and ππ* triplet states should undergo hydrogen bond weakening and strengthening, respectively, relative to the ground state, and these mechanisms are substantiated by TD-DFT calculations. We also hypothesize that the different hydrogen bonding mechanisms exhibited by the two lowest singlet and triplet excited states of PQ could influence its ISC mechanism.

  14. Triplet excited state distortions in a pyrazolate bridged platinum dimer measured by X-ray transient absorption spectroscopy.

    PubMed

    Lockard, Jenny V; Rachford, Aaron A; Smolentsev, Grigory; Stickrath, Andrew B; Wang, Xianghuai; Zhang, Xiaoyi; Atenkoffer, Klaus; Jennings, Guy; Soldatov, Alexander; Rheingold, Arnold L; Castellano, Felix N; Chen, Lin X

    2010-12-09

    The excited-state structure of a dinuclear platinum(II) complex with tert-butyl substituted pyrazolate bridging units, [Pt(ppy)(μ-(t)Bu(2)pz)](2) (ppy = 2-phenylpyridine; (t)Bu(2)pz = 3,5-di-tert-butylpyrazolate) is studied by X-ray transient absorption (XTA) spectroscopy to reveal the transient electronic and nuclear geometry. DFT calculations predict that the lowest energy triplet excited state, assigned to a metal-metal-to-ligand charge transfer (MMLCT) transition, has a contraction in the Pt-Pt distance. The Pt-Pt bond length and other structural parameters extracted from fitting the experimental XTA difference spectra from full multiple scattering (FMS) and multidimensional interpolation calculations indicates a metal-metal distance decrease by approximately 0.2 Å in the triplet excited state. The advantages and challenges of this approach in resolving dynamic transient structures of nonbonding or weak-bonding dinuclear metal complexes in solution are discussed.

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

    NASA Technical Reports Server (NTRS)

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

    1994-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

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

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

    SciTech Connect

    Uvarov, Mikhail N.; Behrends, Jan; Kulik, Leonid V.

    2015-12-28

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

  18. Higher triplet state of fullerene C70 revealed by electron spin relaxation

    NASA Astrophysics Data System (ADS)

    Uvarov, Mikhail N.; Behrends, Jan; Kulik, Leonid V.

    2015-12-01

    Spin-lattice relaxation times T1 of photoexcited triplets 3C70 in glassy decalin were obtained from electron spin echo inversion recovery dependences. In the range 30-100 K, the temperature dependence of T1 was fitted by the Arrhenius law with an activation energy of 172 cm-1. This indicates that the dominant relaxation process of 3C70 is described by an Orbach-Aminov mechanism involving the higher triplet state t2 which lies 172 cm-1 above the lowest triplet state t1. Chemical modification of C70 fullerene not only decreases the intrinsic triplet lifetime by about ten times but also increases T1 by several orders of magnitude. The reason for this is the presence of a low-lying excited triplet state in 3C70 and its absence in triplet C70 derivatives. The presence of the higher triplet state in C70 is in good agreement with the previous results from phosphorescence spectroscopy.

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

    PubMed

    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).

  20. Broadband visible light-harvesting naphthalenediimide (NDI) triad: study of the intra-/intermolecular energy/electron transfer and the triplet excited state.

    PubMed

    Wu, Shuang; Zhong, Fangfang; Zhao, Jianzhang; Guo, Song; Yang, Wenbo; Fyles, Tom

    2015-05-21

    A triad based on naphthalenediimides (NDI) was prepared to study the intersystem crossing (ISC), the fluorescence-resonance-energy-transfer (FRET), as well as the photoinduced electron transfer (PET) processes. In the triad, the 2-bromo-6-alkylaminoNDI moiety was used as singlet energy donor and the spin converter, whereas 2,6-dialkylaminoNDI was used as the singlet/triplet energy acceptor. This unique structural protocol and thus alignment of the energy levels ensures the competing ISC and FRET in the triad. The photophysical properties of the triad and the reference compounds were studied with steady-state UV-vis absorption spectra, fluorescence spectra, nanosecond transient absorption spectra, cyclic voltammetry, and DFT/TDDFT calculations. FRET was confirmed with steady-state UV-vis absorption and fluorescence spectroscopy. Intramolecular electron transfer was observed in polar solvents, demonstrated by the quenching of both the fluorescence and triplet state of the energy acceptor. Nanosecond transient absorption spectroscopy shows that the T1 state of the triad is exclusively localized on the 2,6-dialkylaminoNDI moiety in the triad upon selective photoexcitation into the energy donor, which indicates the intramolecular triplet state energy transfer. The intermolecular triplet state energy transfer between the two reference compounds was investigated with nanosecond transient absorption spectroscopy. The photophysical properties were rationalized by TDDFT calculations.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

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

    2016-10-05

    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.

  3. Valley spin-orbit interaction for the triplet and doublet 1sground states of lithium donor center in monoisotopic {sup 28}Si

    SciTech Connect

    Ezhevskii, Alexander A.; Popkov, Sergey A.; Soukhorukov, Andrey V.; Guseinov, Davud V.; Konakov, Anton A.; Abrosimov, Nikolai V.; Riemann, Helge

    2013-12-04

    Valley spin-orbit interaction for the triplet and doublet 1s-ground states of lithium donor center in monoisotopic {sup 28}Si was studied in order to determine its contribution to the electron spin relaxation rate. We observed new electron paramagnetic resonance spectra of lithium in monoisotopic silicon with g<2.000 and found the spin Hamiltonian parameters for it. Using our experimental results and taking into account spin-orbit coupling between the triplet states and the triplet and doublet states we found that the lithium donor electron spectrum and g-factors for its states strongly depend on both the internal strains in the crystal and the intervalley spin-orbit interactions.

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

    PubMed

    Chen, Zeyuan; Anastasio, Cort

    2017-01-25

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

  5. Photodissociation and radiative association of HeH+ in the metastable triplet state.

    PubMed

    Loreau, J; Vranckx, S; Desouter-Lecomte, M; Vaeck, N; Dalgarno, A

    2013-10-03

    We investigate the photodissociation of HeH(+) in the metastable triplet state as well as its formation through the inverse process, radiative association. In models of astrophysical plasmas, HeH(+) is assumed to be present only in the ground state, and the influence of the triplet state has not been explored. It may be formed by radiative association during collisions between a proton and metastable helium, which are present in significant concentrations in nebulae. The triplet state can also be formed by association of He(+) and H, although this process is less likely to occur. We compute the cross sections and rate coefficients corresponding to the photodissociation of the triplet state by UV photons from a central star using a wave packet method. We show that the photodissociation cross sections depend strongly on the initial vibrational state and that the effects of excited electronic states and nonadiabatic couplings cannot be neglected. We then calculate the cross section and rate coefficient for the radiative association of HeH(+) in the metastable triplet state.

  6. Effect of a triplet to singlet state interaction on photofragmentation dynamics: highly excited states of HBr probed by VMI and REMPI as a case study.

    PubMed

    Glodic, Pavle; Zaouris, Dimitris; Samartzis, Peter C; Hafliðason, Arnar; Kvaran, Ágúst

    2016-09-21

    Analysis of mass resolved spectra as well as velocity map images derived from resonance enhanced multiphoton ionization (REMPI) of HBr via resonance excitations to mixed Rydberg (6pπ (3)Σ(-)(v' = 0)) and valence (ion-pair) (V (1)Σ(+)(v' = m + 17)) states allows characterization of the effect of a triplet-to-singlet state interaction on further photoexcitation and photoionization processes. The analysis makes use of rotational spectra line shifts, line intensity alterations, kinetic energy release spectra as well as angular distributions. Energy-level-dependent state mixing of the resonance excited states is quantified and photoexcitation processes, leading to H(+) formation, are characterized in terms of the states and fragmentation processes involved, depending on the state mixing.

  7. On the population of triplet excited states of 6-aza-2-thiothymine.

    PubMed

    Gobbo, João Paulo; Borin, Antonio Carlos

    2013-07-11

    The mechanisms of population of the lowest excited triplet states of 6-aza-2-thiothymine were investigated by means of CASPT2//CASSCF quantum-chemical calculations, with extensive atomic natural orbital basis sets of double-ζ quality (ANO-L-VDZP). Several key structures corresponding to equilibrium geometries, surface crossings, minimum energy paths, and linear interpolation in internal coordinates were used to explain the ability to sensitize molecular oxygen. After population of the S2(1)(ππ*) state, the system evolves to the state minimum. At this point, and along the minimum energy path of the (1)(ππ*) state, two main mechanisms related to the triplet and singlet manifolds can be visualized, leading the system to the lowest triplet state, T1(3)(ππ*).

  8. Excited state kinetics in crystalline solids: self-quenching in nanocrystals of 4,4'-disubstituted benzophenone triplets occurs by a reductive quenching mechanism.

    PubMed

    Kuzmanich, Gregory; Simoncelli, Sabrina; Gard, Matthew N; Spänig, Fabian; Henderson, Bryana L; Guldi, Dirk M; Garcia-Garibay, Miguel A

    2011-11-02

    We report an efficient triplet state self-quenching mechanism in crystals of eight benzophenones, which included the parent structure (1), six 4,4'-disubstituted compounds with NH(2) (2), NMe(2) (3), OH (4), OMe (5), COOH (6), and COOMe (7), and benzophenone-3,3',4,4'-tetracarboxylic dianhydride (8). Self-quenching effects were determined by measuring their triplet-triplet lifetimes and spectra using femtosecond and nanosecond transient absorption measurements with nanocrystalline suspensions. When possible, triplet lifetimes were confirmed by measuring the phosphorescence lifetimes and with the help of diffusion-limited quenching with iodide ions. We were surprised to discover that the triplet lifetimes of substituted benzophenones in crystals vary over 9 orders of magnitude from ca. 62 ps to 1 ms. In contrast to nanocrystalline suspensions, the lifetimes in solution only vary over 3 orders of magnitude (1-1000 μs). Analysis of the rate constants of quenching show that the more electron-rich benzophenones are the most efficiently deactivated such that there is an excellent correlation, ρ = -2.85, between the triplet quenching rate constants and the Hammet σ(+) values for the 4,4' substituents. Several crystal structures indicate the existence of near-neighbor arrangements that deviate from the proposed ideal for "n-type" quenching, suggesting that charge transfer quenching is mediated by a relatively loose arrangement.

  9. Triplet state formation in photovoltaic blends of DPP-type copolymers and PC71 BM.

    PubMed

    Ochsmann, Julian R; Chandran, Deepak; Gehrig, Dominik W; Anwar, Husna; Madathil, Pramod Kandoth; Lee, Kwang-Sup; Laquai, Frédéric

    2015-06-01

    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:PC71 BM 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 poly-mer 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.

  10. Canonical Watson-Crick base pair interactions in π* type triplet states

    NASA Astrophysics Data System (ADS)

    Noguera, M.; Blancafort, L.; Sodupe, M.; Bertran, J.

    2006-03-01

    Ground state and triplet π → π* states of canonical Watson-Crick base pairs have been studied at the B3LYP level of theory. Excited states were found to be localized at either of the monomers forming the base pair (guanine, cytosine, adenine and thymine), geometry relaxation of the excited base pair being similar to that occurring in the isolated nucleobase. For thymine and cytosine, triplet π → π* excitation produces a significant elongation of the C5-C6 bond whereas for guanine and adenine there is a significant increase of the N3-C2 bond and pyramidalization of the NH2 group. Adenine-thymine energy pairing remains almost unaffected by triplet excitation. However, for guanine-cytosine, with excitation localized at the guanine moiety, base pairing energy decreases about 5 kcal/mol due to pyramidalization of the amino group of guanine.

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

    PubMed

    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.

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

    SciTech Connect

    Wu, Tony C.; Congreve, Daniel N.; Baldo, Marc A.

    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.

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

    NASA Astrophysics Data System (ADS)

    Dyakonov, Vladimir

    2013-03-01

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

  14. VizieR Online Data Catalog: CaII triplet in red giant spectra (Da Costa, 2016)

    NASA Astrophysics Data System (ADS)

    da Costa, G. S.

    2016-07-01

    The data for this study consist of observations of Galactic globular and open clusters, which are used to provide a calibration between CaII triplet line strength and abundance [Fe/H], and observations of a sample of red giants in the disc of the LMC originally studied at high dispersion by Pompeia et al. (2008, Cat. J/A+A/480/379), and for which an updated analysis is available in Van der Swaelmen et al. (2013, Cat. J/A+A/560/A44). All observations were carried out at the Anglo-Australian Telescope using the 2dF multi-object fibre positioner and the AAOmega dual beam spectrograph1. The red arm of the spectrograph was configured with the 1700D grating centred at ~8600Å to give coverage of the CaII triplet lines with a resolution R of approximately 10000. The corresponding blue spectra are not used in this work. (2 data files).

  15. Production and reactions of triplet CS: Matrix infrared and ultraviolet spectra of C{sub 2}S{sub 2}

    SciTech Connect

    Bohn, R.B.; Hannachi, Y.; Andrews, L.

    1992-07-29

    Matrix infrared and visible-ultraviolet absorption spectroscopy and ab initio electronic structure calculations have been used to characterize the reaction products from a Tesla coil Ar/CS{sub 2} discharge. The discharge is an excellent source of CS, which reacts with other molecules to form the major C{sub 3}S{sub 2} product and the transient C{sub 2}S{sub 2} species. The spectra of discharged mixed isotopic samples Ar/{sup 12}CS{sub 2}/{sub 13}CS{sub 2} and Ar/C{sup 32}S{sub 2} exhibit triplet patterns in the CS antisymmetric stretching region, which unambiguously identifies the new C{sub 2}S{sub 2} molecule with two equivalent CS subgroups. The magnitudes of the {sup 12,13}C and {sup 32,34}S isotopic shifts further characterize the diatomic CS subgroup nature of C{sub 2}S{sub 2}. Another product contains two equivalent CS subgroups interacting with inequivalent S atom(s). The formation of C{sub 2}S{sub 2}({sup 3}{Sigma}) from the simple CS{sub 2} discharge requires triplet CS. Evidence was also obtained for other transient cumulene species. 32 refs., 8 figs., 7 tabs.

  16. Tristability arising from singlet-triplet and quartet spin states for dimeric Co(II)salen.

    PubMed

    Min, Kil Sik; Arthur, Jordan; Shum, William W; Bharathy, Muktha; zur Loye, Hans-Conrad; Miller, Joel S

    2009-06-01

    The magnetic behavior of N,N'-ethylenebis(salicylideniminato)cobalt(II) (Co(II)Salen, 1) has been reinvestigated and reveals spin-crossover behavior above 295 K. It has a singlet ground state and a triplet excited state at 30 K (21 cm(-1); 60 cal/mol) above the ground state, and at a higher temperature spin crossover to the quartet, a second excited state occurs.

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

    SciTech Connect

    Huix-Rotllant, Miquel Ferré, Nicolas

    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.

  18. Platinum-acetylide polymer based solar cells: involvement of the triplet state for energy conversion.

    PubMed

    Guo, Fengqi; Kim, Young-Gi; Reynolds, John R; Schanze, Kirk S

    2006-05-07

    Relatively efficient photovoltaic devices were fabricated using blends of a phosphorescent platinum-acetylide polymer and a fullerene (PCBM); involvement of the triplet excited state of the platinum-acetylide polymer in photoinduced charge transfer is believed to contribute to the device efficiency.

  19. Mimicry of the radical pair and triplet states in photosynthetic reaction centers with a synthetic model

    SciTech Connect

    Wasielewski, M.R.; Greenfield, S.R.; Svec, W.A.

    1997-08-01

    Results are presented on a photosynthetic model system that closely mimics the spin dynamics of triplet state formation found in photosynthetic reaction centers. This research will make it possible to design new models to probe the mechanism of the primary events of photosynthesis.

  20. Formation of Triplet Positron-helium Bound State by Stripping of Positronium Atoms in Collision with Ground State Helium

    NASA Technical Reports Server (NTRS)

    Drachman, Richard J.

    2006-01-01

    Formation of triplet positron-helium bound state by stripping of positronium atoms in collision with ground state helium JOSEPH DI RlENZI, College of Notre Dame of Maryland, RICHARD J. DRACHMAN, NASA/Goddard Space Flight Center - The system consisting of a positron and a helium atom in the triplet state e(+)He(S-3)(sup e) was conjectured long ago to be stable [1]. Its stability has recently been established rigorously [2], and the values of the energies of dissociation into the ground states of Ps and He(+) have also been reported [3] and [4]. We have evaluated the cross-section for this system formed by radiative attachment of a positron in triplet He state and found it to be small [5]. The mechanism of production suggested here should result in a larger cross-section (of atomic size) which we are determining using the Born approximation with simplified initial and final wave functions.

  1. Triplet-singlet conversion in ultracold Cs{sub 2} and production of ground-state molecules

    SciTech Connect

    Bouloufa, Nadia; Aymar, Mireille; Dulieu, Olivier; Pichler, Marin

    2011-02-15

    We propose a process to convert ultracold metastable Cs{sub 2} molecules in their lowest triplet state into (singlet) ground-state molecules in their lowest vibrational levels. Molecules are first pumped into an excited triplet state, and the triplet-singlet conversion is facilitated by a two-step spontaneous decay through the coupled A {sup 1{Sigma}}{sub u}{sup +}-b {sup 3{Pi}}{sub u} states. Using spectroscopic data and accurate quantum chemistry calculations for Cs{sub 2} potential curves and transition dipole moments, we show that this process competes favorably with the single-photon decay back to the lowest triplet state. In addition, we demonstrate that this conversion process represents a loss channel for vibrational cooling of metastable triplet molecules, preventing an efficient optical pumping cycle down to low vibrational levels.

  2. The photoexcited triplet state as a probe of chromophore-protein interaction in myoglobin.

    PubMed Central

    Angiolillo, P J; Vanderkooi, J M

    1998-01-01

    The photoexcited metastable triplet state of Mg(2+)-mesoporphyrin IX (MgMPIX) or Mg(2+)-protoporphyrin IX (MgPPIX) located in the heme pocket of horse myoglobin (Mb) was investigated by optical and electron paramagnetic resonance (EPR) spectroscopy, and its properties were compared with the model complexes, MgMPIX, MgPPIX, and Mg2+ etioporphyrin I (MgETIOI), in noncoordinating and coordinating organic glasses. Zero-field splitting parameters, line shape, and Jahn-Teller distortion in the temperature range of 3.8-110 K are discussed in terms of porphyrin-protein interactions. The triplet line shapes for MgMPIXMb and MGPPIXMb show no temperature-dependent spectral line shape changes suggestive of Jahn-Teller dynamics, and it is concluded that the energy splitting is >> 150 cm-1, suggesting symmetry breaking from the anisotropy of intermal electric fields of the protein, and consistent with previous predictions (Geissinger et al. 1995. J. Phys. Chem. 99:16527-16529). Both MgMPIXMb and MgPPIXMb demonstrate electron spin polarization at low temperature, and from the polarization pattern it can be concluded that intersystem crossing occurs predominantly into in-plane spin sublevels of the triplet state. The splitting in the Q0.0 absorption band and the temperature dependence and splitting of the photoexcited triplet state of myoglobin in which the iron was replaced by Mg2+ are interpreted in terms of effects produced by electric field asymmetry in the heme pocket. PMID:9726951

  3. Electron spin resonance of the phosphorescent triplet states of p-phenylphenol and p-phenylphenolate ion in stretched polyvinyl alcohol films

    NASA Astrophysics Data System (ADS)

    Yagi, Mikio; Higuchi, Jiro

    1980-05-01

    Using a stretched polyvinyl alcohol film as a host, electron spin resonance (ESR) of the phosphorescent triplet states of p-phenylphenol and p-phenylphenolate ion has been studied by changing the pH of the medium as an example of the application of ESR to an acid-base equilibrium. In assigning ESR spectra of aromatic acid and conjugated base, the present method is demonstrated to be most convenient and useful.

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

    PubMed Central

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

    2016-01-01

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

  5. DERIVING METALLICITIES FROM THE INTEGRATED SPECTRA OF EXTRAGALACTIC GLOBULAR CLUSTERS USING THE NEAR-INFRARED CALCIUM TRIPLET

    SciTech Connect

    Foster, Caroline; Forbes, Duncan A.; Proctor, Robert N.; Spitler, Lee R.; Strader, Jay; Brodie, Jean P.

    2010-04-15

    The Ca II triplet (CaT) feature in the near-infrared has been employed as a metallicity indicator for individual stars as well as integrated light of Galactic globular clusters (GCs) and galaxies with varying degrees of success, and sometimes puzzling results. Using the DEIMOS multi-object spectrograph on Keck we obtain a sample of 144 integrated light spectra of GCs around the brightest group galaxy NGC 1407 to test whether the CaT index can be used as a metallicity indicator for extragalactic GCs. Different sets of single stellar population models make different predictions for the behavior of the CaT as a function of metallicity. In this work, the metallicities of the GCs around NGC 1407 are obtained from CaT index values using an empirical conversion. The measured CaT/metallicity distributions show unexpected features, the most remarkable being that the brightest red and blue GCs have similar CaT values despite their large difference in mean color. Suggested explanations for this behavior in the NGC 1407 GC system are (1) the CaT may be affected by a population of hot blue stars, (2) the CaT may saturate earlier than predicted by the models, and/or (3) color may not trace metallicity linearly. Until these possibilities are understood, the use of the CaT as a metallicity indicator for the integrated spectra of extragalactic GCs will remain problematic.

  6. Inter-and intraspecific variation in excited-state triplet energy transfer rates in reaction centers of photosynthetic bacteria.

    SciTech Connect

    Laible, P. D.; Morris, Z. S.; Thurnauer, M. C.; Schiffer, M.; Hanson, D. K.

    2003-08-01

    In protein-cofactor reaction center (RC) complexes of purple photosynthetic bacteria, the major role of the bound carotenoid (C) is to quench the triplet state formed on the primary electron donor (P) before its sensitization of the excited singlet state of molecular oxygen from its ground triplet state. This triplet energy is transferred from P to C via the bacteriochlorophyll monomer B{sub B}. Using time-resolved electron paramagnetic resonance (TREPR), we have examined the temperature dependence of the rates of this triplet energy transfer reaction in the RC of three wild-type species of purple nonsulfur bacteria. Species-specific differences in the rate of transfer were observed. Wild-type Rhodobacter capsulatus RCs were less efficient at the triplet transfer reaction than Rhodobacter sphaeroides RCs, but were more efficient than Rhodospirillum rubrum RCs. In addition, RCs from three mutant strains of R. capsulatus carrying substitutions of amino acids near P and B{sub B} were examined. Two of the mutant RCs showed decreased triplet transfer rates compared with wild-type RCs, whereas one of the mutant RCs demonstrated a slight increase in triplet transfer rate at low temperatures. The results show that site-specific changes within the RC of R. capsulatus can mimic interspecies differences in the rates of triplet energy transfer. This application of TREPR was instrumental in defining critical energetic and coupling factors that dictate the efficiency of this photoprotective process.

  7. Mimicry of the radical pair and triplet states in photosynthetic reaction centers with a synthetic model

    SciTech Connect

    Hasharoni, K.; Levanon, H.; Greenfield, S.R.; Gosztola, D.J.; Svec, W.A.; Wasiclewski, M.R. |

    1995-08-02

    Supramolecular systems synthesized to model the photosynthetic reaction center (RC) are designed to mimic several key properties of the RC protein. Thus far, most RC models fulfill only a subset of these criteria, with very few reports employing time-resolved electron paramagnetic resonance spectroscopy (TREPR). We now report TREPR results on a photosynthetic model system (1) in a nematic liquid crystal (LC) that does not contain the natural pigments, yet closely mimics the spin dynamics of triplet state formation found only in photosynthetic RCs. The design of supermolecule 1 follows criteria established for promoting high quantum yield charge separation in glassy media. The observation of this triplet state in 1 by TREPR demonstrates that most of the electronic states found in the primary photochemistry of photosynthetic RCs can be mimicked successfully in synthetic models interacting with LCs. 12 refs., 3 figs.

  8. Temperature and solvent effects on the luminescence spectrum of C{sub 70}: Assignment of the lowest singlet and triplet states

    SciTech Connect

    Argentine, S.M.; Kotz, K.T.; Francis, A.H.

    1995-11-29

    The temperature, solvent, and concentration dependence of the fluorescence and phosphorescence spectra of C{sub 70} in glassy solutions have been examined. Spectra have been recorded over the temperature range 4-200 K. In addition, the AC Stark field modulated phosphorescence and the phosphorescence of {sup 13}C{sub 70} have been recorded and analyzed. The lowest triplet state is identified as a {sup 3}E{sub 1}` state and the vibronic structure consists primarily of Herzberg-Teller active e{sub 2}` modes. The intensity of the electronic origin is comparable to the vibronically induced intensity and is extraordinarily solvent sensitive. The solvent sensitivity exhibited by the spectra is shown to have the same origins as that observed in benzene and pyrene, but is several times greater in magnitude. Analysis of the spectra suggests that two electronic excited states contribute to the observed phosphorescence spectrum. 27 refs., 6 figs., 1 tab.

  9. First-Principles Study of Muon Trapping in Singlet and Triplet States of Oxyhemoglobin

    NASA Astrophysics Data System (ADS)

    Pink, Roger; Badu, S. R.; Das, T. P.; Sahoo, N.; Chow, Lee; Scheicher, R. H.; Nagamine, K.

    2012-02-01

    There is great current interest in the possibility of magnetic character in oxyhemoglobin (OxyHb) due to the detection [1] of muon spin-lattice relaxation in OxyHb. First-Principles variational Hartree-Fock Many Body Perturbation Theory (VHFMBPT) technique investigations on the singlet and triplet states of pure OxyHb have shown^2 that the triplet state is considerably higher than the singlet state ruling out magnetic character. However the charge distribution obtained by the VHFMBPT procedure in both states show a number of sites that have negative charges where the trapping of muon is being investigated to examine if the energy gap in the ordering of singlet and triplet states can be reduced or reversed leading to magnetic effects. Other possible sources of magnetism in Oxyhemoglobin will also be discussed. 1. K. Nagamine et al. Proc. Japan. Acad. B-Physics 83, 120 (2007); 2. S.R. Badu et al. Reported at Third Joint HFI-NQI International Conference, CERN, Geneva, September 2010.

  10. Inelastic collisions of ultracold triplet Rb2 molecules in the rovibrational ground state

    NASA Astrophysics Data System (ADS)

    Drews, Björn; Deiß, Markus; Jachymski, Krzysztof; Idziaszek, Zbigniew; Hecker Denschlag, Johannes

    2017-03-01

    Exploring and controlling inelastic and reactive collisions on the quantum level is a main goal of the developing field of ultracold chemistry. For this, the preparation of precisely defined initial atomic and molecular states in tailored environments is necessary. Here we present experimental studies of inelastic collisions of metastable ultracold Rb2 molecules in an array of quasi-1D potential tubes. In particular, we investigate collisions of molecules in the absolute lowest triplet energy level where any inelastic process requires a change of the electronic state. Remarkably, we find similar decay rates as for collisions between rotationally or vibrationally excited triplet molecules where other decay paths are also available. The decay rates are close to the ones for universal reactions but vary considerably when confinement and collision energy are changed. This might be exploited to control the collisional properties of molecules.

  11. A time-resolved EPR study of short-lived triplet states: Host and temperature dependences of triplet properties of phthalazine

    NASA Astrophysics Data System (ADS)

    Terazima, Masahide; Yamauchi, Seigo; Hirota, Noboru

    1985-10-01

    The triplet properties of phthalazine are investigated by means of the time-resolved EPR technique with laser excitation in various hosts over a wide range of temperature. The host and temperature dependences are interpreted satisfactorily in terms of the vibronic mixing between the 3nπ* and 3ππ* states. From the host dependences of the EPR parameters the zfs of the pure 3nπ* state of phthalazine is deduced to be Xn =0.027 cm-1, Yn =-0.058 cm-1, and Zn =0.031 cm-1. The fraction of the 3nπ* character of the T1 state is estimated to be ˜0% in ethanol, benzoic acid (BAC), and 1, 4-dichlorobenzene (DCB), 14% in 1, 2, 4, 5-tetrachlorobenzene (TCB), 60% in biphenyl (BP), and 84% in durene. The temperature dependences of the zfs, linewidth, phosphorescence spectrum, and lifetime are investigated and the results are explained using a continuum model. From the simulation of the temperature dependence of the triplet lifetime in the DCB host the decay rate constant of the second excited triplet (3nπ*) state is estimated to be 2.5×104 s-1. A drastic increase of the decay rate at higher temperatures suggests the presence of a higher 3nπ* state with a decay rate constant of ˜106 s-1. Possible causes for the lack of phosphorescence and fast radiationless decay are also discussed.

  12. Triplet versus singlet entangled states in teaching the Einstein-Podolsky-Rosen paradox

    NASA Astrophysics Data System (ADS)

    Shegelski, Mark R. A.

    2013-05-01

    The Einstein-Podolsky-Rosen paradox is considered using spin-\\frac{1}{2} singlet and triplet states prepared in the z-direction, after which measurements are made in a different direction, the x-direction, for example. An unexpected outcome and its usefulness for teaching is reported. The material will be of interest to upper-year undergraduate quantum mechanics instructors and students.

  13. Triplet excited state characters and photosensitization mechanisms of alpha-terthienyl: a theoretical study.

    PubMed

    Ji, Hong-Fang; Shen, Liang

    2009-01-09

    The triplet excited (T(1)) state characters of alpha-terthienyl (alpha-T) have been investigated using density functional theory calculations, based on which, its photosensitization mechanisms were explored. Primarily, the direct oxidation to the DNA bases by the T(1) state alpha-T through the electron transfer is not thermodynamically feasible. Secondly, 1O2 can be photogenerated both in benzene and water through the direct energy transfer from the T(1) state alpha-T to 3O2, while O2(.-) can only be formed in water through the electron transfer from the T(1) state alpha-T or alpha-T(-) to 3O2.

  14. Time-resolved spectroscopic studies of sulphonated aluminium phthalocyanine triplet states

    NASA Astrophysics Data System (ADS)

    Simpson, Mary S. C.; Beeby, A.; Bishop, Steven M.; MacRobert, Alexander J.; Parker, Andrew W.; Phillips, David

    1992-04-01

    The photophysical and photochemical properties of sulphonated aluminum and zinc phthalocyanines have been investigated in a range of solvents and model biological systems. Anomalous effects are observed upon deuteration of the solvent and addition of fluoride ions. In D2O the excited singlet and triplet state lifetimes and quantum yields of fluorescence and triplet state formation are increased relative to H2O. No solvent isotope effect is observed between CH3OH and CH3OD. It is proposed that relaxation of the excited state involves a tunnelling type interaction in which the phthalocyanine's highly energetic metal-axial ligand stretching vibrations are coupled to the HO-H or DO-D stretching vibrations. A significant increase in triplet lifetimes of phthalocyanine sensitizers bound to protein substrates is observed which is a function of the degree of sulphonation. The implications of these results to the determination of the quantum yields of singlet oxygen formation in D2O and lipophilic environments are discussed.

  15. Radiative deactivation of the lowest triplet state of dibenzo- p-dioxine

    NASA Astrophysics Data System (ADS)

    Gastilovich, E. A.; Korol'Kova, N. V.; Klimenko, V. G.; Serov, S. A.

    2002-08-01

    A theoretical evaluation of the dipole moments of vibronic transitions (which are governed by vibronic spin-orbit interactions) was carried out for dibenzo- p-dioxin molecules. On the basis of the comparison of the obtained results with the data on the distribution of line intensities in a fine-structure phosphorescence spectrum of dibenzo- p-dioxin at 4.2 K, it is inferred that radiative deactivation of the lowest triplet state T 1 (ππ*) occurs from one of the triplet sublevels. For the molecules of dibenzo- p-dioxin and one of the isomers of tetrachlorodibenzo- p-dioxin, the effect of the form of vibrational modes and individual constants of the spin-orbit coupling in O and Cl atoms on vibronic spin-orbit interactions is discussed.

  16. Quenching of the triplet state of certain porphyrins by cyanocobalamin and co-phthalocyanine

    NASA Astrophysics Data System (ADS)

    Sapunov, V. V.

    1992-10-01

    The bimolecular exchange-resonance energy transfer efficiency from the triplet level of a number of Pd porphyrins to cyanocobalamin (vitamin B-12) is much lower in ethanol than in aqueous solutions. This is explained by a change in a cyanocobalamin-molecule geometry in ethanol from that in aqueous solutions. This change can be the detachment of the nucleotide from the cobalt ion or a change in the cyanocobalamin-molecule conformation. As a result, stearic hindrance of intermolecular energy transfer arises, or the mobility of the cyanocobalamin molecules decreases. No quenching of the triplet state of tetraphenyl tetrahydroporphin by cyanocobalamine is detected, whereas quenching of Co-phthalocyanine occurs with a high rate constant.

  17. Triplet state dissolved organic matter in aquatic photochemistry: reaction mechanisms, substrate scope, and photophysical properties.

    PubMed

    McNeill, Kristopher; Canonica, Silvio

    2016-11-09

    Excited triplet states of chromophoric dissolved organic matter ((3)CDOM*) play a major role among the reactive intermediates produced upon absorption of sunlight by surface waters. After more than two decades of research on the aquatic photochemistry of (3)CDOM*, the need for improving the knowledge about the photophysical and photochemical properties of these elusive reactive species remains considerable. This critical review examines the efforts to date to characterize (3)CDOM*. Information on (3)CDOM* relies mainly on the use of probe compounds because of the difficulties associated with directly observing (3)CDOM* using transient spectroscopic methods. Singlet molecular oxygen ((1)O2), which is a product of the reaction between (3)CDOM* and dissolved oxygen, is probably the simplest indicator that can be used to estimate steady-state concentrations of (3)CDOM*. There are two major modes of reaction of (3)CDOM* with substrates, namely triplet energy transfer or oxidation (via electron transfer, proton-coupled electron transfer or related mechanisms). Organic molecules, including several environmental contaminants, that are susceptible to degradation by these two different reaction modes are reviewed. It is proposed that through the use of appropriate sets of probe compounds and model photosensitizers an improved estimation of the distribution of triplet energies and one-electron reduction potentials of (3)CDOM* can be achieved.

  18. Phase control of the spin-triplet state in S/F/S Josephson junctions

    NASA Astrophysics Data System (ADS)

    Gingrich, Eric C.

    For decades, the proximity effect in superconductor/ferromagnetic (S/F) hybrid systems was thought to be very short-ranged, with coherence lengths on the order of a nanometer. That changed in 2003 when Bergeret et al. suggested systems involving s-wave superconductors and ferromagnets with non-collinear magnetizations could generate spin-triplet supercurrent. This was a significant prediction that radically changed the outlook for these systems, with the possibility of bringing the ferromagnetic coherence length up to ranges similar to the normal metal coherence length. With the experimental confirmation of the spin-triplet state in S/F/S Josephson junctions in 2010, the flood-gates opened into a range of interesting studies. We have performed measurements on the magnetic and superconducting properties of the multilayer Ni/[Co/Ni]n. This arrangement of ferromagnetic materials, when grown with thicknesses of 0.4 nm Ni and 0.2 nm Co, demonstrate a magnetization that lies perpendicular to the plane of the films. Because it will, in the virgin state, possess a non-collinear magnetization with ferromagnets which have magnetizations that lie within the plane, it is a convenient multilayer for the generation of spin-triplet supercurrent. Our measurements of S/F'/F/F'/S Josephson junctions, where F' is a hard ferromagnet and F is the Co/Ni multilayer, confirmed the presence of the spin-triplet state, and demonstrated the viability of the Co/Ni multilayer as a triplet generating ferromagnet. We have also performed studies on the characteristics of a number of soft ferromagnetic alloys. These alloys are important for their potential as a soft ferromagnetic switching layer for application in our triplet control devices. To that end, we have created sputtering targets for four different ferromagnetic alloys: Molybdenum-doped Permalloy, Niobium-doped Permalloy, Copper-doped Permalloy, and Palladium Iron. These studies have included: atomic concentration measurements using EDS

  19. Conformationally Constrained, Stable, Triplet Ground State (S = 1) Nitroxide Diradicals. Antiferromagnetic Chains of S = 1 Diradicals

    SciTech Connect

    Rajca, Andrzej; Takahashi, Masahiro; Pink, Maren; Spagnol, Gaelle; Rajca, Suchada

    2008-06-30

    Nitroxide diradicals, in which nitroxides are annelated to m-phenylene forming tricyclic benzobisoxazine-like structures, have been synthesized and characterized by X-ray crystallography, magnetic resonance (EPR and {sup 1}H NMR) spectroscopy, as well as magnetic studies in solution and in solid state. For the octamethyl derivative of benzobisoxazine nitroxide diradical, the conformationally constrained nitroxide moieties are coplanar with the m-phenylene, leading to large values of 2J (2J/k > 200 K in solution and 2J/k >> 300 K in the solid state). For the diradical, in which all ortho and para positions of the m-phenylene are sterically shielded, distortion of the nitroxide moieties from coplanarity is moderate, such that the singlet-triplet gaps remain large in both solution (2J/k > 200 K) and the solid state (2J/k {approx} 400-800 K), though an onset of thermal depopulation of the triplet ground state is detectable near room temperature. These diradicals have robust triplet ground states with strong ferromagnetic coupling and good stability at ambient conditions. Magnetic behavior of the nitroxide diradicals at low temperature is best fit to the model of one-dimensional S = 1 Heisenberg chains with intrachain antiferromagnetic coupling. The antiferromagnetic coupling between the S = 1 diradicals may be associated with the methyl nitroxide C-H {hor_ellipsis} O contacts, including nonclassical hydrogen bonds. These unprecedented organic S = 1 antiferromagnetic chains are highly isotropic, compared to those of the extensively studied Ni(II)-based chains.

  20. Intermolecular electron transfer from naphthalene derivatives in the higher triplet excited states.

    PubMed

    Sakamoto, Masanori; Cai, Xichen; Hara, Michihiro; Fujitsuka, Mamoru; Majima, Tetsuro

    2004-08-11

    Intermolecular electron transfer (ELT) from a series of naphthalene derivatives (NpD) in the higher triplet excited states (T(n)) to carbon tetrachloride (CCl(4)) in Ar-saturated acetonitrile was observed using the two-color two-laser flash photolysis method. The ELT efficiency depended on the driving force of ELT. Since the ELT from the T(n) state occurred competitively with the internal conversion (IC, T(n) --> T(1)) and the triplet energy transfer (ENT), the ELT became apparent only when sufficient free energy change of ELT was attained. On the other hand, ELT from the T(1) state was not observed, although ELT from the T(1) state with sufficiently long lifetime has a slightly exothermic driving force. The fast ELT from the T(n) state and lack of the reactivity of the T(1) state were explained well by the "sticky" dissociative electron-transfer model based on one-electron reductive attachment to CCl(4) leading to the C-Cl bond cleavage.

  1. Triplet states in isotopically mixed anthracene crystals: High resolution optical spectroscopy

    NASA Astrophysics Data System (ADS)

    Port, H.; Rund, D.; Wolf, H. C.

    1981-08-01

    The triplet O,O transitions of guest and host in isotopically mixed anthracene crystals of various compositions (A- h10, 13C-monosubstituted A- h10, A- d1h9, A- d2hg in A- d10 and A- d10 in A- h10) have been investigated using high resolution laser excitation spectroscopy. The guest aggregate spectra have been studied in polarized light as a function of guest concentration up to 15%. The analyses allow us to identify the monomer, dimer and trimer lines. From the dimer splittings the dominant resonance pair interactions are dedu The comparison of different mixed crystal systems with guest levels below and above the host exciton band reveals that quasiresonance and superexchange corrections are of minor importance. The experimental resonance pair interactions are used to calculate the triplet exciton band structure of anthracen and the observed guest polarization behaviour is interpreted quantitatively by the Rashba effect. Finally, the lower Davydov component of the host is s and broadened with increasing guest concentration. The shift is discussed using a theoretical model of Lifshitz.

  2. Rydberg and autoionizing triplet states in Helium up to the N = 5 threshold

    NASA Astrophysics Data System (ADS)

    Argenti, L.

    2008-11-01

    Energy levels of highly excited bound Rydberg states, the position and widths of autoionizing states, and oscillator strengths are calculated for He 3S, 3P e, 3P o, 3D e and 3D o symmetries up to the N = 5 He + excitation threshold. The calculations are performed with the K-matrix B-spline method with maximum orbital angular momentum ℓ max = 8. Reliable doubly excited-state parameters up to the n = 20 multiplet below each ionization threshold are presented. One thousand and six hundred newly identified bound and metastable states, seven times those available in literature, fill many gaps, reveal a dozen intruder states, and allow new speculations on propensity rules and radiative decays of triplet Rydberg states.

  3. An ab initio investigation of the ground and low-lying singlet and triplet electronic states of XNO{sub 2} and XONO (X = Cl, Br, and I)

    SciTech Connect

    Peterson, Kirk A.; Francisco, Joseph S.

    2014-01-28

    A systematic ab initio treatment of the nitryl halides (XNO{sub 2}) and the cis- and trans- conformers of the halide nitrites (XONO), where X = Cl, Br, and I, have been carried out using highly correlated methods with sequences of correlation consistent basis sets. Equilibrium geometries and harmonic frequencies have been accurately calculated in all cases at the explicitly correlated CCSD(T)-F12b level of theory, including the effects of core-valence correlation for the former. Where experimental values are available for the equilibrium structures (ClNO{sub 2} and BrNO{sub 2}), the present calculations are in excellent agreement; however, the X-O distances are slightly too long by about 0.01 Å due to missing multireference effects. Accurate predictions for the iodine species are made for the first time. The vertical electronic excitation spectra have been calculated using equation-of-motion coupled cluster methods for the low-lying singlet states and multireference configuration interaction for both singlet and triplet states. The latter also included the effects of spin-orbit coupling to provide oscillator strengths for the ground state singlet to excited triplet transitions. While for ClNO{sub 2} the transitions to excited singlet states all occur at wavelengths shorter than 310 nm, there is one longer wavelength singlet transition in BrNO{sub 2} and two in the case of INO{sub 2}. The long wavelength tail in the XNO{sub 2} species is predicted to be dominated by transitions to triplet states. In addition to red-shifting from X = Cl to I, the triplet transitions also increase in oscillator strength, becoming comparable to many of the singlet transitions in the case of INO{sub 2}. Hence in particular, the latter species should be very photolabile. Similar trends are observed and reported for the halogen nitrites, many of which for the first time.

  4. Prediction of a neutral noble gas compound in the triplet state.

    PubMed

    Manna, Debashree; Ghosh, Ayan; Ghanty, Tapan K

    2015-05-26

    Discovery of the HArF molecule associated with H-Ar covalent bonding [Nature, 2000, 406, 874-876] has revolutionized the field of noble gas chemistry. In general, this class of noble gas compound involving conventional chemical bonds exists as closed-shell species in a singlet electronic state. For the first time, in a bid to predict neutral noble gas chemical compounds in their triplet electronic state, we have carried out a systematic investigation of xenon inserted FN and FP species by using quantum chemical calculations with density functional theory and various post-Hartree-Fock-based correlated methods, including the multireference configuration interaction technique. The FXeP and FXeN species are predicted to be stable by all the computational methods employed in the present work, such as density functional theory (DFT), second-order Møller-Plesset perturbation theory (MP2), coupled-cluster theory (CCSD(T)), and multireference configuration interaction (MRCI). For the purpose of comparison we have also included the Kr-inserted compounds of FN and FP species. Geometrical parameters, dissociation energies, transition-state barrier heights, atomic charge distributions, vibrational frequency data, and atoms-in-molecules properties clearly indicate that it is possible to experimentally realize the most stable state of FXeP and FXeN molecules, which is triplet in nature, through the matrix isolation technique under cryogenic conditions.

  5. On the mechanisms of triplet excited state population in 8-azaadenine.

    PubMed

    Gobbo, João Paulo; Borin, Antonio Carlos

    2012-12-06

    The photophysics of 8-azaadenine (8-AA) has been studied with the CASPT2//CASSCF protocol and ANO-L double-ζ basis sets. Stationary equilibrium structures, surface crossings, minimum energy paths, and linear interpolations have been used to study possible mechanisms to populate the lowest triplet state, T(1)(3)(ππ*), capable of sensitizing molecular oxygen. Our results show that two main mechanisms can occur after photoexcitation to the S(2)(1)(ππ*) state. The first one is through the S(2)/S(1) conical intersection (((1)ππ*/(1)nπ*)(CI)), leading to the S(1) ((1)nπ*) state minimum, (S(1) ((1)nπ*))(min), where a singlet-triplet crossing, ((1)nπ*/(3)ππ*)(STC), is accessible. The second one starts with the ((1)ππ*/(3)nπ*)(STC) at the (S(2)((1)ππ*))(min), from which the system can evolve to the (T(2) ((3)nπ*))(min), with subsequent population of the T(1) excited electronic state, due to the ((3)nπ*/(3)ππ*)(CI) conical intersection.

  6. Tunnel magnetoresistance in quantum dots in the presence of singlet and triplet states.

    PubMed

    Michałek, G; Bułka, B R

    2011-05-04

    We study transport through a two-level quantum dot (QD) weakly coupled to ferromagnetic electrodes, the mutual magnetization orientation of which can be changed from a parallel to an antiparallel configuration. Calculations are performed in a sequential tunnelling regime taking into account an inter-level Coulomb and an exchange interaction on the QD with many-body electronic states. Our interests are mainly focused on the role of singlet and triplet states on the tunnel magnetoresistance (TMR). We have found that TMR characteristics strongly depend on different local spin configurations in the QD, which originate from an anti- or ferromagnetic exchange coupling J as well as its strength. A strong inter-channel Coulomb blockade (which influences the TMR) appears when the ground state is singly occupied. Activation of the singlet or the triplet states and competition between various tunnelling rates are responsible for the spin accumulation even in the parallel configuration. We have also found negative TMR and negative differential resistance (NDR) effects in the system with strong coupling asymmetry.

  7. Stability of a spin-triplet nematic state near to a quantum critical point

    NASA Astrophysics Data System (ADS)

    Hannappel, G.; Pedder, C. J.; Krüger, F.; Green, A. G.

    2016-06-01

    We analyze a model of itinerant electrons interacting through a quadrupole density-density repulsion in three dimensions. At the mean-field level, the interaction drives a continuous Pomeranchuk instability towards d -wave, spin-triplet nematic order, which simultaneously breaks the SU(2) spin-rotation and spatial-rotation symmetries. This order is characterized by spin-antisymmetric, elliptical deformations of the Fermi surfaces of up and down spins. We show that the effects of quantum fluctuations are similar to those in metallic ferromagnets, rendering the nematic transition first order at low temperatures. Using the fermionic quantum order-by-disorder approach to self-consistently calculate fluctuations around possible modulated states, we show that the first-order transition is preempted by the formation of a helical spin-triplet d -density wave. Such a state is closely related to d -wave bond density wave order in square-lattice systems. Moreover, we show that it may coexist with a modulated, p -wave superconducting state.

  8. Deuterium isotope effects on the zero-field splittings of the lowest triplet state of benzaldehyde derivatives

    NASA Astrophysics Data System (ADS)

    Neugebauer, S. M.; Tinti, D. S.

    1993-08-01

    The zero-field splitting parameters, D and E, in the lowest triplet state of p-chlorobenzaldehyde, p-methylbenzaldehyde, and their d1 isotopes (aldehyde proton), are determined by ODMR measurements. The results show that the sign of the isotopic change in D reflects the orbital character of the lowest triplet state. The magnitude of D increases in the d1 isotope of both guests in p-dimethoxybenzene where the lowest guest triplet state is 3nπ*, but it decreases in p-xylene where the stae is 3ππ*. The results are interpreted in terms of the spin—orbit interactions between the nearby 3nπ* and 3ππ* states and the isotopic changes in the zero-point energies of the states.

  9. Secondary organic aerosol production from aqueous reactions of atmospheric phenols with an organic triplet excited state.

    PubMed

    Smith, Jeremy D; Sio, Vicky; Yu, Lu; Zhang, Qi; Anastasio, Cort

    2014-01-21

    Condensed-phase chemistry plays a significant role in the formation and evolution of atmospheric organic aerosols. Past studies of the aqueous photoformation of secondary organic aerosol (SOA) have largely focused on hydroxyl radical oxidation, but here we show that triplet excited states of organic compounds ((3)C*) can also be important aqueous oxidants. We studied the aqueous photoreactions of three phenols (phenol, guaiacol, and syringol) with the aromatic carbonyl 3,4-dimethoxybenzaldehyde (DMB); all of these species are emitted by biomass burning. Under simulated sunlight, DMB forms a triplet excited state that rapidly oxidizes phenols to form low-volatility SOA. Rate constants for these reactions are fast and increase with decreasing pH and increasing methoxy substitution of the phenols. Mass yields of aqueous SOA are near 100% for all three phenols. For typical ambient conditions in areas with biomass combustion, the aqueous oxidation of phenols by (3)C* is faster than by hydroxyl radical, although rates depend strongly on pH, oxidant concentrations, and the identity of the phenol. Our results suggest that (3)C* can be the dominant aqueous oxidant of phenols in areas impacted by biomass combustion and that this is a significant pathway for forming SOA.

  10. Photogenerated triplet states in supramolecular porphyrin ladder assemblies: an EPR study.

    PubMed

    Richert, Sabine; Peeks, Martin D; Tait, Claudia E; Anderson, Harry L; Timmel, Christiane R

    2016-09-21

    Introducing bridging ligands such as DABCO to solutions of linear zinc porphyrin oligomers has previously been shown to lead to the formation of ladder-type assemblies in which the single porphyrin units in each strand adopt a predominantly co-planar conformation. Here, we employ transient Electron Paramagnetic Resonance (EPR) to study photogenerated triplet states of these complexes in frozen solution with a particular focus on the extent of spin delocalisation. We make use of two different techniques: (i) the zero-field splitting parameters D and E are determined using transient continuous wave (cw) EPR spectroscopy and (ii) the hyperfine coupling constants, which directly reveal the extent of spin delocalisation, are quantified by orientation-selective proton Electron Nuclear DOuble Resonance (ENDOR) spectroscopy. It is found that ladder formation does not encourage triplet state delocalisation either across the bridging ligand DABCO or along the individual porphyrin strands despite their co-planar conformation, which was previously shown to allow increased electronic delocalisation.

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

    SciTech Connect

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

    2008-02-28

    Ab initio transition dipole moments between states of the triplet manifold of NH radical are determined at the complete active space self-consistent field, followed by the internally contracted multireference singles plus doubles configuration interaction level of theory with a modified aug-cc-pVTZ basis set that accounts for valence-Rydberg interactions. This enables the computation of various radiative characteristics such as Einstein coefficients, radiative lifetimes, and oscillator strengths. These properties concern as well valence and Rydberg states. For the valence states, only the (0, 0) band of the A {sup 3}{pi}-X {sup 3}{sigma}{sup -} transition has received some important amount of attention. Data for the other transitions are rather scarce and sometimes inexistent. The results obtained in this work show good agreement with the available experimental data in comparison to other theoretical numbers reported in the literature.

  12. Direct optical access to the triplet manifold of states in H2

    NASA Astrophysics Data System (ADS)

    Jungen, Ch.; Glass-Maujean, M.

    2016-03-01

    A number of unassigned lines in the absorption spectrum of diatomic hydrogen are attributed to nominally forbidden transitions from the ground state to the n f manifold of states (Rydberg electron with ℓ =3 orbital momentum). They appear via weak ℓ - mixing interactions leading to local level perturbations. Our analysis is based on multichannel quantum defect theory and uses known theoretical information from the literature. The upper levels of most of these transitions are known to give rise to molecular fluorescence, and they are shown to be singlet-triplet mixed. We conclude that the well-known metastable c 3Πu- state can be populated via one-photon absorption of uv photons followed by cascade emission 4 f →3 d →2 p .

  13. Effect of Triplet T 1-State Population on Fluorescence Polarization Kinetics of Organic Fluorophores

    NASA Astrophysics Data System (ADS)

    Stanishevsky, I. V.; Chernyavskii, V. A.

    2015-11-01

    The fluorescence polarization kinetics of fluorescent organic molecules and molecules with two interconverting photoisomeric forms and fixed molecular skeletons were investigated by numerical methods based on the solution of population balance equations. The depolarizing effect of the lowest triplet T 1 state and the polarization time dependence for quasi-continuous-wave (cw) and pulsed photoexcitation were studied using model compounds. The fluorescence depolarization with cw excitation was characterized by times that were shorter than the T 1-state lifetime; for the isomers, also by times that correlated with the photoisomerization times. Intense pulsed photoexcitation distorted significantly the initial oscillator orientation distribution in the singlet S 0 and S 1 states and could lead to sign reversal of the polarization.

  14. Reversible Photoisomerization among Triplet Amino Naphthylnitrene, Triplet Diimine Biradical, and Indazole: Matrix-Isolation IR Spectra of 8-Amino-1-naphthylnitrene, 1,8-Naphthalenediimine, and 1,2-Dihydrobenz[cd]indazole.

    PubMed

    Okamura, Takuya; Akai, Nobuyuki; Nakata, Munetaka

    2017-03-02

    Reaction mechanisms of nitrene, one of the most famous biradicals, have been frequently studied, and many spectral data have been obtained so far. In the present study, the experimental IR spectra of triplet 8-amino-1-naphthylnitrene ((3)ANN), a triplet diimine biradical 1,8-dihydro-1,8-naphthalenediimine ((3)DND), and 1,2-dihydrobenz[cd]indazole (DBI), which are produced in the UV photolysis of 1,8-diaminonaphthalene in an Ar matrix and identified by a combination method of IR spectroscopy and DFT quantum chemical calculations, are first reported. (3)ANN is found to change to DBI by hydrogen-atom migration with bond making between the two nitrogen atoms upon visible-light irradiation (λ > 580 nm) with its backward reaction caused by 350 nm irradiation. In addition, (3)ANN isomerizes to (3)DND by 700 nm irradiation, while its backward reaction occurs upon 500 nm irradiation. The wavelength dependences of these photoisomerizations are explained in terms of their electronic transition energies estimated by time-dependent DFT calculations. It is concluded that the novel reversible photoisomerization system among (3)ANN, (3)DND, and DBI is totally different from the well-known photoisomerization between phenylnitrene and a seven-membered cyclic compound.

  15. Laser-induced reduction of a dye characterised by a high triplet-state yield and dissolved in a polymer

    SciTech Connect

    Sizykh, A G; Tarakanova, E A; Tatarinova, L L

    2000-01-31

    An investigation was made of the photoreduction kinetics of a dye in a solid polymer solution under the influence of laser radiation corresponding to the band of the first singlet - singlet transition. Participation of higher triplet states was considered in a model of the photoreduction of a dye characterised by a high intersystem crossing yield. An analytic solution was obtained for a system of kinetic equations. This solution takes into account the difference between the photoprocess rates. It is shown that a linear dependence of the effective dye-photoreduction rate on the laser radiation intensity can serve as a test of the participation of higher triplet states in the reaction. A comparison of the theoretical and experimental results obtained in the present study is used to determine the ratio of the photoreduction and deactivation rate constants of the higher triplet state of eosin K. (interaction of laser radiation with matter. laser plasma)

  16. Self-homodyne measurement of a dynamic Mollow triplet in the solid state

    NASA Astrophysics Data System (ADS)

    Fischer, Kevin A.; Müller, Kai; Rundquist, Armand; Sarmiento, Tomas; Piggott, Alexander Y.; Kelaita, Yousif; Dory, Constantin; Lagoudakis, Konstantinos G.; Vučković, Jelena

    2016-03-01

    The study of the light-matter interaction at the quantum scale has been enabled by the cavity quantum electrodynamics (CQED) architecture, in which a quantum two-level system strongly couples to a single cavity mode. Originally implemented with atoms in optical cavities, CQED effects are now also observed with artificial atoms in solid-state environments. Such realizations of these systems exhibit fast dynamics, making them attractive candidates for devices including modulators and sources in high-throughput communications. However, these systems possess large photon out-coupling rates that obscure any quantum behaviour at large excitation powers. Here, we have used a self-homodyning interferometric technique that fully employs the complex mode structure of our nanofabricated cavity to observe a quantum phenomenon known as the dynamic Mollow triplet. We expect this interference to facilitate the development of arbitrary on-chip quantum state generators, thereby strongly influencing quantum lithography, metrology and imaging.

  17. Infrared vibrational spectroscopy of [Ru(bpy)2(bpm)]2+ and [Ru(bpy)3]2+ in the excited triplet state.

    PubMed

    Mukuta, Tatsuhiko; Fukazawa, Naoto; Murata, Kei; Inagaki, Akiko; Akita, Munetaka; Tanaka, Sei'ichi; Koshihara, Shin-ya; Onda, Ken

    2014-03-03

    This work involved a detailed investigation into the infrared vibrational spectra of ruthenium polypyridyl complexes, specifically heteroleptic [Ru(bpy)2(bpm)](2+) (bpy = 2,2'-bipyridine and bpm = 2,2'-bipyrimidine) and homoleptic [Ru(bpy)3](2+), in the excited triplet state. Transient spectra were acquired 500 ps after photoexcitation, corresponding to the vibrational ground state of the excited triplet state, using time-resolved infrared spectroscopy. We assigned the observed bands to specific ligands in [Ru(bpy)2(bpm)](2+) based on the results of deuterium substitution and identified the corresponding normal vibrational modes using quantum-chemical calculations. Through this process, the more complex vibrational bands of [Ru(bpy)3](2+) were assigned to normal vibrational modes. The results are in good agreement with the model in which excited electrons are localized on a single ligand. We also found that the vibrational bands of both complexes associated with the ligands on which electrons are little localized appear at approximately 1317 and 1608 cm(-1). These assignments should allow the study of the reaction dynamics of various photofunctional systems including ruthenium polypyridyl complexes.

  18. R-matrix calculations of triplet gerade states of molecular hydrogen and their use for high-resolution spectroscopy

    NASA Astrophysics Data System (ADS)

    Oueslati, H.; Argoubi, F.; Bezzaouia, S.; Telmini, M.; Jungen, Ch.

    2014-03-01

    A variational R-matrix approach combined with multichannel quantum defect theory is used for a computational study of triplet gerade states of H2. Electron-ion reaction (quantum defect) matrices are calculated as functions of internuclear distance and energy for the bound and continuum ranges including singly and doubly excited configurations built on the 1σg (X+2Σg+) and 1σu (A+2Σu+) core states of the H2+ ion. It is shown how these matrices can be reduced to effective quantum defect functions adapted to the analysis of high-resolution spectra in the bound range. These R-matrix effective quantum defects are finally adjusted to the available experimental data [Sprecher et al., J. Phys. Chem. A 117, 9462 (2013), 10.1021/jp311793t], producing agreement with experiment to within 0.5 cm-1, nearly as good as obtained by Sprecher et al. In addition, the R-matrix calculations predict the evolution of the quantum defects for higher energies, in a range extending far into the electronic continuum.

  19. Are there stable excited triplet states of NCS-/CNS- and NCO-/CNO-?

    NASA Astrophysics Data System (ADS)

    Khiri, D.; Gritli, H.; Peterson, K. A.; Chambaud, G.

    2015-07-01

    Highly correlated ab initio wave functions within the UCCSD(T)-F12 approach have been used to map portions of the potential energy surfaces and to study the stability of the first excited triplet states of the NCS-/CNS- and NCO-/CNO- anions. These a3Π states for linear geometries, or their 3A‧ and 3A″ bent components, correlate with the lowest dissociation asymptote of NCX- (X = S and O) along the NC-X coordinates. The X1Σ+ linear ground states of these anions are known to be stable with respect to dissociation to the X2Π ground state of the corresponding neutral molecule with a rather large electron affinity. The a3Π state of the NCS- anion is positioned below the X state of the neutral at long NC-S distances and its minimum of energy is found for bent geometries. The stability of its two components in bent geometries has been investigated, and it is found that some anionic forms are stable with respect to the X state of the neutral. The linear CNS- and CNO- isomers present a minimum only at long CN-X distances, located below the minimum of their corresponding neutral CNX ground states.

  20. The Paternò-Büchi reaction: importance of triplet states in the excited-state reaction pathway.

    PubMed

    Brogaard, Rasmus Y; Schalk, Oliver; Boguslavskiy, Andrey E; Enright, Gary D; Hopf, Henning; Raev, Vitaly; Tarcoveanu, Eliza; Sølling, Theis I; Stolow, Albert

    2012-06-28

    The Paternò-Büchi (PB) reaction between an excited carbonyl compound and an alkene has been widely studied, but so far little is known about the excited-state dynamics of the reaction. In this investigation, we used a compound in which a formyl and a vinyl group are attached to a [2.2]paracyclophane in order to obtain a model system in pre-reactive conformation for the PB reaction. We studied the excited-state dynamics of the isolated molecule in a molecular beam using femtosecond time-resolved photoelectron spectroscopy and ab initio calculations. The results show that inter-system crossing within two picoseconds competes efficiently with the reaction in the singlet manifold. Thus, the PB reaction in this model system takes place in the triplet state on a time scale of nanoseconds. This result stresses the importance of triplet states in the excited-state pathway of the PB reaction involving aromatic carbonyl compounds, even in situations in which the reacting moieties are in immediate vicinity.

  1. Photochemical production of organic matter triplet states in water samples from mountain lakes, located below or above the tree line.

    PubMed

    De Laurentiis, Elisa; Minella, Marco; Maurino, Valter; Minero, Claudio; Brigante, Marcello; Mailhot, Gilles; Vione, Davide

    2012-08-01

    The production of triplet states (T(*)) of chromophoric dissolved organic matter (CDOM), reacting with the probe molecule 2,4,6-trimethylphenol (TMP) was measured upon irradiation of water samples, taken from lakes located in a mountain area (NW Italy) between 1450 and 2750 m above sea level. The lakes are located below or above the tree line and surrounded by different vegetation types (trees, alpine meadows or exposed rocks). The most photoactive samples belonged to lakes below the tree line and their fluorescence spectra and CDOM optical features suggested the presence of a relatively elevated amount of humic (allochthonous) material. The lowest (negligible) photoactivity was found for a lake surrounded by exposed rocks. Its CDOM showed an important autochthonous contribution (due to in-lake productivity) and considerably higher spectral slope compared to the other samples, suggesting low CDOM molecular weight and/or aromaticity. Among the samples, CDOM photoactivity (measured as the rate of TMP-reactive T(*) photoproduction) decreased with changing vegetation type in the order: trees, meadows, rocks. It could be connected with decreasing contribution from catchment runoff and increasing contribution from autochthonous processes and possibly precipitation.

  2. Symmetry analysis of the vibronic States in the upper conical potential (2(3)A') of triplet.

    PubMed

    Viegas, Luis P; Alijah, Alexander; Varandas, António J C

    2005-04-21

    The symmetry properties of the rovibronic resonance states (Slonczewski resonances) supported by an upright conical potential are investigated. These symmetry properties lead to a useful correlation between states calculated with and without consideration of the geometrical phase, which can assist in the assignment of those states. The vibronic resonance states of triplet H3(+) (2(3)A'), which had been studied by us before, have now been assigned to spectroscopic quantum numbers.

  3. Electron-impact-induced allowed transitions between triplet states of H{sub 2}

    SciTech Connect

    Laricchiuta, A.; Celiberto, R.; Janev, R.K.

    2004-02-01

    Electron-impact-induced excitation and dissociation processes between the excited triplet states a {sup 3}{sigma}{sub g}{sup +}{yields}d {sup 3}{pi}{sub u}, c {sup 3}{pi}{sub u}{yields}h {sup 3}{sigma}{sub g}{sup +}, and c {sup 3}{pi}{sub u}{yields}g {sup 3}{sigma}{sub g}{sup +} of molecular hydrogen are studied by using the impact-parameter method. The cross sections for {nu}{sub i}-{nu}{sub f} resolved vibronic transitions between states have been calculated in the energy range from threshold to 100 eV; their maxima being located in the region of 5-10 eV. A special treatment was required for the transition to the h {sup 3}{sigma}{sub g}{sup +} state, whose adiabatic potential-energy curve possesses a barrier at the internuclear distance of about 5a{sub 0}, sustaining three quasi-bound vibrational states with widths of 5.3x10{sup -12}, 1.5x10{sup -3}, and 42.0 cm{sup -1}, respectively. The quasistationary character of these vibrational states is taken into account when calculating the c {sup 3}{pi}{sub u}{yields}h {sup 3}{sigma}{sub g}{sup +} excitation and dissociation cross sections.

  4. Solvent-induced configuration mixing and triplet excited-state inversion: insights from transient absorption and transient dc photoconductivity measurements.

    PubMed

    She, Chunxing; Rachford, Aaron A; Wang, Xianghuai; Goeb, Sébastien; El-Ballouli, Ala'a O; Castellano, Felix N; Hupp, Joseph T

    2009-10-14

    Solvent-induced excited-state configuration mixing in a Pt(II) diimine chromophore with phenylene ethynylene containing acetylide ligands, [Pt((t)Bu2bpy)(PE3)2] (1), was characterized by nanosecond transient absorption spectroscopy and transient dc photoconductivity (TDCP). The mixing is a result of closely spaced triplet charge transfer (3CT) and intraligand-localized (3IL) triplet energy levels that are finely tuned with solvent polarity as ascertained by their parent model chromophores [Pt((t)Bu2bpy)(PE1)2] (2) and [Pt(P2)(PE3)2] (3), respectively. The absorption difference spectrum of the mixed triplet state is dramatically different from those of the 3CT and 3IL state model chromophores. The 3CT, 3IL and configuration-mixed triplet states led to distinct TDCP signals. The TDCP response is of negative polarity for 3CT excited states but of positive polarity for 3IL excited states. TDCP transients for 1 in mixed solvents are a combination of signals from the 3IL and 3CT states, with the signal magnitude depending on the polarity of solvent composition. The fraction of 3CT state character in the configurationally mixed excited state was quantified by TDCP to be approximately 0.24 in pure benzene, while it decreased to approximately 0.05 in 20 : 80 (v : v) benzene-CH2Cl2. The charge transfer fraction appears to increase slightly to approximately 0.11 in the lower polarity 20 : 80 n-hexane-CH2Cl2 medium. TDCP is shown to be a useful tool for the identification of the lowest excited state in electrically neutral metal-organic chromophores.

  5. A triplet of differently shaped spin-zero states in the atomic nucleus 186Pb

    PubMed

    Andreyev; Huyse; Van Duppen P; Weissman; Ackermann; Gerl; Hessberger; Hofmann; Kleinbohl; Munzenberg; Reshitko; Schlegel; Schaffner; Cagarda; Matos; Saro; Keenan; Moore; O'Leary; Page; Taylor; Kettunen; Leino; Lavrentiev; Wyss; Heyde

    2000-05-25

    Understanding the fundamental excitations of many-fermion systems is of significant current interest. In atomic nuclei with even numbers of neutrons and protons, the low-lying excitation spectrum is generally formed by nucleon pair breaking and nuclear vibrations or rotations. However, for certain numbers of protons and neutrons, a subtle rearrangement of only a few nucleons among the orbitals at the Fermi surface can result in a different elementary mode: a macroscopic shape change. The first experimental evidence for this phenomenon came from the observation of shape coexistence in 16O (ref. 4). Other unexpected examples came with the discovery of fission isomers and super-deformed nuclei. Here we find experimentally that the lowest three states in the energy spectrum of the neutron deficient nucleus 186Pb are spherical, oblate and prolate. The states are populated by the alpha-decay of a parent nucleus; to identify them, we combine knowledge of the particular features of this decay with sensitive measurement techniques (a highly efficient velocity filters with strong background reduction, and an extremely selective recoil-alpha-electron coincidence tagging methods). The existence of this apparently unique shape triplet is permitted only by the specific conditions that are met around this particular nucleus.

  6. Spin-Triplet Pairing State of Sr2RuO4 in the c-Axis Magnetic Field

    NASA Astrophysics Data System (ADS)

    Takamatsu, Shuhei; Yanase, Youichi

    2013-06-01

    We investigate the spin-triplet superconducting state of Sr2RuO4 in the magnetic field along the c-axis on the basis of the four-component Ginzburg--Landau (GL) model with a weak spin--orbit coupling. We consider superconducting states described by the d-vector parallel to the ab-plane (\\mbi{d}\\parallel ab), and find that three spin-triplet pairing states are stabilized in the magnetic field--temperature (H--T) phase diagram. Although a helical state is stable at low magnetic fields, a chiral II state is stabilized at high magnetic fields. A non-unitary spin-triplet pairing state appears near the transition temperature owing to the coupling of magnetic field and chirality. We elucidate synergistic and/or competing roles of the magnetic field, chirality, and spin--orbit coupling. It is shown that a fractional vortex lattice is stabilized in the chiral II phase owing to the spin--orbit coupling.

  7. Initial singlet and triplet spin state contributions to -> ppπ0

    NASA Astrophysics Data System (ADS)

    Thörngren Engblom, P.; Meyer, H. O.; Balewski, J. T.; Daehnick, W. W.; Doskow, J.; Haeberli, W.; Lorentz, B.; Pancella, P. V.; Pollock, R. E.; von Przewoski, B.; Rathmann, F.; Rinckel, T.; Saha, Swapan K.; Schwartz, B.; Wellinghausen, A.; Wise, T.

    2000-01-01

    The PINTEX2http://www.iucf.indiana.edu/~pintex/2 facility at the IUCF Cooler ring, dedicated to the study of spin dependence in nucleon-nucleon interactions, has been used to measure polarization observables of the reaction -> ppπ0 at beam energies between 325 and 400 MeV. The stored, polarized proton beam had spin projections both in the longitudinal and the transverse directions with respect to the beam momentum. We report here on the measurements of the relative transverse and longitudinal spin-dependent cross sections3Defined as ΔσT(L) = [σ(⇕) + σ(⇕)] - [σ(⇈ + σ(⇊)] where the arrows denote parallel and antiparallel beam/target spin combinations, either transversely (T) or longitudinally (L) polarized.3, ΔσT/σtot and ΔσL/σtot, and how from these observables the initial spin singlet and triplet cross sections are obtained. Considering angular momentum states less than or equal to one, the contribution of the Ps partial waves to the cross section can be extracted.

  8. Spectroscopic insights on imidazole substituted phthalocyanine photosensitizers: Fluorescence properties, triplet state and singlet oxygen generation

    NASA Astrophysics Data System (ADS)

    Zhang, Xian-Fu; Lin, Yong; Guo, Wenfeng; Zhu, Jingzhong

    2014-12-01

    Imidazole substituted metal phthalocyanine (Pc) complexes were synthesized. UV-vis absorption, steady state and time-resolved fluorescence, as well as laser flash photolysis were used to measure the photophysical and photosensitizing properties. All the imidazole-phthalocyanine conjugates show high ΦT (quantum yield of excited triplet formation), high ΦΔ (singlet oxygen formation yield, >0.50) and good fluorescence properties (quantum yield Φf > 0.20 and lifetime τf > 3.0 ns). Compared to the unsubstituted Pc, both α- and β-imidazole substitutions result in the remarkable decrease in Φf and τf, but the α-substitution is stronger. The imidazole substitution, on the other hand, causes the increase of ΦT, τT, and ΦΔ values. Magnesium phthalocyanine (MgPc) is more susceptible to the substitution than zinc phthalocyanine (ZnPc). The mechanism responsible for the result is suggested based on the involvement of intramolecular photoinduced electron transfer. The high ΦΔ and appropriate fluorescence properties make the Pcs good candidate for PDT photosensitizers.

  9. Influence of substitution on the T-T absorption spectra in furocoumarins

    NASA Astrophysics Data System (ADS)

    Bryantseva, N. G.

    2006-11-01

    The present paper deals with compounds called photosensitizers, namely, psoralen, 3,4-phenyl-4',5'- cyclohexylpsoralen, 4'-methyl-3,4-cycloheptyl psoralen, 4',5'-dimethyl-3,4-cyclohexyl psoralen (fig. 1). The absorption spectra from excited triplets states were investigated. The computed triplet-triplet absorption spectra of research compounds have been determined using INDO method. The experimental triplet-triplet absorption spectra have been obtained using the technique of laser flash photolysis in ethanol. The compare of computed and experimental data is shows that the computed second band wavelenght throughout agree very well (0,5-6 nm) with experimental data.

  10. The Role of Environment in the Nonradiative Relaxation of the Triplet State of Naphthalene Derivatives in Solid Solutions at 77 K

    NASA Astrophysics Data System (ADS)

    Goryaeva, E. M.; Shablya, A. V.; Ermolaev, V. L.

    2001-04-01

    The nonradiative relaxation of the triplet states of oxy-and amino-derivatives of naphthalene and conjugated ions is studied by luminescent and kinetic methods (measurements of the phosphorescence decay and of phosphorescence excitation and phosphorescence spectra) in solid solutions of ethanol- h 6, ethanol- d 6, and mixtures of toluene- h 8 with piperidine- h 11 at 77 K. It is found that, along with intramolecular factors, a microsolvate surrounding a molecule or an ion substantially affects the nonradiative relaxation. The contribution of this factor in ethanol increases in the series cation-polar molecule-anion and in mixtures of toluene with piperidine—with increasing piperidine concentration. The results are interpreted assuming the inductive-resonance dipole-dipole transfer of the triplet energy to the dipole acceptors of intramolecular bonds and bonds with molecules of the environment. The relative arrangement of hydrogen atoms of OH groups of ethanol molecules in microsolvates of cations and anions estimated using the inductive-resonance model agrees with the difference in the structure of solvates of oppositely charged ions, which is caused by the electrostatic charge-dipole interaction and the distribution of the electron density in the ground state of the corresponding emitting center. The inductive-resonance model was used for studying the features of solvation processes involving polar molecules. It is shown that the difference between the structures of microsolvates of 2-oxy-naphthalene molecules in solvents with close dipole moments (ethanol and piperidine) is mainly caused by the different ability of these solvent molecules to form associates. The structure of microsolvates of oxy-derivatives of naphthalene in the associated amphoteric solvent is found to depend on the number and position of substituents. In oxy-derivatives of naphthalene with spatially separated OH groups in ethano- d 6, deuteroexchange occurs in both substituents, whereas in

  11. Contributions of a Higher Triplet Excited State to the Emission Properties of a Thermally Activated Delayed-Fluorescence Emitter

    NASA Astrophysics Data System (ADS)

    Kobayashi, Takashi; Niwa, Akitsugu; Takaki, Kensho; Haseyama, Shota; Nagase, Takashi; Goushi, Kenichi; Adachi, Chihaya; Naito, Hiroyoshi

    2017-03-01

    The temperature dependences of photoluminescence (PL) decay rates and the PL spectrum of a thermally activated delayed-fluorescence emitter, 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN), are investigated. It is found that not only the lowest singlet (S1 ) and triplet (T1) excited states but also an additional triplet excited state (Tn) lying between S1 and T1 play an important role in the exciton decay process, particularly around 100 K. At around this temperature, some of the triplet excitons are thermally activated into Tn but not up to S1, and they then decay into the ground state (S0) with phosphorescence emission. Therefore, two kinds of phosphorescence, originating from Tn and T1, are observed. The temperature dependence of the PL decay rates of 4CzIPN can be explained by a four-level model consisting of S1, T1, Tn, and S0, and its energy gaps between Tn and T1 and between S1 and T1 are determined to be 45 ±5 meV and 135 ±10 meV , respectively.

  12. Triplet states of oxygen vacancy defects in α-quartz: Center \\bf{\\text{E}^{\\prime\\prime}_{9}}

    NASA Astrophysics Data System (ADS)

    Mashkovtsev, R. I.; Pan, Y.

    2014-08-01

    The paramagnetic E^{\\prime\\prime}_{9} center in triplet state occurring in electron-irradiated, synthetic α-quartz has been investigated by using electron paramagnetic resonance (EPR) spectroscopy. The primary spin Hamiltonian parameter matrices g, D and A (hyperfine interactions for five 29Si nuclei) have now been determined. The principal values and principal directions of D and A matrices allow us to suggest the structural model for this stable triplet defect. The E^{\\prime\\prime}_{9} center involves the two unpaired electrons located in the orbitals of two silicon atoms next to one oxygen vacancy each. Firm correlations between the spin Hamiltonian matrix principal axes and crystallographic directions have been attained.

  13. Zero-field magnetic resonance of the photo-excited triplet state of pentacene at room temperature

    NASA Astrophysics Data System (ADS)

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

    2000-12-01

    The pulsed EPR free induction decay (FID) signals of the photo-excited pentacene triplet state are reported for three mixed crystals at room temperature: pentacene-h14 in p-terphenyl, pentacene-h14 in benzoic acid, and pentacene-d14 in p-terphenyl. The recorded FID signals have relatively long decay times of about four microseconds, presumably due to the reduced hyperfine interactions in the zero magnetic field. The time domain FID signals transform to spectral components typically narrower than 500 kHz, allowing us to determine the pentacene triplet zero field splitting parameters to better accuracy than previously reported. Further, a new experimental technique using the high speed magnetic field jumping capability enables us to examine the anisotropic hyperfine and quadrupole interactions.

  14. (π*,σ*), (σ*,π*) and Rydberg triplet excited states of hydrogen peroxide and other molecules bearing two adjacent heteroatoms.

    PubMed

    Hill, J Grant; Bucher, Götz

    2014-03-27

    The properties of the lowest triplet excited states of a series of small molecules containing two or more adjacent heteroatoms have been investigated. High-level coupled cluster and MRCI+Q calculations were employed to probe the properties of the triplet excited states of hydrogen peroxide, hydrazine, hydroxylamine, fluoroamines, oxygen difluoride, hypofluorous acid, chlorine, fluorine, and disulfane. All of the molecules investigated except hydroxylamine are predicted to have bound lowest triplet excited states that are either (π*,σ*) or (σ*,π*) as in H2O2, HOF, OF2, H2S2, Cl2, NH2F, NHF2, or NF3, or are Rydberg states (hydrazine, also H2O2 and H2S2). The heteroatom-heteroatom bond dissociation enthalpies of the triplet states range from very small values as predicted for hydrogen peroxide or fluorine, to BDEs around 8-9 kcal mol(-1) that should allow for an experimental observation of the triplet state, such as in disulfane or monofluoroamine. For all triplet minima investigated except NF3 and F2, CCSD(T) gave results in agreement with the multireference method MRCI+Q, and in excellent agreement with available experimental data (BDEs, ground-state geometries). Due to multireference problems, CCSD(T) does not provide a good description for longer heteroatom-heteroatom distances, and in some cases (e.g., Cl2) it wrongly predicts the presence of a transition state for bond formation on the triplet spin manifold, where the reaction is known experimentally and, as predicted by MRCI+Q, is known to be barrierless. Finally, the (3)Π(u) state of F2 is poorly described by CCSD(T) theory, the equilibrium bond distance is significantly underestimated relative to MRCI+Q, and CCSD(T) places the triplet state above the energy of two fluorine atoms. The T1 diagnostic, frequently used to assess the quality of CCSD(T) calculations, does not appear to provide a valid criterion for the systems studied. The formation of H2O2 on the triplet potential energy hypersurface might

  15. Multiscale analysis of the influence of the triplet helicoidal geometry on the strain state of a Nb 3Sn based strand for ITER coils

    NASA Astrophysics Data System (ADS)

    Boso, D. P.; Lefik, M.; Schrefler, B. A.

    2005-09-01

    A theoretical model of a beam of unidirectional composites—based on the homogenisation theory and a refined kinematical hypothesis—is used for the analysis of the influence of the helicoidal geometry of a superconducting strand triplet on its strain state. The triplet is the first cabling stage of the superconducting cables used to wind the coils of ITER fusion reactor. The multiscale modelling strategy is presented, for which a finite element code has been developed. A triplet of Nb 3Sn based strands subjected to an axial stretch is analysed, and the resulting complete 3D strain state in the Nb 3Sn filament is recovered. An "extra" strain is found due to the helicoidal geometry of the triplet. Discussion of the results concludes the paper.

  16. Suppression of strong field ionization in diatomic molecules with triplet ground states

    NASA Astrophysics Data System (ADS)

    Dewitt, M. J.; Wells, E.; Jones, R. R.

    2001-05-01

    The ionization rates of S_2, SO, and F2 when subjected to 800 nm, 100 fs laser pulses are measured as a function of laser pulse intensity and compared to those of Xe and Ar. Contrary to recent theoretical predictions, the ionization behavior of F2 is observed to be nearly identical to that of both N2 and Ar, and therefore behaves as would be predicted by a structureless, atom-like ionization model. The ionization rates of triplet S2 and SO are shown to be suppressed, much like triplet O_2, relative to expectations based solely on their ionization potentials. Measurements made with 1360 nm, 80 fs laser pulses show that the ionization suppression of S2 and SO persists at longer wavelengths.

  17. Electron spin polarization transfer to the charge-separated state from locally excited triplet configuration: theory and its application to characterization of geometry and electronic coupling in the electron donor-acceptor system.

    PubMed

    Kobori, Yasuhiro; Fuki, Masaaki; Murai, Hisao

    2010-11-18

    We present a theoretical model of analysis of the time-resolved electron paramagnetic resonance (TREPR) spectrum of the charge-separated (CS) state generated by the photoinduced electron transfer (ET) reaction via the locally excited triplet state in an electron donor-acceptor (D-A) system with a fixed molecular orientation. We show, by the stochastic-Liouville equation, that chemically induced dynamic electron polarization (CIDEP) of the triplet mechanism is explained by lack of transfer of quantum coherence terms in the primary triplet spin state, resulting in net emissive or absorptive electron spin polarization (ESP) which is dependent on anisotropy of the singlet-triplet intersystem crossing in the precursor excited state. This disappearance of the coherence is clearly shown to occur when the photoinduced ET rate is smaller than the angular frequency of the Zeeman splitting: the transferred coherence terms are averaged to be zero due to effective quantum oscillations during the time that the chemical reaction proceeds. The above theory has been applied to elucidate the molecular geometries and spin-spin exchange interactions (2J) of the CS states for both folded and extended conformers by computer simulations of TREPR spectra of the zinc porphyrin-fullerene dyad (ZnP-C(60)) bridged by diphenyldisilane. On the extended conformation, the electronic coupling is estimated from the 2J value. It has been revealed that the coupling term is smaller than the reported electronic interactions of the porphyrin-C(60) systems bridged by diphenylamide spacers. The difference in the electronic couplings has been explained by the difference in the LUMO levels of the bridge moieties that mediate the superexchange coupling for the long-range ET reaction.

  18. Hyperfine Structure and Predissociation of the Odd TRIPLET-B-PI-PLUS(0) State of Bromine.

    NASA Astrophysics Data System (ADS)

    Booth, James Lawrence

    Investigations have been carried out in bromine of the hyperfine structure of the B ^3 prod_{0_sp{u}{+ }} and X ^1sum_sp {rm g}{+} electronic states and of the predissociation of the B ^3prod _{0_sp{rm u}{+} } state by the ^1prod _{rm 1u} dissociative level. The technique of laser induced fluoresence of a molecular beam was used. ^{79}rm Br^ {81}Br hyperfine spectra were recorded for various B-X vibrational bands (v^{ '}>=ts v^{'' }) with v^' = 11 through 17 and v^{' '} = 0, 1, and 2, and for various rotational transitions (rm J^' >=ts J^{''}) with J^' from 0 and 11 and J^{''} from 0 to 10. As well, the ^ {79}Br_2 and ^ {81}Br_2 hyperfine spectra of the (13^' - 0^{' '}) and (17^' - 2^{''}) bands over the same range of rotational states were measured. The spectra are well described using one X state parameter: the electric quadrupole coupling constant eqQ_ {rm X}; and two B state parameters: the electric quadrupole coupling constant eqQ_ {rm B} and the nuclear spin-rotation constant C_{rm sr}. The results show that eqQ_{rm B}( ^{79}rm Br) = (177.0+/- 0.6) MHz for v^{'} = 11 and increases by approximately 0.5 MHz per vibrational quantum up to (180.6 +/- 1.4) MHz for v^{'} = 17. Similarly the ground state electric quadrupole coupling constant, eqQ_{rm X}(^ {79}Br) = (808.1 +/- 1.4) MHz for v^{'' } = 0 and increases by about 1 MHz per vibrational quantum to (811.4 +/- 1.4) MHz for v^{''} = 2. The hyperfine data also provided a check on the accuracy of some of the published rovibronic constants ^1 for each isotopomer. In order to reproduce the observed relative spacings of the transitions for all three isotopomers, the published term values, T _{00}, have to be modified; this can be done by decreasing the published values of T_{00} for ^ {81}rm Br_2 and ^{79}Br^{81}Br by (177 +/- 8) MHz and (326 +/- 8) MHz, respectively. The phase shift technique was applied to the study of the predissociation of the v^' = 13 B ^3prod_{0 _sp{rm u}{+}} electronic state of bromine. The

  19. Identification of singlet and triplet states of negatively charged excitons in CdTe-based quantum wells

    NASA Astrophysics Data System (ADS)

    Astakhov, G. V.; Yakovlev, D. R.; Crooker, S. A.; Ossau, W.; Christianen, P. C. M.; Rudenkov, V. V.; Karczewski, G.; Wojtowicz, T.; Kossut, J.

    2004-02-01

    We present comprehensive study of negatively charged exciton in high magnetic fields for filling factors < 1. In magneto-optical spectra the fine structure was found to be contributed by neutral exciton and different a set of bound states of charged exciton. These states were identified due to their unique polarization properties charecteristics in emission and absorption spectra.

  20. Experimental evidence for the triplet-like spin state appearing in ground-state singlet biradicals as a key feature for generalized ferrimagnetic spin alignment.

    PubMed

    Maekawa, Kensuke; Shiomi, Daisuke; Ise, Tomoaki; Sato, Kazunobu; Takui, Takeji

    2006-02-09

    The authors have previously proposed a theoretical model for exotic spin alignment in organic molecular assemblages: The alternating chain of organic biradicals in a singlet (Sb=0) ground state and monoradicals with S=1/2 has a ferrimagnetic ground state for the whole chain, which has been termed generalized ferrimagnetism. An important feature of the generalized ferrimagnetic spin alignment has been found in the deviation of the expectation value Sb2 of the biradical spin from zero. Even a triplet-like spin state Sb2=2 (Sb=1) has been predicted in the theoretical calculations. In this study, we have found experimental evidence for the pseudo-triplet state appearing in the ground-state singlet biradical of a real open-shell compound. At first, we have demonstrated from theoretical calculations that the singlet biradical has Sb2=2 (Sb=1) in a molecular pair with an S=1 metal ion as well as with the S=1/2 monoradical. The pseudo-triplet state of the biradical affords a singlet state of the whole system of the biradical-metal ion pair, which is readily detectable in experiments for verifying the theoretical prediction. As a model compound for the biradical-metal ion pair, a transition metal complex, [(bnn)(Ni(hfac)2)1.5(H2O)] (1), has been synthesized from a nitronyl nitroxide-based ground-state singlet biradical bnn and Ni(hfac)2. From X-ray crystallographic analyses, the compound contains a molecular pair of bnn and Ni(hfac)2, which serves as a model system under the above theoretical studies. It has been found from the analysis of the temperature dependence of magnetic susceptibility that the bnn-Ni(hfac)2 pair has the singlet (S=0) ground state. The singlet ground state of the pair results from an antiparallel coupling of the pseudo-triplet of the biradical and the S=1 spin on the Ni ion. The pseudo-triplet state in the ground-state singlet biradical has thus been verified experimentally, which is crucially important to realize the generalized ferrimagnetic spin

  1. Direct observation of the solvent effects on the low-lying nπ* and ππ* excited triplet states of acetophenone derivatives in thermal equilibrium.

    PubMed

    Narra, Sudhakar; Shigeto, Shinsuke

    2015-03-05

    Low-lying excited triplet states of aromatic carbonyl compounds exhibit diverse photophysical and photochemical properties of fundamental importance. Despite tremendous effort in studying those triplet states, the effects of substituents and solvents on the energetics of the triplet manifold and on photoreactivity remain to be fully understood. We have recently studied the ordering of the low-lying nπ* and ππ* excited triplet states and its substituent dependence in acetophenone derivatives using nanosecond time-resolved near-IR (NIR) spectroscopy. Here we address the other important issue, the solvent effects, by directly observing the electronic bands in the NIR that originate from the lowest nπ* and ππ* states of acetophenone derivatives in four solvents of different polarity (n-heptane, benzene, acetonitrile, and methanol). The two transient NIR bands decay synchronously in all the solvents, indicating that the lowest nπ* and ππ* states are in thermal equilibrium irrespective of the solvent polarity studied here. We found that the ππ* band increases in intensity relative to the nπ* band as solvent polarity increases. These results are compared with the photoreduction rate constant for the acetophenone derivatives in the solvents to which 2-propanol was added as a hydrogen-atom donor. Based on the present findings, we present a comprehensive, solvent- and substituent-dependent energy level diagram of the low-lying nπ* and ππ* excited triplet states.

  2. DFT spin-orbit coupling between singlet and triplet excited states: A case of psoralen compounds

    NASA Astrophysics Data System (ADS)

    Chiodo, Sandro G.; Russo, Nino

    2010-04-01

    We present a computational protocol in which our method is used to compute spin-orbit (SO) matrix elements on time-dependent-density functional theory (TD-DFT). These SO contributions, computed employing our SO program package, MolSOC, have been expressed, in turn, in terms of weighted coefficients and SO matrix elements between singlet and triplet wave functions arising from a given one-electron transition. The protocol has been applied to study psoralen compound and its derivatives obtained from the replacement of one oxygen with sulfur or selenium. The obtained results have been compared with those reported in literature.

  3. Auroral N2 emissions and the effect of collisional processes on N2 triplet state vibrational populations

    NASA Astrophysics Data System (ADS)

    Morrill, Jeff S.; Benesch, William M.

    1996-01-01

    Previous model results have shown that the N2 triplet vibrational level populations in the aurora are strongly affected by cascade and quenching by atomic and molecular oxygen. As the aurora penetrates to lower altitudes (less than 100 km) the role of quenching by atomic oxygen becomes less important and processes involving N2 collisions begin to play a more prominent part. We are developing a model which will yield steady state vibrational level populations for both the singlet and triplet valence states of N2. The model currently provides results for the seven low-lying N2 triplet states (A3Σ+u, B3Πg, W3Δu, B'3Σ-u, C3Πu, D3Σ+u, and E3Σ+g). These states are responsible for auroral emissions from the UV (Vegard-Kaplan (VK), second positive (2PG)) through the visible to the infrared (first positive (1PG), infrared afterglow (IRA), Wu-Benesch (WB)). We have included two additional collisional processes in the current model which were not treated previously. These are the intersystem collisional transfer of excitation (ICT) between the B state and the A, W, and B' states and vibrational redistribution within the A state vibrational manifold, both due to collisions with ground state N2. The present work compares our current model results with those of a previous model as well as ground, airborne, and rocket observations. The comparison between N2(A) (VK) and N2(B) (1PG) vibrational level populations predicted by our model and a number of auroral observations indicate that the current model achieves a significant improvement in the fit between calculation and observation. In addition, the current model predicts a shift in the band intensity distribution of the 1PG Δν=3 sequence from the infrared into the visible red at the lower altitudes (less than 90 km) as well as an overall enhancement in the entire 1PG system. Consequently, this provides a possible explanation of a dominate feature of type b aurora, the auroral red lower border.

  4. ODMR of carotenoid and chlorophyll triplets in CP43 and CP47 complexes of spinach

    NASA Astrophysics Data System (ADS)

    Carbonera, Donatella; Giacometti, Giovanni; Agostini, Giancarlo; Angerhofer, Alexander; Aust, Volker

    1992-07-01

    Optically detected magnetic resonance (ODMR) of the light-harvesting complexes CP43 and CP47 of the spinach photosynthetic machinery revealed triplet states both from carotenoids and chlorophylls. The triplet state of the only carotenoid present in the complexes (β-carotene) is observed by ODMR using fluorescence detection (FDMR) in the main chlorophyll emission band in the 680 nm region, and absorption detection in the visible region. Chlorophyll triplet signals are also obtained by microwave sweeping in the chlorophyll emission and absorption regions. MIA spectra are obtained and discussed for both complexes.

  5. Tuning ground states of bis(triarylamine) dications: from a closed-shell singlet to a diradicaloid with an excited triplet state.

    PubMed

    Su, Yuanting; Wang, Xingyong; Zheng, Xin; Zhang, Zaichao; Song, You; Sui, Yunxia; Li, Yizhi; Wang, Xinping

    2014-03-10

    Three bis(triarylamine) dications were isolated by using weakly coordinating anions. Their electronic structures in the ground state were investigated by various experiments in conjunction with theoretical calculations. The ground-state electronic structures of these species were tunable by substituent effects, with two of them as closed-shell singlets and one of them as an open-shell singlet in the solid state. The excited state of the latter is thermally accessible, indicated by EPR and SQUID measurements. The work provides a new and stable diradicaloid structure motif with an excited triplet sate.

  6. More on the catalysis of internal conversion in chlorophyll a by an adjacent carotenoid in light-harvesting complex (Chl a/ b LHCII) of higher plants: time-resolved triplet-minus-singlet spectra of detergent-perturbed complexes

    NASA Astrophysics Data System (ADS)

    Naqvi, K. Razi; Jávorfi, Tamás; Melø, T. B.; Garab, Gyözö

    1998-12-01

    Wavelength-selective photo-excitation of samples containing a detergent and LHCII (the main light-harvesting complex pertaining to photosystem II of green plants) is used for recording time-resolved triplet-minus-singlet (TmS) difference spectra, with a view to probing interactions between chlorophyll a (Chl a) and chlorophyll b (Chl b), and between Chl a and lutein (Lut). Once the detergent concentration ( CD) exceeds a threshold, C©, the TmS spectrum becomes sensitive to λ⊗, the wavelength of excitation, and to t, the delay between excitation and observation. Each increment in CD brings about a diminution in the efficiency of a†→ x† transfer (triplet-triplet transfer from Chl a to Lut) and a rise in both the triplet formation yield and the fluorescence yield of Chl a. What is more, b*→ a* transfer (singlet-singlet transfer from Chl b to Chl a) slackens to such an extent that Chl b*→Chl b† intersystem crossing, negligible when CD is below C©, begins to vie with transfer, for the deactivation of Chl b* (in the foregoing an asterisk/dagger denotes singlet/triplet excitation). The reduction in the efficiencies of the two transfers is easily understood by: (i) invoking the Kühlbrandt-Wang-Fujiyoshi model of LHCII, which posits each Chl b in contact with a Chl a and each Chl a in contact with a Lut, and (ii) assuming that the detergent severs contact between adjacent chromophores. That a growth in the triplet yield of Chl a* accompanies the detergent-induced decrease in the efficiency of a†→ x† transfer becomes intelligible if one assumes, further, that internal conversion in Chla* is faster than that in overlineChla * , where under or over lining betokens the presence or absence of a carotenoid neighbour. When CD is close to C©, most Chl a molecules are adjacent to a Lut, internal conversion dominates, and the overall triplet yield is low. As CD is gradually raised the Chla → overlineChla transformation sets in, causing concomitant drops in

  7. The spectroscopy of singlets and triplets excites electronic states, spatial and electronic structure of hydrocarbons and quantum classifications in chemmotology

    NASA Astrophysics Data System (ADS)

    Obukhov, A. E.

    2016-12-01

    In this work we demonstrate the physical foundations of the spectroscopy of the grounds states: E- and X-ray, (RR) Raman scattering the NMR 1H and 13C and IR-, EPR- absorption and the singlets and triplets electronic excited states in the multinuclear hydrocarbons in chemmotology. The parameters of UV-absorption, RR-Raman scattering of light, the fluorescence and the phosphorescence and day-lasers at the pumping laser and lamp, OLEDs and OTETs- are measurements. The spectral-energy properties are briefly studied. The quantum-chemical LCAO-MO SCF expanded-CI PPP/S and INDO/S methods in the electronic and spatial structure hidrocarbons are considered.

  8. Spin-triplet negatively charged excitons in GaAs quantum wells

    NASA Astrophysics Data System (ADS)

    Shields, A. J.; Pepper, M.; Simmons, M. Y.; Ritchie, D. A.

    1995-09-01

    We observe magnetic-field-induced transitions in the interband optical spectra of GaAs quantum wells with a small excess electron density. Their strengthening with excess electron density, in addition to their light polarization dependence, demonstrate that these correspond to (excited) spin-triplet states of the negatively charged exciton. The second-electron binding energy of both singlet and triplet X- strengthens with field.

  9. Heteroatom effects in XC5H5C Arduengo-type carbenes (X = CH, N, P, and As) in singlet and triplet states

    NASA Astrophysics Data System (ADS)

    Vessally, Esmail; Poorheravi, Mohammad Reza; Edjlali, Ladan; Motallebzadeh, Maryam

    2014-07-01

    Internal energy difference, Δ E s-t; enthalpy difference, Δ H s-t; Gibbs free energy difference, Δ G s-t, between the singlet (s) and triplet states (t) of XC5H5C, 1X (X = CH, N, P, and As) were computed at B3LYP/6-311++G** and MP2/6-311++G**//B3LYP/6-311++G** levels of theory. The Δ G s-t between the singlet and triplet states of 1 X were changed in the order: 1 P > 1 As > 1 N .

  10. Matrix effects on the triplet state of the OLED emitter Ir(4,6-dFppy)2(pic) (FIrpic): investigations by high-resolution optical spectroscopy.

    PubMed

    Rausch, Andreas F; Thompson, Mark E; Yersin, Hartmut

    2009-03-02

    The sky-blue emitting compound Ir(4,6-dFppy)(2)(pic) (iridium(III)bis[2-(4',6'-difluorophenyl)pyridinato-N,C(2')]-picolinate), commonly referred to as FIrpic and representing a well-known emitter material for organic light emitting diodes (OLEDs), has been investigated in detail by optical spectroscopy. Studies at temperatures from T = 1.5 K to T = 300 K were carried out in CH(2)Cl(2) and tetrahydrofuran (THF). In CH(2)Cl(2), two discrete sites were observed at cryogenic temperatures and studied by site-selective, high-resolution spectroscopy. The investigations reveal that the molecules located at the two sites exhibit distinctly different photophysical properties. For example, the three substates I, II, and III of the emitting triplet state T(1) of the low-energy site A show a distinctly larger zero-field splitting (ZFS) and exhibit shorter individual decay times than observed for the high-energy site B. The vibrational satellite structures in the emission spectra of the substates I(A) and I(B) exhibit clear differences in the ranges of metal-ligand (M-L) vibrations. For the compound studied in a polycrystalline THF host, giving only strongly inhomogeneously broadened spectra, the ZFS parameters and substate decay times vary in a similar range as observed for the two discrete sites in the CH(2)Cl(2) matrix. Thus, the amount of ZFS, the emission decay times, and also the intensities of the M-L vibrational satellites are affected by the matrix cage, that is, the host environment of the emitting complex. These properties are discussed with respect to variations of spin-orbit coupling routes. In particular, changes of d-orbital admixtures, that is, differences of the metal-to-ligand charge transfer (MLCT) character in the emitting triplet, play an important role. The matrix effects are expected to be also of importance for FIrpic and other Ir(III) compounds when applied as emitters in amorphous OLED matrixes.

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

    NASA Technical Reports Server (NTRS)

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

    1993-01-01

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

  12. Phase transitions of dense neutron matter with generalized Skyrme interaction to superfluid states with triplet pairing in strong magnetic field

    NASA Astrophysics Data System (ADS)

    Tarasov, A. N.

    2012-12-01

    A generalized non-relativistic Fermi-liquid approach was used to find analytical formulas for temperatures Tc1(n, H) and Tc2(n, H) (which are functions nonlinear of density n and linear of magnetic field H) of phase transitions in spatially uniform dense pure neutron matter from normal to superfluid states with spin-triplet p-wave pairing (similar to anisotropic superfluid phases 3He-A1 and 3He-A2) in steady and homogeneous strong magnetic field (but |μn| H ll Ec < ɛF(n), where μn is the magnetic dipole moment of a neutron, Ec is the cutoff energy and ɛF(n) is the Fermi energy in neutron matter). General formulas for Tc1, 2 (n, H) (valid for arbitrary parameterization of the effective Skyrme interaction in neutron matter) are specified here for generalized BSk18 parameterization of the Skyrme forces (with additional terms dependent on density n) on the interval 0.3 n0 < n < nc (BSk18) ≍ 2.7952 · n0, where n0 = 0.17 fm-3 is nuclear density and at critical density nc(BSk18) triplet superfluidity disappears, Tc0(n, cH = 0) = 0. Expressions for phase transition temperatures Tc0(n)<0.09MeV (at Ec = 10MeV) and Tc1, 2(n, H) are realistic non-monotone functions of density n for BSk18 parameterization of the Skyrme forces (contrary to their monotone increase for all previous BSk parameterizations). Phase transitions to superfluid states of such type might occur in liquid outer core of magnetars (strongly magnetized neutron stars).

  13. Energy landscapes of dynamic ensembles of rolling triplet repeat bulge loops: implications for DNA expansion associated with disease states.

    PubMed

    Völker, Jens; Gindikin, Vera; Klump, Horst H; Plum, G Eric; Breslauer, Kenneth J

    2012-04-04

    DNA repeat domains can form ensembles of canonical and noncanonical states, including stable and metastable DNA secondary structures. Such sequence-induced structural diversity creates complex conformational landscapes for DNA processing pathways, including those triplet expansion events that accompany replication, recombination, and/or repair. Here we demonstrate further levels of conformational complexity within repeat domains. Specifically, we show that bulge loop structures within an extended repeat domain can form dynamic ensembles containing a distribution of loop positions, thereby yielding families of positional loop isomers, which we designate as "rollamers". Our fluorescence, absorbance, and calorimetric data are consistent with loop migration/translocation between sites within the repeat domain ("rollamerization"). We demonstrate that such "rollameric" migration of bulge loops within repeat sequences can invade and disrupt previously formed base-paired domains via an isoenthalpic, entropy-driven process. We further demonstrate that destabilizing abasic lesions alter the loop distributions so as to favor "rollamers" with the lesion positioned at the duplex/loop junction, sites where the flexibility of the abasic "universal hinge" relaxes unfavorable interactions and/or facilitates topological accommodation. Another strategic siting of an abasic site induces directed loop migration toward denaturing domains, a phenomenon that merges destabilizing domains. In the aggregate, our data reveal that dynamic ensembles within repeat domains profoundly impact the overall energetics of such DNA constructs as well as the distribution of states by which they denature/renature. These static and dynamic influences within triplet repeat domains expand the conformational space available for selection and targeting by the DNA processing machinery. We propose that such dynamic ensembles and their associated impact on DNA properties influence pathways that lead to DNA

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

    PubMed

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

    2016-06-01

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

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

    PubMed

    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 CH3NH3PbI3 (MAPbI3) perovskite in film phase. Through the observation of the shorter fluorescence lifetime in TIPS-pentacene/MAPbI3 perovskite bilayer film (5 ns) compared with pristine MAPbI3 perovskite film (20 ns), we verified electron-transfer processes between TIPS-pentacene and MAPbI3 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/MAPbI3 perovskite bilayer film indicate that electron transfer occurs from triplet state of TIPS-pentacene generated by singlet fission processes to MAPbI3 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.

  16. The Role of Local Triplet Excited States and D‐A Relative Orientation in Thermally Activated Delayed Fluorescence: Photophysics and Devices

    PubMed Central

    Santos, Jose; Graves, David R.; Data, Przemyslaw; Nobuyasu, Roberto S.; Fox, Mark A.; Batsanov, Andrei S.; Palmeira, Tiago; Berberan‐Santos, Mário N.; Bryce, Martin R.; Monkman, Andrew P.

    2016-01-01

    Here, a comprehensive photophysical investigation of a the emitter molecule DPTZ‐DBTO2, showing thermally activated delayed fluorescence (TADF), with near‐orthogonal electron donor (D) and acceptor (A) units is reported. It is shown that DPTZ‐DBTO2 has minimal singlet–triplet energy splitting due to its near‐rigid molecular geometry. However, the electronic coupling between the local triplet (3LE) and the charge transfer states, singlet and triplet, (1CT, 3CT), and the effect of dynamic rocking of the D–A units about the orthogonal geometry are crucial for efficient TADF to be achieved. In solvents with low polarity, the guest emissive singlet 1CT state couples directly to the near‐degenerate 3LE, efficiently harvesting the triplet states by a spin orbit coupling charge transfer mechanism (SOCT). However, in solvents with higher polarity the emissive CT state in DPTZ‐DBTO2 shifts below (the static) 3LE, leading to decreased TADF efficiencies. The relatively large energy difference between the 1CT and 3LE states and the extremely low efficiency of the 1CT to 3CT hyperfine coupling is responsible for the reduction in TADF efficiency. Both the electronic coupling between 1CT and 3LE, and the (dynamic) orientation of the D–A units are thus critical elements that dictate reverse intersystem crossing processes and thus high efficiency in TADF. PMID:27981000

  17. Difluorodiazirine (CF2N2): A comparative quantum mechanical study of the first triplet and first singlet excited states

    NASA Astrophysics Data System (ADS)

    Terrabuio, Luiz Alberto; Haiduke, Roberto Luiz Andrade; Matta, Chérif F.

    2016-07-01

    3,3‧-Difluorodiazirine is a precursor of difluorocarbene radical (:CF2) which is used in organic synthesis and photo affinity labelling. This molecule possesses no dipole moment in the ground electronic state (S0) but has a significant dipole moment (of magnitude ~0.97 D) in both its first (triplet, T1) and second (singlet S1) excited states. These equal dipole moments are shown to originate from widely differing atomic polarization and inter-atomic charge transfer terms (defined by the Quantum Theory of Atoms in Molecules (QTAIM)). The calculated vertical/adiabatic excitation energies for the T1 and S1 states are 2.81/2.63 and 3.99/3.78 eV, respectively. Geometries, vibrational frequencies, atomic charges and spin populations, and the localization-delocalization matrices (LDMs) (Matta, J. Comput. Chem. 35 (2014) 1165) of the excited states are compared with those of the ground state. All calculations have been conducted at the (U)QCISD/aug-cc-pVTZ level of theory.

  18. Inhibition of humic substances mediated photooxygenation of furfuryl alcohol by 2,4,6-trimethylphenol. Evidence for reactivity of the phenol with humic triplet excited states.

    PubMed

    Halladja, Sabrina; Ter Halle, Alexandra; Aguer, Jean-Pierre; Boulkamh, Abdelaziz; Richard, Claire

    2007-09-01

    To probe the reactivity of 2,4,6-trimethylphenol with humic triplet excited states, we investigated its influence on the humic substances-mediated photooxygenation offurfuryl alcohol. Elliott soil humic and fulvic acids were employed for these experiments. When added in the concentration range of 10(-4) - 10(-3) M, 2,4,6-trimethylphenol inhibited furfuryl alcohol photooxygenation to an extent depending on its concentration. The inhibiting effect decreased as the oxygen concentration was increased. By postulating that 2,4,6-trimethylphenol competes with oxygen for reaction with humic triplet excited states and with furfuryl alcohol for reaction with singlet oxygen, we obtained kinetic laws describing the consumption profiles of furfuryl alcohol and 2,4,6-trimethylphenol. Experimental rates of 2,4,6-trimethylphenol and furfuryl alcohol loss could be satisfactorily fitted with 1.09-1.16 for the ratio k2/k3, where k2 and k3 are the reaction rate constants of humic triplet excited states with oxygen and 2,4,6-trimethylphenol, respectively. These types of experiments could be extended to a variety of substrates to measure their reaction rate constants with humic triplet excited states.

  19. Effect of H2 binding on the nonadiabatic transition probability between singlet and triplet states of the [NiFe]-hydrogenase active site.

    PubMed

    Kaliakin, Danil S; Zaari, Ryan R; Varganov, Sergey A

    2015-02-12

    We investigate the effect of H2 binding on the spin-forbidden nonadiabatic transition probability between the lowest energy singlet and triplet electronic states of [NiFe]-hydrogenase active site model, using a velocity averaged Landau-Zener theory. Density functional and multireference perturbation theories were used to provide parameters for the Landau-Zener calculations. It was found that variation of the torsion angle between the terminal thiolate ligands around the Ni center induces an intersystem crossing between the lowest energy singlet and triplet electronic states in the bare active site and in the active site with bound H2. Potential energy curves between the singlet and triplet minima along the torsion angle and H2 binding energies to the two spin states were calculated. Upon H2 binding to the active site, there is a decrease in the torsion angle at the minimum energy crossing point between the singlet and triplet states. The probability of nonadiabatic transitions at temperatures between 270 and 370 K ranges from 35% to 32% for the active site with bound H2 and from 42% to 38% for the bare active site, thus indicating the importance of spin-forbidden nonadiabatic pathways for H2 binding on the [NiFe]-hydrogenase active site.

  20. Density functional theory calculations on rhodamine B and pinacyanol chloride. Optimized ground state, dipole moment, vertical ionization potential, adiabatic electron affinity and lowest excited triplet state.

    PubMed

    Delgado, Juan C; Selsby, Ronald G

    2013-01-01

    The ground state configuration of the gas phase cationic dyes pinacyanol chloride and rhodamine B are optimized with HF/6-311 + G(2d,2p) method and basis set. B3PW91/6-311 + G(2df,2p) functional and basis set is used to calculate the Mulliken atom charge distribution, total molecular energy, the dipole moment, the vertical ionization potential, the adiabatic electron affinity and the lowest excited triplet state, the last three as an energy difference between separately calculated open shell and ground states. The triplet and extra electron states are optimized to find the relaxation energy. In the ground state optimization of both dyes the chloride anion migrates to a position near the center of the chromophore. For rhodamine B the benzoidal group turns perpendicular to the chromophore plane. For both dyes, the LUMO is mostly of π character associated with the aromatic part of the molecule containing the chromophore. The highest occupied MOs consist of three almost degenerate eigenvectors involving the chloride anion coordinated with σ electrons in the molecular framework. The fourth highest MO is of π character. For both molecules in the gas phase ionization process the chloride anion loses the significant fraction of electric charge. In electron capture, the excess charge goes mainly on the dye cation.

  1. Rate of carotenoid triplet formation in solubilized light-harvesting complex II (LHCII) from spinach.

    PubMed Central

    Schödel, R; Irrgang, K D; Voigt, J; Renger, G

    1998-01-01

    In the present study the rate of triplet transfer from chlorophyll to carotenoids in solubilized LHCII was investigated by flash spectroscopy using laser pulses of approximately 2 ns for both pump and probe. Special attention has been paid to calibration of the experimental setup and to avoid saturation effects. Carotenoid triplets were identified by the pronounced positive peak at approximately 507 nm in the triplet-singlet difference spectra. DeltaOD (507 nm) exhibits a monoexponential relaxation kinetics with characteristic lifetimes of 2-9 micros (depending on the oxygen content) that was found to be independent of the pump pulse intensity. The rise of DeltaOD (507 nm) was resolved via a pump probe technique where an optical delay of up to 20 ns was used. A thorough analysis of these experimental data leads to the conclusion that the kinetics of carotenoid triplet formation in solubilized LHCII is almost entirely limited by the lifetime of the excited singlet state of chlorophyll but neither by the pulse width nor by the rate constant of triplet-triplet transfer. Within the experimental error the rate constant of triplet-triplet transfer from chlorophyll to carotenoids was estimated to be kTT > (0.5 ns)-1. This value exceeds all data reported so far by at least one order of magnitude. The implications of this finding are briefly discussed. PMID:9826635

  2. Benchmark calculations on the lowest-energy singlet, triplet, and quintet states of the four-electron harmonium atom

    SciTech Connect

    Cioslowski, Jerzy; Strasburger, Krzysztof; Matito, Eduard

    2014-07-28

    For a wide range of confinement strengths ω, explicitly-correlated calculations afford approximate energies E(ω) of the ground and low-lying excited states of the four-electron harmonium atom that are within few μhartree of the exact values, the errors in the respective energy components being only slightly higher. This level of accuracy constitutes an improvement of several orders of magnitude over the previously published data, establishing a set of benchmarks for stringent calibration and testing of approximate electronic structure methods. Its usefulness is further enhanced by the construction of differentiable approximants that allow for accurate computation of E(ω) and its components for arbitrary values of ω. The diversity of the electronic states in question, which involve both single- and multideterminantal first-order wavefunctions, and the availability of the relevant natural spinorbitals and their occupation numbers make the present results particularly useful in research on approximate density-matrix functionals. The four-electron harmonium atom is found to possess the {sup 3}P{sub +} triplet ground state at strong confinements and the {sup 5}S{sub −} quintet ground state at the weak ones, the energy crossing occurring at ω ≈ 0.0240919.

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

    PubMed

    Gu, Jiande; Wang, Jing; Leszczynski, Jerzy

    2015-02-12

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

  4. Conservation of spin polarization during triplet-triplet energy transfer in reconstituted peridinin-chlorophyll-protein complexes.

    PubMed

    Di Valentin, Marilena; Tait, Claudia; Salvadori, Enrico; Ceola, Stefano; Scheer, Hugo; Hiller, Roger G; Carbonera, Donatella

    2011-11-17

    Peridinin-chlorophyll-protein (PCP) complexes, where the N-terminal domain of native PCP from Amphidinium carterae has been reconstituted with different chlorophyll (Chl) species, have been investigated by time-resolved EPR in order to elucidate the details of the triplet-triplet energy transfer (TTET) mechanism. This spectroscopic approach exploits the concept of spin conservation during TTET, which leads to recognizable spin-polarization effects in the observed time-resolved EPR spectra. The spin polarization produced at the acceptor site (peridinin) depends on the initial polarization of the donor (chlorophyll) and on the relative geometric arrangement of the donor-acceptor spin axes. A variation of the donor triplet state properties in terms of population probabilities or triplet spin axis directions, as produced by replacement of chlorophyll a (Chl a) with non-native chlorophyll species (ZnChl a and BacterioChl a) in the reconstituted complexes, is unambiguously reflected in the polarization pattern of the carotenoid triplet state. For the first time, in the present investigation spin-polarization conservation has been shown to occur among natural cofactors in protein complexes during the TTET process. Proving the validity of the assumption of spin conservation adopted in the EPR spectral analysis, the results reinforce the hypothesis that in PCP proteins peridinin 614, according to X-ray nomenclature (Hofmann, E.; et al. Science 1996, 272, 1788-1791), is the carotenoid of election in the photoprotection mechanism based on TTET.

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

    PubMed Central

    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

  6. Time-resolved EPR studies of charge recombination and triplet-state formation within donor-bridge-acceptor molecules having wire-like oligofluorene bridges.

    PubMed

    Miura, Tomoaki; Carmieli, Raanan; Wasielewski, Michael R

    2010-05-13

    Spin-selective charge recombination of photogenerated radical ion pairs within a series of donor-bridge-acceptor (D-B-A) molecules, where D = phenothiazine (PTZ), B = oligo(2,7-fluorenyl), and A = perylene-3,4:9,10-bis(dicarboximide) (PDI), PTZ-FL(n)-PDI, where n = 1-4 (compounds 1-4), is studied using time-resolved electron paramagnetic resonance (TREPR) spectroscopy in which the microwave source is either continuous-wave or pulsed. Radical ion pair TREPR spectra are observed for 3 and 4 at 90-294 K, while the neutral triplet state of PDI ((3)*PDI) is observed at 90-294 K for 2-4 and at 90 K for 1. (3)*PDI is produced by three mechanisms, as elucidated by its zero-field splitting parameters and spin polarization pattern. The mechanisms are spin-orbit-induced intersystem crossing (SO-ISC) in PDI aggregates, direct spin-orbit charge-transfer intersystem crossing (SOCT) from the singlet radical pair within 1, and radical pair intersystem crossing (RP-ISC) as a result of S-T(0) mixing of the radical ion pair states in 2-4. The temperature dependence of the spin-spin exchange interaction (2J) shows a dramatic decrease at low temperatures, indicating that the electronic coupling between the radical ions decreases due to an increase in the average fluorene-fluorene dihedral angle at low temperatures. The charge recombination rates for 3 and 4 decrease at low temperature, but that for 2 is almost temperature-independent. These results strongly suggest that the dominant mechanism of charge recombination for n >or= 3 is incoherent thermal hopping, which results in wire-like charge transfer.

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

    PubMed

    Ahmed, Ghada H; Aly, Shawkat M; Usman, Anwar; Eita, Mohamed S; Melnikov, Vasily A; Mohammed, Omar F

    2015-05-11

    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.

  8. Low-lying singlet and triplet electronic states of RhB.

    PubMed

    Borin, Antonio Carlos; Gobbo, João Paulo

    2008-05-08

    The low-lying XSigma+, a3Delta, A1Delta, b3Sigma+, B1Pi, c3Pi, C1Phi, D1Sigma+, E1Pi, d3Phi, and e3Pi electronic states of RhB have been investigated at the ab initio level, using the multistate multiconfigurational second-order perturbation (MS-CASPT2) theory, with extended atomic basis sets and inclusion of scalar relativistic effects. Among the eleven electronic states included in this work, only three (the X1Sigma+, D1Sigma+, and E1Pi states) have been investigated experimentally. Potential energy curves, spectroscopic constants, dipole moments, binding energies, and chemical bonding aspects are presented for all electronic states.

  9. Cryptanalysis and Improvement for the Quantum Private Comparison Protocol Based on Triplet Entangled State and Single-Particle Measurement

    NASA Astrophysics Data System (ADS)

    Ting, Xu; Tian-Yu, Ye

    2017-03-01

    Quantum private comparison (QPC) aims to accomplish the equality comparison of secret inputs from two users on the basis of not leaking their contents out. Recently, Chen et al. proposed the QPC protocol based on triplet GHZ state and single-particle measurement (Optics Communications 283, 1561-1565 (2010)). In this paper, they suggested the standard model of a semi-honest third party (TP) for the first time, and declared that their protocol is secure. Subsequently, Lin et al. pointed out that in Chen et al.'s protocol, one user can extract the other user's secret without being discovered by performing the intercept-resend attack, and suggested two corresponding improvements (Optics Communications 284, 2412-2414 (2011)). However, Yang et al. first pointed out that the model of TP adopted by both Chen et al.'s protocol and Lin et al.'s improved protocols is unreasonable, and thought that a practical TP may also try any possible means to steal the users' secrets except being corrupted by the adversary including the dishonest user (Quantum Inf Process 12, 877-885 (2013). In this paper, after taking the possible attacks from TP into account, we propose the eavesdropping strategy of TP toward Lin et al.'s improved protocols and suggest two feasible solutions accordingly.

  10. Communication: DMRG-SCF study of the singlet, triplet, and quintet states of oxo-Mn(Salen)

    SciTech Connect

    Wouters, Sebastian Van Speybroeck, Veronique; Van Neck, Dimitri; Bogaerts, Thomas; Van Der Voort, Pascal

    2014-06-28

    We use CHEMPS2, our free open-source spin-adapted implementation of the density matrix renormalization group (DMRG) [S. Wouters, W. Poelmans, P. W. Ayers, and D. Van Neck, Comput. Phys. Commun. 185, 1501 (2014)], to study the lowest singlet, triplet, and quintet states of the oxo-Mn(Salen) complex. We describe how an initial approximate DMRG calculation in a large active space around the Fermi level can be used to obtain a good set of starting orbitals for subsequent complete-active-space or DMRG self-consistent field calculations. This procedure mitigates the need for a localization procedure, followed by a manual selection of the active space. Per multiplicity, the same active space of 28 electrons in 22 orbitals (28e, 22o) is obtained with the 6-31G{sup *}, cc-pVDZ, and ANO-RCC-VDZP basis sets (the latter with DKH2 scalar relativistic corrections). Our calculations provide new insight into the electronic structure of the quintet.

  11. Excited State Absorption Measurements In Some Scintillator Dye Solutions

    NASA Astrophysics Data System (ADS)

    Dharamsi, A., N.; Jong, Shawpin; Hassam, A. B.

    1986-11-01

    Time-resolved excited state triplet-triplet absorption spectra were measured for solutions of 2,5 diphenyloxazole (PPO) and 2,1 napthyl, 5 phenyloxazole (aNPO) in several solvents. Concentration quenching effects due to excimer formation in nonaromatic solvents were observed. A numerical analysis of the experimental results yielded the rate constants for intersystem crossing, triplet quenching by 02, triplet self quenching and the formation of excimers.

  12. Statistical Enrichment of Epigenetic States Around Triplet Repeats that Can Undergo Expansions

    PubMed Central

    Essebier, Alexandra; Vera Wolf, Patricia; Cao, Minh Duc; Carroll, Bernard J.; Balasubramanian, Sureshkumar; Bodén, Mikael

    2016-01-01

    More than 30 human genetic diseases are linked to tri-nucleotide repeat expansions. There is no known mechanism that explains repeat expansions in full, but changes in the epigenetic state of the associated locus has been implicated in the disease pathology for a growing number of examples. A comprehensive comparative analysis of the genomic features associated with diverse repeat expansions has been lacking. Here, in an effort to decipher the propensity of repeats to undergo expansion and result in a disease state, we determine the genomic coordinates of tri-nucleotide repeat tracts at base pair resolution and computationally establish epigenetic profiles around them. Using three complementary statistical tests, we reveal that several epigenetic states are enriched around repeats that are associated with disease, even in cells that do not harbor expansion, relative to a carefully stratified background. Analysis of over one hundred cell types reveals that epigenetic states generally tend to vary widely between genic regions and cell types. However, there is qualified consistency in the epigenetic signatures of repeats associated with disease suggesting that changes to the chromatin and the DNA around an expanding repeat locus are likely to be similar. These epigenetic signatures may be exploited further to develop models that could explain the propensity of repeats to undergo expansions. PMID:27013954

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

    SciTech Connect

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

    2004-11-01

    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. Is Nitrate Anion Photodissociation Mediated by Singlet-Triplet Absorption?

    PubMed

    Svoboda, Ondřej; Slavíček, Petr

    2014-06-05

    Photolysis of the nitrate anion is involved in the oxidation processes in the hydrosphere, cryosphere, and stratosphere. While it is known that the nitrate photolysis in the long-wavelength region proceeds with a very low quantum yield, the mechanism of the photodissociation remains elusive. Here, we present the quantitative modeling of singlet-singlet and singlet-triplet absorption spectra in the atmospherically relevant region around 300 nm, and we argue that a spin-forbidden transition between the singlet ground state and the first triplet state contributes non-negligibly to the nitrate anion photolysis. We further propose that the nitrate anion excited into the first singlet excited state relaxes nonradiatively into its ground state. The full understanding of the nitrate anion photolysis can improve modeling of the asymmetric solvation in the atmospheric processes, e.g., photolysis on the surfaces of ice or snow.

  15. One electron oxidation potential as a predictor of rate constants of N-containing compounds with carbonate radical and triplet excited state organic matter.

    PubMed

    Arnold, William A

    2014-04-01

    Photo-generated transient species, such as the carbonate radical and triplet excited state natural organic matter, mediate the oxidation of pollutants in various sunlit or artificially irradiated systems. In this work, one-electron oxidation potentials for 70 nitrogen-containing compounds were computed, and literature data were used to develop quantitative structure-activity relationships (QSARs) for prediction of the second order reaction rate constants with these two oxidants. For carbonate radical, separate QSARs were necessary for compounds with and without resonance stabilization of the resulting radical, and predicted rate constants were, on average, within a factor of three of experimental values. With the limited data set available, results suggest that one-electron oxidation potential is also a viable descriptor variable for predictions of rate constants with triplet excited states.

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

    SciTech Connect

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

    1992-01-01

    We present a comprehensive analysis of existing measurements of the 1s2s [sup 3]S[sub 1] [minus] 1s2p[sup 3]P[sub 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 [vert bar]Drake except for the transitions from the 1s2p [sup 3]P[sub o] state. We find a deviation equal to 2.3x(Z/10)[sup 4] cm[sup [minus]1] for the most precise existing measurements.

  17. Temperature study of indole, tryptophan and N-acetyl-L-tryptophanamide (NATA) triplet-state quenching by iodide in aqueous solution.

    PubMed

    Kowalska-Baron, Agnieszka; Gałęcki, Krystian; Wysocki, Stanisław

    2013-07-01

    In this study, the temperature dependence of the measured phosphorescence lifetimes of aqueous indole, tryptophan and N-acetyl-L-tryptophanamide (NATA) between 6 and 55 °C in the absence and in the presence of iodide, a suitable intersystem crossing enhancer, has been determined. The obtained results suggest the existence of one process for the temperature-dependent, non-radiative deactivation of triplet states of the aqueous indoles in the absence of iodide. This process may be associated with the high sensitivity of indole triplet state lifetime to the subtle changes in the local viscosity of the surrounding aqueous environment or may be attributed to diffusional quenching by solvent molecules and/or by possible impurities present in water. However, the steep decrease in the measured phosphorescence lifetimes of indole and tryptophan with temperature suggests that diffusion-mediated quenching processes are not prevailing. Upon increasing concentration of iodide (up to 0.1 M), the obtained Arrhenius plots for the deactivation rate (1/τph) of the triplet states of the studied indoles were linear, which provided strong support for the hypothesis of the existence of one temperature dependent non-radiative process for the de-excitation of indoles triplet state. Our results showed that this process is attributed to the diffusion-controlled solute-quenching by iodide and, most probably, proceeds via reversibly formed exciplex. At concentration of iodide higher than 0.1M highly curved Arrhenius plots were obtained, which may indicate a change in the rate determining step with a change in temperature. This change most probably is associated with a transition from diffusion-controlled exciplex formation followed by rate-determining exciplex deactivation at high temperature.

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

    SciTech Connect

    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.

  19. Effect of zeolite properties on ground-state and triplet-triplet absorption, prompt and oxygen induced delayed fluorescence of tetraphenylporphyrin at gas/solid interface

    NASA Astrophysics Data System (ADS)

    Levin, P. P.; Costa, Silvia M. B.; Lopes, J. M.; Serralha, F. N.; Ribeiro, F. Ramôa

    2000-08-01

    The ground-state and transient absorption, prompt and delayed fluorescence of tetraphenylporphyrin (TPP) adsorbed onto the external surface of different zeolites was monitored using diffuse-reflectance steady-state and laser flash photolysis. The delayed fluorescence (DF) of TPP detected in the presence of O 2 is attributed to the energy transfer from 3TPP to 3O 2 to form 1O 2 and subsequent energy transfer from 1O 2 to some other 3TPP within the organised molecular ensembles on the zeolite surface. The spectroscopic and kinetic parameters, namely the yield of DF (2-20% relative to prompt fluorescence), depend on the zeolite properties: the observed differences were correlated with the acid-base properties of the two zeolite series studied in this work (KA, NaA, CaA) and (NaA, NaX, NaY).

  20. Photodecomposition profiles of beta-bond cleavage of phenylphenacyl derivatives in the higher triplet excited states during stepwise two-color two-laser flash photolysis.

    PubMed

    Yamaji, Minoru; Cai, Xichen; Sakamoto, Masanori; Fujitsuka, Mamoru; Majima, Tetsuro

    2008-11-13

    Photochemical properties of p-phenylphenacyl derivatives (PP-X) having C-halide, C-S, and C-O bonds in the lowest (T 1) and higher (T n ) triplet excited states were investigated in solution by using single-color and stepwise two-color two-laser flash photolysis techniques. PP-Xs (X = Br, SH, and SPh) undergo beta-bond dissociation in the lowest singlet excited states (S 1) while the C-X bonds of other PP-Xs are stable upon 266-nm laser photolysis. The T 1(pi,pi*) states of PP-X were efficiently produced during 355-nm laser photolysis of benzophenone as a triplet sensitizer. Triplet PP-Xs deactivate to the ground state without photochemical reactions. Upon 430-nm laser photolysis of the T 1 states of PP-X (X = Br, Cl, SH, SPh, OH, OMe, and OPh), decomposition of PP-X in the T n states was found. On the basis of the changes in the transient absorption, quantum yields (Phi dec) of the decomposition of PP-X in the T n states were determined, while bond dissociation energies (BDE) of the C-X bonds were calculated by computations. According to the relationship between the Phi dec and BDE values, it was shown that the decomposition of PP-X in the T n state is due to beta-cleavage of the corresponding C-X bond, and that the state energy of the reactive T n for the C-O bond cleavage differs from that for the C-halide and C-S bond cleavage. The reaction profiles of the C-X bond cleavage of PP-X in the T n states were discussed.

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

    PubMed

    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.

  2. Neutron interferometric measurement of the scattering length difference between the triplet and singlet states of n -3He

    NASA Astrophysics Data System (ADS)

    Huber, M. G.; Arif, M.; Chen, W. C.; Gentile, T. R.; Hussey, D. S.; Black, T. C.; Pushin, D. A.; Shahi, C. B.; Wietfeldt, F. E.; Yang, L.

    2014-12-01

    We report a determination of the n -3He scattering length difference Δ b'=b1'-b0'=[-5.411 ±0.031 (statistical)±0.039 (systematic)] fm between the triplet and singlet states using a neutron interferometer. This revises our previous result Δ b'=[-5.610 ±0.027 (statistical)±0.032 (systematic)] fm obtained using the same technique in 2008 [Huber et al., Phys. Rev. Lett. 102, 200401 (2009), 10.1103/PhysRevLett.102.200401; Huber et al., Phys. Rev. Lett. 103, 179903(E) (2009), 10.1103/PhysRevLett.103.179903]. This revision is attributable to a reanalysis of the 2008 experiment that now includes a systematic correction caused by magnetic-field gradients near the 3He cell which had been previously underestimated. Furthermore, we more than doubled our original data set from 2008 by acquiring 6 months of additional data in 2013. Both the new data set and a reanalysis of the older data are in good agreement. Scattering lengths of low-Z isotopes are valued for use in few-body nuclear effective field theories, provide important tests of modern nuclear potential models, and, in the case of 3He, aid in the interpretation of neutron scattering from quantum liquids. The difference Δ b' was determined by measuring the relative phase shift between two incident neutron polarizations caused by the spin-dependent interaction with a polarized 3He target. The target 3He gas was sealed inside a small, flat-windowed glass cell that was placed in one beam path of the interferometer. The relaxation of 3He polarization was monitored continuously with neutron transmission measurements. The neutron polarization and spin-flipper efficiency were determined separately using 3He analyzers and two different polarimetry analysis methods. A summary of the measured scattering lengths for n -3He with a comparison to nucleon interaction models is given.

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

    PubMed

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

    2015-06-15

    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.

  4. 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.

    PubMed

    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

  5. A first detection of singlet to triplet conversion from the 1 1B u- to the 1 3A g state and triplet internal conversion from the 1 3A g to the 1 3B u state in carotenoids: dependence on the conjugation length

    NASA Astrophysics Data System (ADS)

    Rondonuwu, Ferdy S.; Watanabe, Yasutaka; Fujii, Ritsuko; Koyama, Yasushi

    2003-07-01

    Subpicosecond time-resolved absorption spectra were recorded in the visible region for a set of photosynthetic carotenoids having different numbers of conjugated double bonds ( n), which include neurosporene ( n=9), spheroidene ( n=10), lycopene ( n=11), anhydrorhodovibrin ( n=12) and spirilloxanthin ( n=13). Singular-value decomposition and global fitting of the spectral-data matrices lead us to a branched relaxation scheme including both (1) the singlet internal conversion in the sequence of 1 1B u+ → 1 1B u- → 2 1A g- → 1 1A g-(ground), and (2) the singlet-to-triplet conversion of 1 1B u- → 1 3A g followed by triplet internal conversion of 1 3A g → 1 3B u.

  6. Organic triplet excited states of gold(I) complexes with oligo(o- or m-phenyleneethynylene) ligands: conjunction of steady-state and time-resolved spectroscopic studies on exciton delocalization and emission pathways.

    PubMed

    Lu, Wei; Kwok, Wai-Ming; Ma, Chensheng; Chan, Chris Tsz-Leung; Zhu, Ming-Xin; Che, Chi-Ming

    2011-09-07

    governing the dual emission character of the complexes. By extrapolation from the plot of emission energy against the PE chain length of the [Au(PCy(3))](+) complexes with oligo(o-PE) or oligo(m-PE) ligands, the triplet emission energies were estimated to be ∼530 and ∼470 nm for poly(o-PE) and poly(m-PE), respectively. Additionally, we assign the unusual red shifts of 983 cm(-1) from [PhC≡CAu(PCy(3))] (1) to [μ-{1,3-(C≡C)(2)C(6)H(4)}{Au(PCy(3))}(2)] (7a) and 462 cm(-1) from 7a to [μ(3)-{1,3,5-(C≡C)(3)C(6)H(3)}{Au(PCy(3))}(3)] (8) in the phosphorescence energies to excitonic coupling interactions between the C≡CAu(PCy(3)) arms in the triplet excited states. These complexes, together with those previously reported [Au(PCy(3))](+) complexes containing oligo(p-PE) ligands ( J. Am. Chem. Soc. 2002 , 124 , 14696 - 14706 ), form a collection of oligo(phenyleneethynylene) complexes exhibiting organic triplet emission in solution under ambient conditions. The remarkable feature of these complexes in exhibiting TTA prompted DF in conjunction with high formation efficiency of T(1)((3)ππ*) affords an opportunity for emission spectra to cover a wide range of wavelengths. This may have implication in the development of PE-based molecular materials for future optical applications.

  7. Triplet properties and interactions of the primary electron donor and antenna chromophores in membranes of Heliobacterium chlorum, studied with ADMR spectroscopy.

    PubMed

    Vrieze, J; van de Meent, E J; Hoff, A J

    1998-10-20

    The triplet states of antenna and reaction center bacteriochlorophyll (BChl) g in membranes of Heliobacterium chlorum were studied by optically detected magnetic resonance in zero magnetic field, using absorbance detection. A variety of triplet states was detected, which were all localized on single BChl g chromophores as concluded from a comparison with the triplet state of monomeric BChl g in organic solvents. With the aid of the microwave-induced absorbance difference spectra, we assign a triplet state with zero-field splitting parameters |D| = 727.5 and |E| = 254. 5 MHz to that of the primary donor. The low |E| value indicates that the BChls of the primary donor are monoligated. The intensities of the zero-field transitions were strongly dependent on the redox state of the secondary electron acceptors. A triplet state with |D| = 690-705 MHz and |E| =230 MHz, present under all redox conditions, is associated with antenna BChl g absorbing at 814 nm. Its triplet yield was independent of the redox conditions; we conclude therefore that the antenna chromophores absorbing at 814 nm are not connected with the reaction center at cryogenic temperatures (1.2 K). In addition, relatively strong signals were detected belonging to triplet states with |D| and |E| of 663-680 and 220-227 MHz, respectively, whose amplitudes were dependent on the redox conditions. Triplet states with these zero-field splitting parameters are located on antenna chromophores absorbing between 798-814 nm; their zero-field transitions and absorbance difference spectra indicate a considerable heterogeneity. The concentration of triplet states of antenna chromophores absorbing around 800 nm decreased markedly upon prolonged excitation at 1.2 K. This phenomenon is attributed to quenching of excitations on antenna pigments by stable charge separation in the closely connected reaction center, possibly involving a low-quantum yield menaquinone electron acceptor.

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

    NASA Astrophysics Data System (ADS)

    Johnson, Philip M.; Sears, Trevor J.

    2015-07-01

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

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

    PubMed

    Johnson, Philip M; Sears, Trevor J

    2015-07-28

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

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

    SciTech Connect

    Johnson, Philip M.; Sears, Trevor J.

    2015-07-28

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

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

    DOE PAGES

    Johnson, Philip M.; Sears, Trevor J.

    2015-07-28

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

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

    SciTech Connect

    Johnson, Philip M.; Sears, Trevor J.

    2015-07-28

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

  13. π-Conjugated Organometallic Isoindigo Oligomer and Polymer Chromophores: Singlet and Triplet Excited State Dynamics and Application in Polymer Solar Cells.

    PubMed

    Goswami, Subhadip; Gish, Melissa K; Wang, Jiliang; Winkel, Russell W; Papanikolas, John M; Schanze, Kirk S

    2015-12-09

    An isoindigo based π-conjugated oligomer and polymer that contain cyclometalated platinum(II) "auxochrome" units were subjected to photophysical characterization, and application of the polymer in bulk heterojunction polymer solar cells with PCBM acceptor was examined. The objective of the study was to explore the effect of the heavy metal centers on the excited state properties, in particular, intersystem crossing to a triplet (exciton) state, and further how this would influence the performance of the organometallic polymer in solar cells. The materials were characterized by electrochemistry, ground state absorption, emission, and picosecond-nanosecond transient absorption spectroscopy. Electrochemical measurements indicate that the cyclometalated units have a significant impact on the HOMO energy level of the chromophores, but little effect on the LUMO, which is consistent with localization of the LUMO on the isoindigo acceptor unit. Picosecond-nanosecond transient absorption spectroscopy reveals a transient with ∼100 ns lifetime that is assigned to a triplet excited state that is produced by intersystem crossing from a singlet state on a time scale of ∼130 ps. This is the first time that a triplet state has been observed for isoindigo π-conjugated chromophores. The performance of the polymer in bulk heterojunction solar cells was explored with PC61BM as an acceptor. The performance of the cells was optimum at a relatively high PCBM loading (1:6, polymer:PCBM), but the overall efficiency was relatively low with power conversion efficiency (PCE) of 0.22%. Atomic force microscopy of blend films reveals that the length scale of the phase separation decreases with increasing PCBM content, suggesting a reason for the increase in PCE with acceptor loading. Energetic considerations show that the triplet state in the polymer is too low in energy to undergo charge separation with PCBM. Further, due to the relatively low LUMO energy of the polymer, charge transfer

  14. Zethrene biradicals: how pro-aromaticity is expressed in the ground electronic state and in the lowest energy singlet, triplet, and ionic states.

    PubMed

    Zafra, José Luis; González Cano, Rafael C; Ruiz Delgado, M Carmen; Sun, Zhe; Li, Yuan; López Navarrete, Juan T; Wu, Jishan; Casado, Juan

    2014-02-07

    A analysis of the electronic and molecular structures of new molecular materials based on zethrene is presented with particular attention to those systems having a central benzo-quinoidal core able to generate Kekulé biradicals whose stability is provided by the aromaticity recovery in this central unit. These Kekulé biradicals display singlet ground electronic states thanks to double spin polarization and have low-energy lying triplet excited states also featured by the aromaticity gain. Pro-aromatization is also the driving force for the stabilization of the ionized species. Moreover, the low energy lying singlet excited states also display a profound biradical fingerprint allowing to singlet exciton fission. These properties are discussed in the context of the size of the zethrene core and of its substitution. The work encompasses all known long zethrenes and makes use of a variety of experimental techniques, such as Raman, UV-Vis-NIR absorption, transient absorption, in situ spectroelectrochemistry and quantum chemical calculations. This study reveals how the insertion of suitable molecular modules (i.e., quinoidal) opens the door to new intriguing molecular properties exploitable in organic electronics.

  15. Zethrene biradicals: How pro-aromaticity is expressed in the ground electronic state and in the lowest energy singlet, triplet, and ionic states

    SciTech Connect

    Zafra, José Luis; González Cano, Rafael C.; Ruiz Delgado, M. Carmen; López Navarrete, Juan T.; Casado, Juan

    2014-02-07

    A analysis of the electronic and molecular structures of new molecular materials based on zethrene is presented with particular attention to those systems having a central benzo-quinoidal core able to generate Kekulé biradicals whose stability is provided by the aromaticity recovery in this central unit. These Kekulé biradicals display singlet ground electronic states thanks to double spin polarization and have low-energy lying triplet excited states also featured by the aromaticity gain. Pro-aromatization is also the driving force for the stabilization of the ionized species. Moreover, the low energy lying singlet excited states also display a profound biradical fingerprint allowing to singlet exciton fission. These properties are discussed in the context of the size of the zethrene core and of its substitution. The work encompasses all known long zethrenes and makes use of a variety of experimental techniques, such as Raman, UV-Vis-NIR absorption, transient absorption, in situ spectroelectrochemistry and quantum chemical calculations. This study reveals how the insertion of suitable molecular modules (i.e., quinoidal) opens the door to new intriguing molecular properties exploitable in organic electronics.

  16. The photoexcited triplet state of sapphyrin dication: Unusual spin alignment in monomers and spin delocalization in dimers

    SciTech Connect

    Levanon, H. |; Michaeli, S.; Regev, A.; Galili, T.; Cyr, M.; Sessler, J.L.

    1990-01-31

    Sapphyrin (Sap) and its stable dicationic form, Sap{sup 2+}, originally prepared by Woodawrd and Johnson, are large porphyrin-like systems which exhibit unique photophysical and photochemical properties. We report on the triplet diode detection, by time-resolved CW EPR, of (Sap{sup 2+}){sup T} randomly oriented in toluene (as monomers), ethanol (as dimers), and partially oriented in a nematic liquid crystal (as monomers). The substantial reduction of both zero-field splitting (ZFS) parameters (D and E) in the dimer, is interpreted in terms of spin delocalization (charge transfer) among the monomers within the dimer, (Sap{sup 2+}){sub 2}. The EPR line shape of Sap{sup 2+} in the liquid crystal suggests that, unlike other known porphyrinoid systems, the ZFS term D is associated with the in-plane alignment of the triplet spins along the C{sub 2v} symmetry axis, Z.

  17. Ground and Excited State Spectra of a Quantum Dot

    NASA Astrophysics Data System (ADS)

    Stewart, D. R.; Sprinzak, D.; Patel, S. R.; Marcus, C. M.; Duruoz, C. I.; Harris, J. S.

    1998-03-01

    We present linear and nonlinear magnetoconductance measurements of the ground and excited state spectra for successive electron occupancy in a gate defined lateral quantum dot. Previous measurementsfootnote D.R. Stewart, D. Sprinzak, C.M. Marcus, C.I. Duruoz and J.S. Harris Jr., Science 278, (1997). showed a direct correlation between the mth excited state of the N-electron system and the ground state of the (N+m)-electron system for m up to 4, consistent to a large degree with a single-particle picture. Here we report quantitative deviations of the excited state spectra from the spectrum of ground state magnetoconductances, attributed to many-body interactions in the finite system of N ~200 electrons. We also describe the behaviour of anticrossings in the ground state magnetoconductances. We acknowledge the support of JSEP (DAAH04-94-G-0058), ARO (DAAH04-95-1-0331), ONR-YIP (N00014-94-1-0622) and the NSF-PECASE program. D.S. acknowledges the support of MINERVA grant.

  18. Real-time readout and lifetime measurements of single-triplet states in a Si/SiGe double quantum dot

    NASA Astrophysics Data System (ADS)

    Prance, Jonathan; Shi, Zhan; Simmons, Christie; Savage, Don; Lagally, Max; Schreiber, Lars; Vandersypen, Lieven; Friesen, Mark; Joynt, Robert; Coppersmith, Sue; Eriksson, Mark

    2012-02-01

    The singlet and triplet states of a two-electron double quantum dot can be used as the basis for a logical qubit that combines fast gating and robust readout via Pauli spin blockade. We present measurements of the lifetimes of these states in a Si/SiGe double dot at magnetic fields between 1T and 0T [1]. The lifetimes are found by analyzing the statistics of repeated single-shot measurements of the spin state of the system. This technique allows multiple relaxation processes to be observed simultaneously. At zero magnetic field we find that all four spin states have lifetimes of approximately 10ms. With increasing magnetic field the lifetimes of the S and T0 states show no noticeable change, while the lifetime of the T- state rises, reaching 3 seconds at 1T. [1] J. R. Prance, et al., e-print: arxiv.org/abs/1110.6431

  19. Diphotons from electroweak triplet-singlet mixing

    DOE PAGES

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

    2016-08-23

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

  20. Diphotons from electroweak triplet-singlet mixing

    SciTech Connect

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

    2016-08-23

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

  1. First-principles Calculation of Excited State Spectra in QCD

    SciTech Connect

    Jozef Dudek,Robert Edwards,Michael Peardon,David Richards,Christopher Thomas

    2011-05-01

    Recent progress at understanding the excited state spectra of mesons and baryons is described. I begin by outlining the application of the variational method to compute the spectrum of QCD, and then present results for the excited meson spectrum, with continuum quantum numbers of the states clearly delineated. I emphasise the need to extend the calculation to encompass multi-hadron contributions, and describe a recent calculation of the I=2 pion-pion energy-dependent phase shifts as a precursor to the study of channels with resonant behavior. I conclude with recent results for the low lying baryon spectrum, and the prospects for future calculations.

  2. Rotational Spectra in 29 Vibrationally Excited States of Interstellar Aminoacetonitrile

    NASA Astrophysics Data System (ADS)

    Kolesniková, L.; Alonso, E. R.; Mata, S.; Alonso, J. L.

    2017-04-01

    We report a detailed spectroscopic investigation of the interstellar aminoacetonitrile, a possible precursor molecule of glycine. Using a combination of Stark and frequency-modulation microwave and millimeter wave spectroscopies, we observed and analyzed the room-temperature rotational spectra of 29 excited states with energies up to 1000 cm‑1. We also observed the 13C isotopologues in the ground vibrational state in natural abundance (1.1%). The extensive data set of more than 2000 new rotational transitions will support further identifications of aminoacetonitrile in the interstellar medium.

  3. LASER APPLICATIONS AND OTHER TOPICS IN LASER TECHNOLOGY: Influence of transitions between excited singlet and triplet states on the phase response of dye solutions

    NASA Astrophysics Data System (ADS)

    Kabanov, V. V.; Rubanov, A. S.; Tolstik, A. L.

    1988-08-01

    An investigation is made of the transitions between excited singlet and triplet states, and of the effects of stereoisomerism molecules on the light-induced change in the refractive index of a dye solution. It is shown that the contribution of the ground and excited channels to the total phase response varies within a wide range depending on the spectroscopic characteristics of the medium and the parameters of the exciting radiation. An estimate is obtained of the ratio of the contributions of the resonant and thermal nonlinearities to the total change in the refractive index.

  4. Unimolecular photodissociation dynamics of ketene (CH{sub 2}CO): The singlet/triplet branching ratio and experimental observation of the vibrational level thresholds of the transition-state

    SciTech Connect

    Kim, S.K.

    1993-05-01

    The rotational distributions of CO products from the dissociation of ketene at photolysis energies 10 cm{sup {minus}1} below, 56, 110, 200, 325, 425, 1,107, 1,435, 1,720, and 2,500 cm{sup {minus}1} above the singlet threshold, are measured in a supersonic free jet of ketene. The CO(v{double_prime} = 0) rotational distributions at 56, 110, 200, 325, and 425 cm{sup {minus}1} are bimodal. The peaks at low J`s, which are due to CO from the singlet channel, show that the product rotational distribution of CO product from ketene dissociation on the singlet surface is well described by phase space theory (PST). For CO(v{double_prime} = 0) rotational distributions at higher excess energies, the singlet and triplet contributions are not clearly resolved, and the singlet/triplet branching ratios are estimated by assuming that PST accurately predicts the CO rotational distribution from the singlet channel and that the distribution from the triplet channel changes little from that at 10 cm{sup {minus}1} below the singlet threshold. At 2,500 cm{sup {minus}1} excess energy, the CO(v{double_prime} = 1) rotational distribution is obtained, and the ratio of CO(v{double_prime} = 1) to CO(v{double_prime} = 0) products for the singlet channel is close to the variational RRKM calculation, 0.038, and the separate statistical ensembles (SSE) prediction, 0.041, but much greater than the PST prediction, 0.016. Rate constants for the dissociation of ketene (CH{sub 2}CO) and deuterated ketene (CD{sub 2}CO) have been measured at the threshold for the production of the CH(D){sub 2} and CO. Sharp peaks observed in photofragment excitation (PHOFEX) spectra probing CO (v = 0, J = 2) product are identified with the C-C-O bending mode of the transition state. RRKM calculations are carried out for two limiting cases for the dynamics of K-mixing in highly vibrationally excited reactant states.

  5. Long-lived two-dimensional triplet magnetoexcitons in a Hall insulator

    NASA Astrophysics Data System (ADS)

    Kulik, L. V.; Gorbunov, A. V.; Zhuravlev, A. S.; Timofeev, V. B.; Kukushkin, I. V.

    2016-03-01

    An experimental technique is developed to perform photoexcitation of an ensemble of translationinvariant triplet excitons, to manipulate this ensemble, and to detect the properties of its components. In particular, the influence of temperature on the radiationless decay during the relaxation of an exciton spin into the ground state of a Hall insulator at a filling factor ν = 2 is studied. The generation of photoexcited electrons and holes is controlled using photoinduced resonance reflection spectra, which makes it possible to estimate the density of light-generated electron-hole pairs and to independently control the self-consistent generation of electrons at the first Landau level and holes (vacancies) at the ground (zero) cyclotron electronic level. The existence of triplet excitons is established from inelastic light scattering spectra, which are used to determine the singlet-triplet exciton splitting. The lifetimes of triplet excitons, which are closely related to the relaxation time of an electron spin, are extremely long: they reach 100 μs in perfect GaAs/AlGaAs heterostructures with a high mobility of two-dimensional electrons at low temperatures. These long spin relaxation times are qualitatively explained, and the expected collective behavior of high-density triplet magnetoexcitons at sufficiently low temperatures, which is related to their Bose nature, is discussed.

  6. Singlet-triplet splittings and electron affinities of selected cyanocarbenes, XCCN (X = H, F, Cl, C 2H, CN): carbenes with a stable excited negative ion state

    NASA Astrophysics Data System (ADS)

    Kalcher, Josef

    2005-02-01

    The title compounds have been investigated using the ROHF-ACPF and CAS(2,2)-ACPF method in conjunction with the aug-cc-pVTZ basis sets. All cyanocarbenes have triplet ground states except FCCN and ClCCN, which conform to the halocarbenes in having singlet ground states. The ground state electron affinities are found to be rather high, i.e., 1.972, 2.061, 2.474, 3.359, 2.301 eV for HCCN, FCCN, ClCCN, C(CN) 2 and (HC 2)CCN, respectively. The existence of bound excited negative ion states has been discovered for the first time within the carbenes.

  7. Excited state mass spectra of doubly heavy Ξ baryons

    NASA Astrophysics Data System (ADS)

    Shah, Zalak; Rai, Ajay Kumar

    2017-02-01

    In this paper, the mass spectra are obtained for doubly heavy Ξ baryons, namely, Ξ _{cc}+, Ξ _{cc}^{++}, Ξ _{bb}-, Ξ _{bb}0, Ξ _{bc}0 and Ξ _{bc}+. These baryons consist of two heavy quarks ( cc, bb, and bc) with a light ( d or u) quark. The ground, radial, and orbital states are calculated in the framework of the hypercentral constituent quark model with Coulomb plus linear potential. Our results are also compared with other predictions, thus, the average possible range of excited states masses of these Ξ baryons can be determined. The study of the Regge trajectories is performed in ( n, M2) and ( J, M2) planes and their slopes and intercepts are also determined. Lastly, the ground state magnetic moments of these doubly heavy baryons are also calculated.

  8. Understanding the Photoreactivity of Dissolved Organic Carbon in Natural Waters: The Role of the Triplet Excited-State of Allochthonous and Autochthonous DOC

    NASA Astrophysics Data System (ADS)

    Cottrell, B. A.; Timko, S. A.; Robinson, A. K.; Weiden, L. M.; Cooper, W.

    2012-12-01

    The photochemical reactivity of DOC in sunlit waters is a major factor for the in situ processing of DOC itself and trace contaminants in streams, lakes and the ocean. There is an increasing interest in the use of wetlands to mitigate contaminant removal. Laser flash photolysis is used to determine the reaction rate constants of dissolved organic carbon (DOC) with emerging contaminants in natural waters. DOC, produced by the decomposition of plant and microbial material, is one of the most complex naturally occurring mixtures. DOC plays a major role in the global carbon cycle, the sequestration and transport of trace chemicals and contaminants, and the biogeochemistry of natural waters. Hydrolysis, direct photolysis and reactions with singlet oxygen and the hydroxyl radical account for up to 25% of the photo reactivity of natural organic matter. The remaining 75% is attributed to reactions with the triplet-excited state of DOC (3DOC*). In this study, 1H NMR is used to characterize DOC from the Black River (NC), the San Joaquin Wetlands (Irvine, CA), and coastal seawater (Crystal Cove, CA). These sites encompass both allochthonous and autochthonous organic matter from catchment, wetlands, and marine waters. We then determine the reaction rate constants of known triplet state reactants and pharmaceuticals with the 3DOC* in the natural waters and with the DOC isolated by solid phase extraction. Studies of 3DOC* could provide a measure of DOC reactivity, essential in the design of constructed wetlands for contaminant removal.

  9. Time-resolved photoelectron spectroscopy of a dinuclear Pt(II) complex: Tunneling autodetachment from both singlet and triplet excited states of a molecular dianion

    SciTech Connect

    Winghart, Marc-Oliver Unterreiner, Andreas-Neil; Yang, Ji-Ping; Vonderach, Matthias; Huang, Dao-Ling; Wang, Lai-Sheng; Kruppa, Sebastian; Riehn, Christoph; Kappes, Manfred M.

    2016-02-07

    Time-resolved pump-probe photoelectron spectroscopy has been used to study the relaxation dynamics of gaseous [Pt{sub 2}(μ-P{sub 2}O{sub 5}H{sub 2}){sub 4} + 2H]{sup 2−} after population of its first singlet excited state by 388 nm femtosecond laser irradiation. In contrast to the fluorescence and phosphorescence observed in condensed phase, a significant fraction of the photoexcited isolated dianions decays by electron loss to form the corresponding monoanions. Our transient photoelectron data reveal an ultrafast decay of the initially excited singlet {sup 1}A{sub 2u} state and concomitant rise in population of the triplet {sup 3}A{sub 2u} state, via sub-picosecond intersystem crossing (ISC). We find that both of the electronically excited states are metastably bound behind a repulsive Coulomb barrier and can decay via delayed autodetachment to yield electrons with characteristic kinetic energies. While excited state tunneling detachment (ESETD) from the singlet {sup 1}A{sub 2u} state takes only a few picoseconds, ESETD from the triplet {sup 3}A{sub 2u} state is much slower and proceeds on a time scale of hundreds of nanoseconds. The ISC rate in the gas phase is significantly higher than in solution, which can be rationalized in terms of changes to the energy dissipation mechanism in the absence of solvent molecules. [Pt{sub 2}(μ-P{sub 2}O{sub 5}H{sub 2}){sub 4} + 2H]{sup 2−} is the first example of a photoexcited multianion for which ESETD has been observed following ISC.

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

    PubMed

    Schmidt, Reinhard

    2006-05-11

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

  11. Quasiclassical asymptotics and coherent states for bounded discrete spectra

    SciTech Connect

    Gorska, K.; Penson, K. A.; Horzela, A.; Blasiak, P.; Duchamp, G. H. E.; Solomon, A. I.

    2010-12-15

    We consider discrete spectra of bound states for nonrelativistic motion in attractive potentials V{sub {sigma}}(x)=-|V{sub 0}| |x|{sup -}{sigma}, 0<{sigma}{<=}2. For these potentials the quasiclassical approximation for n{yields}{infinity} predicts quantized energy levels e{sub {sigma}}(n) of a bounded spectrum varying as e{sub {sigma}}(n){approx}-n{sup -}2{sigma}/(2-{sigma}). We construct collective quantum states using the set of wavefunctions of the discrete spectrum assuming this asymptotic behavior. We give examples of states that are normalizable and satisfy the resolution of unity, using explicit positive functions. These are coherent states in the sense of Klauder and their completeness is achieved via exact solutions of Hausdorff moment problems, obtained by combining Laplace and Mellin transform methods. For {sigma} in the range 0 < {sigma}{<=} 2/3 we present exact implementations of such states for the parametrization {sigma}= 2(k-l)/(3k-l) with k and l positive integers satisfying k>l.

  12. Favorable performance of the DFT methods in predicting the minimum-energy structure of the lowest triplet state of WF{sub 4}

    SciTech Connect

    Gutowski, M. |

    1999-06-15

    The tetrahedral structure of the lowest triplet state of the WF{sub 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{sub 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{sub 2v} leads to a minimum on the lowest triplet potential energy surface and the electronic energy difference between the T{sub d} and C{sub 2v} stationary points amounts to 0.85 and 0.96 kcal/mol at the B3LYP and CCSD(T) levels, respectively.

  13. Triplet absorption spectroscopy and electromagnetically induced transparency

    NASA Astrophysics Data System (ADS)

    Ghafoor, F.; Nazmitdinov, R. G.

    2016-09-01

    Coherence phenomena in a four-level atomic system, cyclically driven by three coherent fields, are investigated thoroughly at zero and weak magnetic fields. Each strongly interacting atomic state is converted to a triplet due to a dynamical Stark effect. Two dark lines with a Fano-like profile arise in the triplet absorption spectrum with anomalous dispersions. We provide conditions to control the widths of the transparency windows by means of the relative phase of the driving fields and the intensity of the microwave field, which closes the optical system loop. The effect of Doppler broadening on the results of the triplet absorption spectroscopy is analysed in detail.

  14. On the Photoelectron Spectra of Li4

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Arnold, James O. (Technical Monitor)

    1996-01-01

    The most stable structure for Li4(-) is found to be the rhombus. Electron detachment from this structure does not seem able to fully explain the photoelectron spectra. The computed results are consistent with those Rao, Jena, and Ray who have proposed that the experimental spectra consists of a superposition of detachment from the Li4(-) rhombus and tetrahedron, forming the singlet and triplet states of Li4, respectively.

  15. The predicted spectrum and singlet-triplet interaction of the hypermetallic molecule SrOSr.

    PubMed

    Ostojić, B; Jensen, Per; Schwerdtfeger, P; Bunker, P R

    2013-10-03

    In accordance with previous studies in our group on Be, Mg, and Ca hypermetallic oxides, we find that SrOSr has a linear X̃1Σ(g)+ ground electronic state and a very low lying first excited ã3Σ(u)+ triplet electronic state. No gas-phase spectrum of this molecule has been assigned yet, and to encourage and assist in its discovery we present a complete ab initio simulation, with absolute intensities, of the infrared absorption spectrum for both electronic states. The three-dimensional potential energy surfaces and the electric dipole moment surfaces of the X̃1Σ(g)+ and ã3Σ(u)+ electronic states are calculated using a multireference configuration interaction (MRCISD) approach in combination with internally contracted multireference perturbation theory (RS2C) based on complete active space self-consistent field (CASSCF) wave functions applying a Sadlej pVTZ basis set for both O and Sr and the Stuttgart relativistic small-core effective core potential for Sr. The infrared spectra are simulated using the MORBID program system. We also calculate vertical excitation energies and transition moments for several excited singlet and triplet electronic states in order to predict the positions and intensities of the most prominent singlet and triplet electronic absorption bands. Finally, for this heavy molecule, we calculate the singlet–triplet interaction matrix elements between close-lying vibronic levels of the X̃ and ã electronic states and find them to be very small.

  16. Assignment of IR bands of isolated and protein-bound Peridinin in its fundamental and triplet state by static FTIR, time-resolved step-scan FTIR and DFT calculations

    NASA Astrophysics Data System (ADS)

    Mezzetti, Alberto; Kish, Elizabeth; Robert, Bruno; Spezia, Riccardo

    2015-06-01

    The vibrational properties of Peridinin in its fundamental state and in the excited triplet state have been investigated by DFT calculations and static and time-resolved FTIR spectroscopy. The infrared spectrum of Peridinin in its fundamental state has been explored in the whole 2000-600 cm-1 range, and interpreted in term of molecular vibrations. In particular, new infrared bands have been identified and assigned to specific molecular vibrations. 3Peridinin molecular vibrations have also been investigated by DFT calculations. In addition, putative IR bands belonging to Peridinin and 3Peridinin have been identified in the step-scan FTIR difference spectrum of the Peridinin-Chlorophyll a-Protein from Amphidinium carterae, where light induce formation of a triplet state localized on one or more Peridinins. The exact nature of the triplet state formed in Peridinin-Chlorophyll a-Protein from dinoflagellates, in particular the possible involvement in this triplet state of 3Chlorophyll a, has been largely debated in the last few years (see Carbonera et al., 2014 [3]); time-resolved differential FTIR experiments have played a key role in this debate. Identification of IR marker bands for the main molecule (Peridinin) implicated in this photophysical process is therefore particularly important and makes this study a significant step towards the full understanding of Peridinin-Chlorophyll-a-Proteins photophysics.

  17. Determination of the spin triplet p Λ scattering length from the final state interaction in the p ⃗p →p K+Λ reaction

    NASA Astrophysics Data System (ADS)

    Hauenstein, F.; Borodina, E.; Clement, H.; Doroshkevich, E.; Dzhygadlo, R.; Ehrhardt, K.; Eyrich, W.; Gast, W.; Gillitzer, A.; Grzonka, D.; Haidenbauer, J.; Hanhart, C.; Jowzaee, S.; Kilian, K.; Klaja, P.; Kober, L.; Krapp, M.; Mertens, M.; Moskal, P.; Ritman, J.; Roderburg, E.; Röder, M.; Schroeder, W.; Sefzick, T.; Wintz, P.; Wüstner, P.; COSY-TOF Collaboration

    2017-03-01

    The p ⃗p →p K+Λ reaction has been measured with the COSY-TOF detector at a beam momentum of 2.7 GeV /c . The polarized proton beam enables the measurement of the beam analyzing power by the asymmetry of the produced kaon (ANK). This observable allows the p Λ spin triplet scattering length to be extracted for the first time model independently from the final state interaction in the reaction. The obtained value is at=(-2 .55-1.39+0.72stat .±0 .6syst .±0 .3theo .) fm . This value is compatible with theoretical predictions and results from model-dependent analyses.

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

    NASA Astrophysics Data System (ADS)

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

    2014-11-01

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

  19. Excited state absorption spectra and intersystem crossing kinetics in diazanaphthalenes

    NASA Astrophysics Data System (ADS)

    Scott, Gary W.; Talley, Larry D.; Anderson, Robert W.

    1980-05-01

    Picosecond time-resolved, excited state absorption spectra in the visible following excitation at 355 nm are discussed for room temperature solutions of four diazanaphthalenes (DN)—quinoxaline (1,4-DN), quinazoline (1,3-DN), cinnoline (1,2-DN), and phthalazine (2,3-DN). Kinetics of singlet state decay are obtained by monitoring the decay of Sn←S1 bands. The intersystem crossing rate constant (kisc) is found to vary as kisc(1,4-DN)≳kisc(1,3-DN)≳kisc(1,2-DN). The kisc in phthalazine could not be determined from the weak, visible Sn←S1 absorption. Assuming rapid singlet vibrational relaxation and only minor effects due to energy gap variations, these experimental results agree with statistical limit predictions for the relative nonradiative rate. Calculations of the spin-orbit coupling matrix element βel= , using INDO wave functions, give the ordering βel(1,4-DN)≳βel(2,3-DN)≳βel(1,3-DN) ≳βel(1,2-DN).

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

    PubMed

    Kvíčalová, Zuzana; Alster, Jan; Hofmann, Eckhard; Khoroshyy, Petro; Litvín, Radek; Bína, David; Polívka, Tomáš; Pšenčík, Jakub

    2016-04-01

    Room temperature transient absorption spectroscopy with nanosecond resolution was used to study quenching of the chlorophyll triplet states by carotenoids in two light-harvesting complexes of the dinoflagellate Amphidinium carterae: the water soluble peridinin-chlorophyll protein complex and intrinsic, membrane chlorophyll a-chlorophyll c2-peridinin protein complex. The combined study of the two complexes facilitated interpretation of a rather complicated relaxation observed in the intrinsic complex. While a single carotenoid triplet state was resolved in the peridinin-chlorophyll protein complex, evidence of at least two different carotenoid triplets was obtained for the intrinsic light-harvesting complex. Most probably, each of these carotenoids protects different chlorophylls. In both complexes the quenching of the chlorophyll triplet states by carotenoids occurs with a very high efficiency (~100%), and with transfer times estimated to be in the order of 0.1ns or even faster. The triplet-triplet energy transfer is thus much faster than formation of the chlorophyll triplet states by intersystem crossing. Since the triplet states of chlorophylls are formed during the whole lifetime of their singlet states, the apparent lifetimes of both states are the same, and observed to be equal to the carotenoid triplet state rise time (~5ns).

  1. Simultaneous analysis of the Ballik-Ramsay and Phillips systems of C2 and observation of forbidden transitions between singlet and triplet states

    NASA Astrophysics Data System (ADS)

    Chen, Wang; Kawaguchi, Kentarou; Bernath, Peter F.; Tang, Jian

    2015-02-01

    6229 lines of the Ballik-Ramsay system (b3Σg--a3Πu) and the Phillips system (A1Πu-X1Σg+) of C2 up to v = 8 and J = 76, which were taken from the literature or assigned in the present work, were analyzed simultaneously by least-squares fitting with 82 Dunham-like molecular parameters and spin-orbit interaction constants between the b3Σg- and X1Σg+ states with a standard deviation of 0.0037 cm-1 for the whole data set. As a result of the deperturbation analysis, the spin-orbit interaction constant AbX was determined as 6.333(7) cm-1 and the energy difference between the X1Σg+ and a3Πu states was determined as 720.008(2) cm-1 for the potential minima or 613.650(3) cm-1 for the v = 0 levels with Merer and Brown's N2 Hamiltonian for 3Π states, which is about 3.3 cm-1 larger than the previously determined value. Due to this sizable change, a new energy-level crossing was found at J = 2 for v = 3 (F1) of b3Σg- state and v = 6 of X1Σg+ state, where the strong interaction causes a nearly complete mixing of the wave functions of the b3Σg- and X1Σg+ states and the forbidden transitions become observable. Using the predictions of our deperturbation analysis, we were able to identify 16 forbidden transitions between the singlet and triplet states at the predicted frequencies with the expected intensities, which verifies our value for the energy difference between the X1Σg+ and a3Πu states.

  2. Simultaneous analysis of the Ballik-Ramsay and Phillips systems of C2 and observation of forbidden transitions between singlet and triplet states.

    PubMed

    Chen, Wang; Kawaguchi, Kentarou; Bernath, Peter F; Tang, Jian

    2015-02-14

    6229 lines of the Ballik-Ramsay system (b(3)Σg (-)-a(3)Πu) and the Phillips system (A(1)Πu-X(1)Σg (+)) of C2 up to v = 8 and J = 76, which were taken from the literature or assigned in the present work, were analyzed simultaneously by least-squares fitting with 82 Dunham-like molecular parameters and spin-orbit interaction constants between the b(3)Σg (-) and X(1)Σg (+) states with a standard deviation of 0.0037 cm(-1) for the whole data set. As a result of the deperturbation analysis, the spin-orbit interaction constant AbX was determined as 6.333(7) cm(-1) and the energy difference between the X(1)Σg (+) and a(3)Πu states was determined as 720.008(2) cm(-1) for the potential minima or 613.650(3) cm(-1) for the v = 0 levels with Merer and Brown's N(2) Hamiltonian for (3)Π states, which is about 3.3 cm(-1) larger than the previously determined value. Due to this sizable change, a new energy-level crossing was found at J = 2 for v = 3 (F1) of b(3)Σg (-) state and v = 6 of X(1)Σg (+) state, where the strong interaction causes a nearly complete mixing of the wave functions of the b(3)Σg (-) and X(1)Σg (+) states and the forbidden transitions become observable. Using the predictions of our deperturbation analysis, we were able to identify 16 forbidden transitions between the singlet and triplet states at the predicted frequencies with the expected intensities, which verifies our value for the energy difference between the X(1)Σg (+) and a(3)Πu states.

  3. Triplet-triplet energy transfer between luminescent probes bound to albumins

    NASA Astrophysics Data System (ADS)

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

    2010-08-01

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

  4. Statistical equilibrium in cometary C2. III - Triplet-singlet, Phillips, Ballik-Ramsay, and Mulliken bands

    NASA Technical Reports Server (NTRS)

    Swamy, K. S. K.; Odell, C. R.

    1981-01-01

    A new series of vibrational bands is predicted which arises from transitions between the lowest electron states of the triplet and singlet states of homonuclear C2. The predictions are useful for C2 identifications and for disentangling congested low resolution spectra that characterize new observations. Predictions are also made for Mulliken, Phillips, and Ballik-Ramsay band sequences, and all calculations are made with the assumed molecular constants and computational methods of KSO-II.

  5. Degradation of organic pollutants in/on snow and ice by singlet molecular oxygen (¹O₂*) and an organic triplet excited state.

    PubMed

    Bower, Jonathan P; Anastasio, Cort

    2014-04-01

    Singlet molecular oxygen (¹O₂*) can be a significant sink for a variety of electron-rich pollutants in surface waters and atmospheric drops. We recently found that ¹O₂* concentrations are enhanced by up to a factor of 10(4) on illuminated ice compared to in the equivalent liquid solution, suggesting that ¹O₂* could be an important oxidant for pollutants in snow. To examine this, here we study the degradation of three model organic pollutants: furfuryl alcohol (to represent furans), tryptophan (for aromatic amino acids), and bisphenol A (for phenols). Each compound was studied in illuminated aqueous solution and ice containing Rose Bengal (RB, a sensitizer for ¹O₂*) and sodium chloride (to adjust the concentration of total solutes). The RB-mediated loss of each organic compound is enhanced on illuminated ice compared to in solution, by factors of 6400 for furfuryl alcohol, 8300 for tryptophan, and 50 for bisphenol A for ice containing 0.065 mM total solutes. Rates of loss of furfuryl alcohol and tryptophan decrease at a higher total solute concentration, in qualitative agreement with predictions from freezing-point depression. In contrast, the loss of bisphenol A on ice is independent of total solute concentration. Relative to liquid tests, the enhanced loss of tryptophan on ice during control experiments made with deoxygenated solutions and solutions in D₂O show that the triplet excited state of Rose Bengal may also contribute to loss of pollutants on ice.

  6. Far infrared spectra of solid state aliphatic amino acids in different protonation states.

    PubMed

    Trivella, Aurélien; Gaillard, Thomas; Stote, Roland H; Hellwig, Petra

    2010-03-21

    Far infrared spectra of zwitterionic, cationic, and anionic forms of aliphatic amino acids in solid state have been studied experimentally. Measurements were done on glycine, L-alanine, L-valine, L-leucine, and L-isoleucine powder samples and film samples obtained from dried solutions prepared at pH ranging from 1 to 13. Solid state density functional theory calculations were also performed, and detailed potential energy distributions were obtained from normal mode results. A good correspondence between experimental and simulated spectra was achieved and this allowed us to propose an almost complete band assignment for the far infrared spectra of zwitterionic forms. In the 700-50 cm(-1) range, three regions were identified, each corresponding to a characteristic set of normal modes. A first region between 700 and 450 cm(-1) mainly contained the carboxylate bending, rocking, and wagging modes as well as the ammonium torsional mode. The 450-250 cm(-1) region was representative of backbone and sidechain skeletal bending modes. At last, the low wavenumber zone, below 250 cm(-1), was characteristic of carboxylate and skeletal torsional modes and of lattice modes. Assignments are also proposed for glycine cationic and anionic forms, but could not be obtained for all aliphatic amino acids due to the lack of structural data. This work is intended to provide fundamental information for the understanding of peptides vibrational properties.

  7. Simultaneous analysis of the Ballik-Ramsay and Phillips systems of C{sub 2} and observation of forbidden transitions between singlet and triplet states

    SciTech Connect

    Chen, Wang; Kawaguchi, Kentarou; Tang, Jian; Bernath, Peter F.

    2015-02-14

    6229 lines of the Ballik-Ramsay system (b{sup 3}Σ{sub g}{sup −}–a{sup 3}Π{sub u}) and the Phillips system (A{sup 1}Π{sub u}–X{sup 1}Σ{sub g}{sup +}) of C{sub 2} up to v = 8 and J = 76, which were taken from the literature or assigned in the present work, were analyzed simultaneously by least-squares fitting with 82 Dunham-like molecular parameters and spin-orbit interaction constants between the b{sup 3}Σ{sub g}{sup −} and X{sup 1}Σ{sub g}{sup +} states with a standard deviation of 0.0037 cm{sup −1} for the whole data set. As a result of the deperturbation analysis, the spin-orbit interaction constant A{sub bX} was determined as 6.333(7) cm{sup −1} and the energy difference between the X{sup 1}Σ{sub g}{sup +} and a{sup 3}Π{sub u} states was determined as 720.008(2) cm{sup −1} for the potential minima or 613.650(3) cm{sup −1} for the v = 0 levels with Merer and Brown’s N{sup 2} Hamiltonian for {sup 3}Π states, which is about 3.3 cm{sup −1} larger than the previously determined value. Due to this sizable change, a new energy-level crossing was found at J = 2 for v = 3 (F{sub 1}) of b{sup 3}Σ{sub g}{sup −} state and v = 6 of X{sup 1}Σ{sub g}{sup +} state, where the strong interaction causes a nearly complete mixing of the wave functions of the b{sup 3}Σ{sub g}{sup −} and X{sup 1}Σ{sub g}{sup +} states and the forbidden transitions become observable. Using the predictions of our deperturbation analysis, we were able to identify 16 forbidden transitions between the singlet and triplet states at the predicted frequencies with the expected intensities, which verifies our value for the energy difference between the X{sup 1}Σ{sub g}{sup +} and a{sup 3}Π{sub u} states.

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

    PubMed

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

    2014-01-01

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

  9. Mapping Agricultural Crops with AVIRIS Spectra in Washington State

    NASA Technical Reports Server (NTRS)

    Green, Robert; Pavri, Betina; Roberts, Dar; Ustin, Susan

    1998-01-01

    Spectroscopy is used in the laboratory to measure the molecular components and concentrations of plant constituents to answer questions about the plant type, status, and health. Imaging spectrometers measure the upwelling spectral radiance above the Earth's surface as images. Ideally, imaging spectrometer data sets should be used to understand plant type, plant status, and health of plants in an agricultural setting. An Airborne Visible/Infrared Imaging Spectrometer (AVIRIS) data set was acquired over agricultural fields near Wallula, Washington on July 23rd, 1997. AVIRIS measures upwelling radiance spectra through 224 spectral channels with contiguous 10-nm sampling from 400 to 2500 nm in the solar-reflected spectrum. The spectra are measured as images of 11 by up to 800 km with 20-m spatial resolution. The spectral images measured by AVIRIS represent the integrated signal resulting from: the solar irradiance; two way transmittance and scattering of the atmosphere; the absorptions and scattering of surface materials; as well as the spectral, radiometric and spatial response functions of AVIRIS. This paper presents initial research to derive properties of the agricultural fields near Wallula from the calibrated spectral images measured by AVIRIS near the top of the atmosphere.

  10. Mapping Agricultural Crops with AVIRIS Spectra in Washington State

    NASA Technical Reports Server (NTRS)

    Green, Robert O.; Pavri, Betina; Roberts, Dar; Ustin, Susan

    2000-01-01

    Spectroscopy is used in the laboratory to measure the molecular components and concentrations of plant constituents to answer questions about the plant type, status, and health. Imaging spectrometers measure the upwelling spectral radiance above the Earth's surface as images. Ideally, imaging spectrometer data sets should be used to understand plant type, plant status, and health of plants in an agricultural setting. An Airborne Visible/Infrared Imaging Spectrometer (AVIRIS) data set was acquired over agricultural fields near Wallula, Washington on July 23rd, 1997. AVIRIS measures upwelling radiance spectra through 224 spectral channels with contiguous 10-nm sampling from 400 to 2500 run in the solar-reflected spectrum. The spectra are measured as images of 11 by up to 800 km with 20-m spatial resolution. The spectral images measured by AVIRIS represent the integrated signal resulting from: the solar irradiance; two way transmittance and scattering of the atmosphere; the absorptions and scattering of surface materials; as well as the spectral, radiometric and spatial response functions of AVIRIS. This paper presents initial research to derive properties of the agricultural fields near Wallula from the calibrated spectral images measured by AVIRIS near the top of the atmosphere.

  11. Excited State Mass Spectra of Ω0 c Baryon

    NASA Astrophysics Data System (ADS)

    Shah, Z.; Thakkar, K.; Rai, A. K.; Vinodkumar, P. C.

    2016-10-01

    We have calculated the radial and orbital excited states of singly charmed baryon Oc using the Hypercentral Constituent Quark Model (hCQM). The confinement potential is assumed as coulomb plus power potential (CPP V ). The ground state and excited state masses are determined with and with out first order correction to the potential. Furthermore, we plot graph between Mass(M) → Potential Index(v). Our calculated results are in good agreement with experimental and other theoretical predictions.

  12. Chemical characterization of SOA formed from aqueous-phase reactions of phenols with the triplet excited state of carbonyl and hydroxyl radical

    SciTech Connect

    Yu, Lu; Smith, Jeremy; Laskin, Alexander; Anastasio, Cort N.; Laskin, Julia; Zhang, Qi

    2014-01-01

    Phenolic compounds, which are emitted in significant amounts from biomass burning, can undergo fast reactions in atmospheric aqueous phases to form secondary organic aerosol (aqSOA). In this study, we investigate the reactions of phenol and two methoxy-phenols (syringol and guaiacol) with two major aqueous phase oxidants – the triplet excited states of an aromatic carbonyl (3C*) and hydroxyl radical (•OH). We thoroughly characterize the low-volatility species produced from these reactions and interpret their formation mechanisms using aerosol mass spectrometry (AMS), desorption electrospray ionization mass spectrometry (DESIMS), and ion chromatography (IC). A large number of oxygenated molecules are identified, including oligomers containing up to six monomer units, functionalized monomer and oligomers with carbonyl, carboxyl, and hydroxyl groups, and small organic acid anions (e.g., formate, acetate, oxalate, and malate). The average atomic oxygen-to-carbon (O/C) ratios of phenolic aqSOA are in the range of 0.85-1.23, similar to those of low-volatility oxygenated organic aerosol (LV-OOA) observed in ambient air. The aqSOA compositions are overall similar for the same precursor, but the reactions mediated by 3C* are faster than •OH-mediated reactions and produce more oligomers and hydroxylated species at the point when 50% of the phenol had reacted. Profiles determined using a thermodenuder indicate that the volatility of phenolic aqSOA is influenced by both oligomer content and O/C ratio. In addition, the aqSOA shows enhanced light absorption in the UV-vis region, suggesting that aqueous-phase reactions of phenols are likely an important source of brown carbon in the atmosphere, especially in regions influenced by biomass burning.

  13. Chemical characterization of SOA formed from aqueous-phase reactions of phenols with the triplet excited state of carbonyl and hydroxyl radical

    DOE PAGES

    Yu, L.; Smith, J.; Laskin, A.; ...

    2014-08-19

    Phenolic compounds, which are emitted in significant amounts from biomass burning, can undergo fast reactions in atmospheric aqueous phases to form secondary organic aerosol (aqSOA). In this study, we investigate the reactions of phenol and two methoxy-phenols (syringol and guaiacol) with two major aqueous phase oxidants – the triplet excited states of an aromatic carbonyl (3C*) and hydroxyl radical (·OH). We thoroughly characterize the low-volatility species produced from these reactions and interpret their formation mechanisms using aerosol mass spectrometry (AMS), nanospray desorption electrospray ionization mass spectrometry (nano-DESI MS), and ion chromatography (IC). A large number of oxygenated molecules are identified,more » including oligomers containing up to six monomer units, functionalized monomer and oligomers with carbonyl, carboxyl, and hydroxyl groups, and small organic acid anions (e.g., formate, acetate, oxalate, and malate). The average atomic oxygen-to-carbon (O / C) ratios of phenolic aqSOA are in the range of 0.85–1.23, similar to those of low-volatility oxygenated organic aerosol (LV-OOA) observed in ambient air. The aqSOA compositions are overall similar for the same precursor, but the reactions mediated by 3C* are faster than ·OH-mediated reactions and produce more oligomers and hydroxylated species at the point when 50% of the phenol had reacted. Profiles determined using a thermodenuder indicate that the volatility of phenolic aqSOA is influenced by both oligomer content and O / C ratio. In addition, the aqSOA shows enhanced light absorption in the UV-vis region, suggesting that aqueous-phase reactions of phenols are likely an important source of brown carbon in the atmosphere, especially in regions influenced by biomass burning.« less

  14. Chemical characterization of SOA formed from aqueous-phase reactions of phenols with the triplet excited state of carbonyl and hydroxyl radical

    DOE PAGES

    Yu, L.; Smith, J.; Laskin, A.; ...

    2014-12-23

    Phenolic compounds, which are emitted in significant amounts from biomass burning, can undergo fast reactions in atmospheric aqueous phases to form secondary organic aerosol (aqSOA). In this study, we investigate the reactions of phenol (compound with formula C6H5OH)), guaiacol (2-methoxyphenol), and syringol (2,6-dimethoxyphenol) with two major aqueous-phase oxidants – the triplet excited states of an aromatic carbonyl (3C*) and hydroxyl radical (· OH). We thoroughly characterize the low-volatility species produced from these reactions and interpret their formation mechanisms using aerosol mass spectrometry (AMS), nanospray desorption electrospray ionization mass spectrometry (nano-DESI MS), and ion chromatography (IC). A large number of oxygenatedmore » molecules are identified, including oligomers containing up to six monomer units, functionalized monomer and oligomers with carbonyl, carboxyl, and hydroxyl groups, and small organic acid anions (e.g., formate, acetate, oxalate, and malate). The average atomic oxygen-to-carbon (O / C) ratios of phenolic aqSOA are in the range of 0.85–1.23, similar to those of low-volatility oxygenated organic aerosol (LV-OOA) observed in ambient air. The aqSOA compositions are overall similar for the same precursor, but the reactions mediated by 3C* are faster than · OH-mediated reactions and produce more oligomers and hydroxylated species at the point when 50% of the phenolic compound has reacted. Profiles determined using a thermodenuder indicate that the volatility of phenolic aqSOA is influenced by both oligomer content and O / C ratio. In addition, the aqSOA shows enhanced light absorption in the UV–visible region, suggesting that aqueous-phase reactions of phenols may contribute to formation of secondary brown carbon in the atmosphere, especially in regions influenced by biomass burning.« less

  15. Photochemical properties of C 60. Triplet-excited C 60 quenching by electron acceptors TCNQ and TCNE in solution. Laser photolysis study

    NASA Astrophysics Data System (ADS)

    Nadtochenko, Victor A.; Denisov, Nikolai N.; Rubtsov, Igor V.; Lobach, Anatolii S.; Moravskii, Alexander P.

    1993-06-01

    The quenching of triplet-excited 3C 60 by electron acceptors TCNQ and TCNE has been established in nonpolar toluene and moderately polar benzonitrile solutions. The quenching constants kq are 5.5 × 10 9 in toluene, 2.2 × 10 9 in benzonitrile for TCNQ and 7.9 × 10 5 in toluene, 4.2 × 10 8 (M s) -1 in benzonitrile for TCNE. The 3C 60 quenching can be explained by triplet exciplex formation. The time-resolved spectra of the C 60/TCNE system exhibit a well pronounced charge-transfer excited state [C δ60 … TCNE δ-] in benzonitrile.

  16. Bandgaps of zigzag finite-length nanotubes ab initio calculations: ground state degeneracy and single-electron spectra

    NASA Astrophysics Data System (ADS)

    Mestechkin, Mikhail; Zubkov, Vladimir

    2005-05-01

    Different versions of ab initio quantum chemical models (cluster and periodic boundary conditions approximations) have been used to analyze the effect of finite length and the partial filling of the highest occupied orbital on the band-gaps of carbon nanotubes. In agreement with the previous calculations in the tight-binding approximation and pi-electron open shell model, it has been shown that the ground state of the nanotube with the zigzag structure is triplet. It has been confirmed that these tubes exhibit metallic or semiconductor properties with a very narrow half-filled conduction band. The band-gap is of order few tens of eV, and it is estimated that approximately 0.1-0.2% of pi-electrons belong to the conduction band of finite zigzag nanotubes. The triplet state is predicted to be the ground state of finite-length carbon nanotubes.

  17. Intramolecular triplet energy transfer in anthracene-based platinum acetylide oligomers.

    PubMed

    Li, Yongjun; Köse, Muhammet E; Schanze, Kirk S

    2013-08-01

    Platinum acetylide oligomers that contain an anthracene moiety have been synthesized and subjected to photophysical characterization. Spectroscopic measurement and DFT calculations reveal that both the singlet and triplet energy levels of the anthracene segment are lower than those of the platinum acetylide segment. Thus, the platinum acetylide segment acts as a sensitizer to populate the triplet state of the anthrancene segment via intramolecular triplet-triplet energy transfer. The objective of this work is to understand the mechanisms of energy-transfer dynamics in these systems. Fluorescence quenching and the dominant triplet absorption that arises from the anthracene segment in the transient absorption spectrum of Pt4An give clear evidence that energy transfer adopts an indirect mechanism, which begins with singlet-triplet energy transfer from the anthracene segment to the platinum acetylide segment followed by triplet-triplet energy transfer to the anthracene segment.

  18. Equilibrium excited state and emission spectra of molecular aggregates from the hierarchical equations of motion approach.

    PubMed

    Jing, Yuanyuan; Chen, Liping; Bai, Shuming; Shi, Qiang

    2013-01-28

    The hierarchical equations of motion (HEOM) method was applied to calculate the emission spectra of molecular aggregates using the Frenkel exciton model. HEOM equations for the one-exciton excited state were first propagated until equilibration. The reduced density operator and auxiliary density operators (ADOs) were used to characterize the coupled system-bath equilibrium. The dipole-dipole correlation functions were then calculated to obtain the emission spectra of model dimers, and the B850 band of light-harvesting complex II (LH2) in purple bacteria. The effect of static disorder on equilibrium excited state and the emission spectra of LH2 was also explicitly considered. Several approximation schemes, including the high temperature approximation (HTA) of the HEOM, a modified version of the HTA, the stochastic Liouville equation approach, the perturbative time-local and time-nonlocal generalized quantum master equations, were assessed in the calculation of the equilibrium excited state and emission spectra.

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

    NASA Astrophysics Data System (ADS)

    Zhang, Yifan; Forrest, Stephen R.

    2013-12-01

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

  20. System diagnosability using triplet assertion

    SciTech Connect

    Lombardi, F.

    1982-01-01

    A new technique for system diagnosability is presented. It is based on a triplet assertion strategy to overcome the asymmetric invalidation and the requirement of a central test controller. The basic characteristics of the triplet assertion are generalized to higher networks. The application of this technique to parallel processing is outlined. 24 references.

  1. Rotational spectra of the X 2Sigma(+) states of CaH and CaD

    NASA Technical Reports Server (NTRS)

    Frum, C. I.; Oh, J. J.; Cohen, E. A.; Pickett, H. M.

    1993-01-01

    The rotational spectra of the 2Sigma(2+) ground states of calcium monohydride and monodeuteride have been recorded in absorption between 250 and 700 GHz. The gas phase free radicals have been produced in a ceramic furnace by the reaction of elemental calcium with molecular hydrogen or deuterium in the presence of an electrical discharge. The molecular constants including the rotational constant, centrifugal distortion constants, spin-rotation constants, and magnetic hyperfine interaction constants have been extracted from the spectra.

  2. Experimental Study of the Triplet Synchronization of Coupled Nonidentical Mechanical Metronomes

    PubMed Central

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

    2015-01-01

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

  3. Observation of the Triplet Metastable State of Shallow Donor Pairs in AlN Crystals with a Negative-U Behavior: A High-Frequency EPR and ENDOR Study

    NASA Astrophysics Data System (ADS)

    Orlinskii, Sergei B.; Schmidt, Jan; Baranov, Pavel G.; Bickermann, Matthias; Epelbaum, Boris M.; Winnacker, Albrecht

    2008-06-01

    Theoretical predictions about the n-type conductivity in nitride semiconductors are discussed in the light of results of a high-frequency EPR an ENDOR study. It is shown that two types of effective-mass-like, shallow donors with a delocalized wave function exist in unintentionally doped AlN. The experiments demonstrate how the transformation from a shallow donor to a deep (DX) center takes place and how the deep DX center can be reconverted into a shallow donor forming a spin triplet and singlet states.

  4. In vivo absorption spectra of the two stable states of the Euglena photoreceptor photocycle.

    PubMed

    Barsanti, Laura; Coltelli, Primo; Evangelista, Valtere; Passarelli, Vincenzo; Frassanito, Anna Maria; Vesentini, Nicoletta; Santoro, Fabrizio; Gualtieri, Paolo

    2009-01-01

    Euglena gracilis possesses a simple but sophisticated light detecting system, consisting of an eyespot formed by carotenoids globules and a photoreceptor. The photoreceptor of Euglena is characterized by optical bistability, with two stable states. In order to provide important and discriminating information on the series of structural changes that Euglena photoreceptive protein(s) undergoes inside the photoreceptor in response to light, we measured the in vivo absorption spectra of the two stable states A and B of photoreceptor photocycle. Data were collected using two different devices, i.e. a microspectrophotometer and a digital microscope. Our results show that the photocycle and the absorption spectra of the photoreceptor possess strong spectroscopic similarities with a rhodopsin-like protein. Moreover, the analysis of the absorption spectra of the two stable states of the photoreceptor and the absorption spectrum of the eyespot suggests an intriguing hypothesis for the orientation of microalgae toward light.

  5. Excitation spectra and wave functions of quasiparticle bound states in bilayer Rashba superconductors

    NASA Astrophysics Data System (ADS)

    Higashi, Yoichi; Nagai, Yuki; Yoshida, Tomohiro; Kato, Masaru; Yanase, Youichi

    2015-11-01

    We study the excitation spectra and the wave functions of quasiparticle bound states at a vortex and an edge in bilayer Rashba superconductors under a magnetic field. In particular, we focus on the quasiparticle states at the zero energy in the pair-density wave state in a topologically non-trivial phase. We numerically demonstrate that the quasiparticle wave functions with zero energy are localized at both the edge and the vortex core if the magnetic field exceeds the critical value.

  6. Effects of Electronic-State-Dependent Solute Polarizability: Application to Solute-Pump/Solvent-Probe Spectra.

    PubMed

    Sun, Xiang; Ladanyi, Branka M; Stratt, Richard M

    2015-07-23

    Experimental studies of solvation dynamics in liquids invariably ask how changing a solute from its electronic ground state to an electronically excited state affects a solution's dynamics. With traditional time-dependent-fluorescence experiments, that means looking for the dynamical consequences of the concomitant change in solute-solvent potential energy. But if one follows the shift in the dynamics through its effects on the macroscopic polarizability, as recent solute-pump/solvent-probe spectra do, there is another effect of the electronic excitation that should be considered: the jump in the solute's own polarizability. We examine the spectroscopic consequences of this solute polarizability change in the classic example of the solvation dye coumarin 153 dissolved in acetonitrile. After demonstrating that standard quantum chemical methods can be used to construct accurate multisite models for the polarizabilities of ground- and excited-state solvation dyes, we show via simulation that this polarizability change acts as a contrast agent, significantly enhancing the observable differences in optical-Kerr spectra between ground- and excited-state solutions. A comparison of our results with experimental solute-pump/solvent-probe spectra supports our interpretation and modeling of this spectroscopy. We predict, in particular, that solute-pump/solvent-probe spectra should be sensitive to changes in both the solvent dynamics near the solute and the electronic-state-dependence of the solute's own rotational dynamics.

  7. Photofragmentations, state interactions, and energetics of Rydberg and ion-pair states: two-dimensional resonance enhanced multiphoton ionization of HBr via singlet-, triplet-, Ω = 0 and 2 states.

    PubMed

    Long, Jingming; Hróðmarsson, Helgi Rafn; Wang, Huasheng; Kvaran, Ágúst

    2012-06-07

    Mass spectra were recorded for one-colour resonance enhanced multiphoton ionization (REMPI) of H(i)Br (i = 79, 81) for the two-photon resonance excitation region 79,040-80,300 cm(-1) to obtain two-dimensional REMPI data. The data were analysed in terms of rotational line positions, intensities, and line-widths. Quantitative analysis of the data relevant to near-resonance interactions between the F(1)Δ(2)(v' = 1) and V(1)Σ(+)(v' = m + 7) states gives interaction strengths, fractional state mixing, and parameters relevant to dissociation of the F state. Qualitative analysis further reveals the nature of state interactions between ion-pair states and the E(1)Σ(+) (v' = 1) and H(1)Σ(+)(v' = 0) Rydberg states in terms of relative strengths and J' dependences. Large variety in line-widths, depending on electronic states and J' quantum numbers, is indicative of number of different predissociation channels. The relationship between line-widths, line-shifts, and signal intensities reveals dissociation mechanisms involving ion-pair to Rydberg state interactions prior to direct or indirect predissociations of Rydberg states. Quantum interference effects are found to be important. Moreover, observed bromine atom (2 + 1) REMPI signals support the importance of Rydberg state predissociation channels. A band system, not previously observed in REMPI, was observed and assigned to the k(3)Π(0)(v' = 0) ←← X transition with band origin 80,038 cm(-1) and rotational parameter B(v('))=7.238 cm(-1).

  8. Triplet-extinction coefficients of some laser dyes. 1

    SciTech Connect

    Pavlopoulos, T.G.; Golich, D.J.

    1989-03-01

    For flashlamp-pumped dye lasers, the negative effect of triplet-state losses on laser action efficiency is well known. Oscilloscope traces of laser pulses showed that laser action diminishes much sooner than the flashlamp excitation pulse. This effect was attributed to the buildup of triplet-state dye molecules during the excitation from the flashlamp pulse. Triplet-extinction coefficients epsilon(T) were measured over the laser-action spectral region of Rhodamine 6G; Rhodamine B; Rhodamine 110; Fluorol-7GA; Coumarin 540A; Coumarin 522; Coumarin 1; Coumarin 120; 4,4'-diphenyl stilbene; and 2,7-bis(4-methoxy-phenyl)-9,9-dipropylfluorene. The different lines from an argon-ion cw laser were employed for excitation. McClure's method was used to obtain the triplet extinction coefficients Epsilon(T). The method requires the measurement of triplet optical densities OD(T) as a function of different cw laser-excitation intensities (powers) I(ex). The importance of triplet-state losses on dye-laser efficiency is reviewed. The laser action properties of the laser dyes studied are briefly discussed as they relate to the measured epsilon=(T) values.

  9. Crossing behavior of the singlet and triplet state of the negatively charged magnetoexciton in a GaAs/Al0.55Ga0.45As quantum well

    NASA Astrophysics Data System (ADS)

    Munteanu, F. M.; Kim, Yongmin; Perry, C. H.; Rickel, D. G.; Simmons, J. A.; Reno, J. L.

    2000-02-01

    Polarized magnetophotoluminescence (MPL) measurements on a high-mobility δ-doped GaAs/Al0.55Ga0.45As single quantum well from 0 to 60 T at temperatures between 0.37 and 2.1 K are reported. In addition to the neutral heavy-hole magnetoexciton (X0), the singlet (X-s) and triplet (X-t) states of the negatively charged magnetoexciton are observed in both polarizations. The energy-dispersive and time-resolved MPL data suggest that their development is fundamentally related to the formation of the neutral magnetoexciton. At a magnetic field of 40 T the singlet and the triplet states cross as a result of the role played by the higher Landau levels and higher-energy subbands in their energetic evolution, confirming theoretical predictions. We also observed the formation of two higher-energy peaks. One of them is completely right circularly polarized and its appearance can be considered a result of the electron-hole exchange interaction enhancement with an associated electron g factor of 3.7 times the bulk value. The other peak completely dominates the MPL spectrum at fields around 30 T. Its behavior with magnetic field and temperature indicates that it may be related to previous anomalies observed in the integer and fractional quantum Hall regimes.

  10. Laser flash photolysis of 1,2-diketopyracene and a theoretical study of the phenolic hydrogen abstraction by the triplet state of cyclic alpha-diketones.

    PubMed

    de Lucas, Nanci C; Correa, Rodrigo J; Albuquerque, Ana Carla C; Firme, Caio L; Garden, Simon J; Bertoti, Ada Ruth; Netto-Ferreira, José C

    2007-02-15

    Laser flash photolysis (LFP) studies, atoms in molecules (AIM) studies, and density functional theory (DFT) calculations have been performed in order to study the mechanism of the hydrogen abstraction by alpha-diketones in the presence of phenols. Laser irradiation of a degassed solution of 1,2-diketopyracene in acetonitrile resulted in the formation of a readily detectable transient with absorption at 610 nm, but with very low absorptivity. This transient decays with a lifetime of around 2 micros. The quenching rate constant for substituted phenols, kq, ranged from 1.10x10(8) L mol-1 s-1 (4-cyanophenol) to 3.87x10(9) L mol-1 s-1 (4-hydroxyphenol). The Hammett plot for the reaction of the triplet of 1,2-diketopyracene with phenols gave a reaction constant rho=-0.9. DFT calculations (UB3LYP/6-311++G**//UB3LYP/6-31G*) of the triplet complex ketone-phenol revealed that hydrogen transfer has predominantly occurred and that the reaction with alpha-diketones are generally 7 kcal/mol less endothermic than the respective reactions of the monoketones. These results together with the geometries obtained from the DFT calculations, natural bond order (NBO) analysis, and AIM results indicate that hydrogen abstraction for alpha-diketones is facilitated by the electrophilicity of the ketone, instead of neighboring group participation by the second carbonyl group.

  11. Twins, Triplets, and Other Multiples

    MedlinePlus

    ... complications Pregnancy loss Know your pregnancy rights Getting ready for baby Childbirth and ... Twins, triplets, and other multiples If you are pregnant with more than one baby, you are far from alone. In the ...

  12. Triplet quenching by diacyl peroxides

    NASA Astrophysics Data System (ADS)

    Ingold, K. U.; Johnston, L. J.; Lusztyk, J.; Scaiano, J. C.

    1984-10-01

    Benzoyl and decanoyl peroxides are efficient quenchers of various triplet sensitizers: kinetic studies using laser photolysis techniques indicate that electronic energy transfer and charge transfer to the peroxide are important factors contributing to the quenching process.

  13. Alpha particle spectra in coincidence with normal and superdeformed states in {sup 150}Tb

    SciTech Connect

    Viesti, G.; Lunardon, M.; Bazzacco, D. |

    1996-12-31

    The study of correlations between particle evaporation from highly excited compound nuclei at large angular momenta and the states in the final evaporation residues (ER) is a field of investigation which has been opened, in the last years, with the advent of the new large {gamma}-ray arrays. It is now possible to correlate the evaporation spectra to various bands with shapes ranging from spherical to superdeformed (SD) in the same final nucleus. It is generally accepted that the particle evaporation from the compound nucleus is chaotic and that only in the near-yrast {gamma} cascade, where the feeding of different classes of states takes place, the ordered motion is restored. The sensitivity of the particle spectra on the feeding of specific states in the residual nuclei can be taken as an indication that additional degrees of freedom might be important in the evaporation process or that particular regions of the phase space open to the decay populate preferentially some selected structures in the final cold nucleus. This latter point is important for the understanding of the feeding mechanism of SD states. Several experiments performed so far did not find a clear dependence of the shapes of the particle spectra on the excited states having different deformations in the ER. For example, the proton spectra in coincidence with transitions in the SD bands of {sup 133}Nd and {sup 152}Dy nuclei were found to be similar to those in coincidence with transitions in the normal deformed (ND) bands. Alpha particles have been proposed since long as a sensitive probe of the deformation of the emitting nucleus. Results are presented here of an experiment in which the authors have measured the energy spectra of alpha particles associated with different classes of states (ND and SD) in the {sup 150}Tb nucleus populated in the reaction {sup 37}Cl({sup 120}Sn, {alpha}3n{gamma}){sup 150}Tb.

  14. On the nature of excited electronic states in cyanine dyes: implications for visual pigment spectra

    NASA Astrophysics Data System (ADS)

    Dinur, Uri; Honig, Barry; Schulten, Klaus

    1980-06-01

    CNDO/S CI calculations are carried out on polyenes and on cyanine dyes. In contrast to polyenes, doubly excited configurations have a strong effect on the first optically allowed excited state in cyanines. Protonated Schiff bases of retinal are closely related to cyanine dyes, with important consequences for models of visual pigment spectra and photochemistry.

  15. Triplet extinction coefficients of some laser dyes I

    SciTech Connect

    Pavlopoulos, T.G.; Golich, D.J.

    1988-07-15

    We measured the triplet extinction coefficients epsilon/sub T/ over the laser action spectral region of Rhodamine 6G; Rhodamine B; Rhodamine 110; Fluorol-7GA; Coumarin 540A; Coumarin 522; Coumarin 1; Coumarin 120; 4,4'-diphenyl stilbene; and 2,7-bis-(4-methoxy-phenyl)-9,9-dipropylfluorene. We employed the different lines from an argon ion cw laser for excitation. McClure's method was used to obtain the triplet extinction coefficients epsilon/sub T/. The method requires the measurement of triplet optical densities OD/sub T/ as a function of different cw laser excitation intensities (powers) I/sub ex/ . The importance of triplet-state losses on dye laser efficiency is reviewed. The laser action properties of the laser dyes we studied are briefly discussed as they relate to the measured epsilon/sub T/ values.

  16. Spectra of random operators with absolutely continuous integrated density of states

    SciTech Connect

    Rio, Rafael del E-mail: delriomagia@gmail.com

    2014-04-15

    The structure of the spectrum of random operators is studied. It is shown that if the density of states measure of some subsets of the spectrum is zero, then these subsets are empty. In particular follows that absolute continuity of the integrated density of states implies singular spectra of ergodic operators is either empty or of positive measure. Our results apply to Anderson and alloy type models, perturbed Landau Hamiltonians, almost periodic potentials, and models which are not ergodic.

  17. NC-(CF2)4-CNSSN radical containing 1,2,3,5-dithiadiazolyl radical dimer exhibiting triplet excited states at low temperature and thermal hysteresis on melting-solidification: structural, spectroscopic, and magnetic characterization.

    PubMed

    Shuvaev, Konstantin V; Decken, Andreas; Grein, Friedrich; Abedin, Tareque S M; Thompson, Laurence K; Passmore, Jack

    2008-08-14

    A high yield, one-pot synthesis of the 1,2,3,5-dithiadiazolyl radical NC-(CF2)4-CNSSN radical by reduction of the corresponding 1,3,2,4-dithiadiazolium salt is reported. In the solid state, the title compound is dimerized in trans-cofacial fashion with intra-dimeric Sdelta+...N(delta-) interactions of ca. 3.2 angstroms, and the dimeric units are linked by electrostatic -C triple bond N(delta-)...Sdelta+ interactions forming an infinite chain. Magnetic susceptibility measurements performed on the solid state sample indicate a magnetic moment of 1.8 microB per dimer (1.3 microB per monomer) at 300 K and a good fit to the Bleaney-Bowers model in the temperature range 2-300 K with 2J = -1500 +/- 50 cm(-1), g = 2.02(5), rho = 0.90(3)%, and TIP = 1.25(4) x 10(-3) emu mol(-1). The [NC-(CF2)4-CNSSN radical]2 dimer is the second example of a 1,2,3,5-dithiadiazolyl radical dimer with an experimentally detected triplet excited state as probed by solid-state EPR [2J = -1730 +/- 100 cm(-1), |D| = 0.0278(5) cm(-1), |E| = 0.0047(5) cm(-1)]. The value of the singlet-triplet gap has enabled us to estimate the "in situ" dimerization energy of the radical dimer as ca. -10 kJ mol(-1). The diradical character of the dimer was calculated [CASSCF(6,6)/6-31G*] as 35%. The title radical shows magnetic bistability in the temperature range of 305-335 K as probed by the solid-state EPR presumably arising from the presence of a metastable paramagnetic supercooled phase. Bistability is accompanied by thermochromic behavior with a color change from dark green (dimeric solid) to dark brown (paramagnetic liquid).

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

    PubMed

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

    2011-01-01

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

  19. Influences of the Mie resonance on reflectance spectra of Si nanopillar arrays with different wetting states

    NASA Astrophysics Data System (ADS)

    Kim, Sujung; Gwon, Minji; Li, Jiaqi; Xu, Xiumei; Kim, Sun-Kyung; Lee, Eunsongyi; Kim, Dong-Wook; Chen, Chang

    The reflectance spectra of crystalline Si nanopillar (SiNP) arrays with various diameters were investigated by finite-difference time-domain (FDTD) simulations. The spectra exhibited distinct features depending on the wetting states. The FDTD-simulated reflectance dips of the 40-nm-diameter SiNP array were in good agreement with those estimated from destructive interference conditions at the top and bottom of the SiNPs: the SiNP arrays and the surrounding medium were treated as one optically homogeneous medium with an effective permittivity estimated from the effective medium approximation (EMA) model. However, the dip positions of the simulated spectra for 70-, 100-, and 130-nm-diameter SiNP arrays deviated from the results of interference calculations, particularly for short wavelengths. The optical reflectance spectra were significantly affected by the strong diameter-dependent Mie resonances in SiNPs, which were sensitive to the refractive index of the surrounding medium (i.e., the wetting state). Optical reflectance measurements provide an easy and efficient means of inspecting the wetting behavior of nano-patterned surfaces.

  20. Characterization of short necklace states in the logarithmic transmission spectra of localized systems.

    PubMed

    Chen, Liang; Jiang, Xunya

    2013-05-01

    High transmission plateaus exist widely in the logarithmic transmission spectra of localized systems. Their physical origins are short chains of coupled localized states embedded inside the localized system, which are dubbed as 'short necklace states'. In this work, we define the essential quantities and then, based on these quantities, we investigate the properties of the short necklace states statistically and quantitatively. Two different approaches are utilized and their results agree very well. In the first approach, the typical plateau-width and the typical order of short necklace states are obtained from the correlation function of the logarithmic transmission. In the second approach, we investigate the statistical distribution of the peak/plateau-width measured in the logarithmic transmission spectra. A novel distribution is found, which can be exactly fitted by the summation of two Gaussian distributions. These two distributions are the results of sharp peaks of localized states and the high plateaus of short necklace states. The center of the second distribution also tells us the typical plateau-width of short necklace states. With increasing system length, the scaling property of the typical plateau-width is very special since it hardly decreases. The methods and quantities defined in this work can be widely used in Anderson localization studies.

  1. Dipole moment of benzonitrile in its excited S 1 state from thermochromic shifts of fluorescence spectra

    NASA Astrophysics Data System (ADS)

    Kawski, A.; Kukliński, B.; Bojarski, P.

    2006-02-01

    The effect of temperature T ranging from 293 to 393 K on absorption and fluorescence spectra of benzonitrile (BN) in ethyl acetate is studied. The absorption spectra of BN remain unchanged with increasing T. The analysis of fluorescence band shift by the Bilot and Kawski theory [L. Bilot, A. Kawski, Z. Naturforsch. 17a (1962) 621], for the known dipole moment value in the ground state μg = 4.18 D and α/ a3 = 0.5 ( α is the polarizability and a is the Onsager interaction radius of the solute), yield the average value of excited state dipole moment μe = 4.42 D. This value is in satisfactory agreement with 4.45, 4.51 and 4.57 D obtained previously from the Stark shift of rotational lines.

  2. Sulphur Kβ emission spectra reveal protonation states of aqueous sulfuric acid

    PubMed Central

    Niskanen, Johannes; Sahle, Christoph J.; Ruotsalainen, Kari O.; Müller, Harald; Kavčič, Matjaž; Žitnik, Matjaž; Bučar, Klemen; Petric, Marko; Hakala, Mikko; Huotari, Simo

    2016-01-01

    In this paper we report an X-ray emission study of bulk aqueous sulfuric acid. Throughout the range of molarities from 1 M to 18 M the sulfur Kβ emission spectra from H2SO4 (aq) depend on the molar fractions and related deprotonation of H2SO4. We compare the experimental results with results from emission spectrum calculations based on atomic structures of single molecules and structures from ab initio molecular dynamics simulations. We show that the S Kβ emission spectrum is a sensitive probe of the protonation state of the acid molecules. Using non-negative matrix factorization we are able to extract the fractions of different protonation states in the spectra, and the results are in good agreement with the simulation for the higher part of the concentration range. PMID:26888159

  3. Symmetry breaking gives rise to energy spectra of three states of matter

    PubMed Central

    Bolmatov, Dima; Musaev, Edvard T.; Trachenko, K.

    2013-01-01

    A fundamental task of statistical physics is to start with a microscopic Hamiltonian, predict the system's statistical properties and compare them with observable data. A notable current fundamental challenge is to tell whether and how an interacting Hamiltonian predicts different energy spectra, including solid, liquid and gas phases. Here, we propose a new idea that enables a unified description of all three states of matter. We introduce a generic form of an interacting phonon Hamiltonian with ground state configurations minimising the potential. Symmetry breaking SO(3) to SO(2), from the group of rotations in reciprocal space to its subgroup, leads to emergence of energy gaps of shear excitations as a consequence of the Goldstone theorem, and readily results in the emergence of energy spectra of solid, liquid and gas phases. PMID:24077388

  4. An isolated compact galaxy triplet

    NASA Astrophysics Data System (ADS)

    Feng, Shuai; Shao, Zheng-Yi; Shen, Shi-Yin; Argudo-Fernández, Maria; Wu, Hong; Lam, Man-I.; Yang, Ming; Yuan, Fang-Ting

    2016-05-01

    We report the discovery of an isolated compact galaxy triplet SDSS J084843.45+164417.3, which is first detected by the LAMOST spectral survey and then confirmed by a spectroscopic observation of the BFOSC mounted on the 2.16 meter telescope located at Xinglong Station, which is administered by National Astronomical Observatories, Chinese Academy of Sciences. It is found that this triplet is an isolated and extremely compact system, which has an aligned configuration and very small radial velocity dispersion. The member galaxies have similar colors and show marginal star formation activities. These results support the opinion that the compact triplets are well-evolved systems rather than hierarchically forming structures. This serendipitous discovery reveals the limitations of fiber spectral redshift surveys in studying such a compact system, and demonstrates the necessity of additional observations to complete the current redshift sample.

  5. Magnetic correction of RHIC triplets

    SciTech Connect

    Wei, J.; Gupta, R.; Peggs, S.

    1993-01-01

    Triplets of large bore quadrupoles will be antisymmetrically placed on either side of all six intersection points of the Relativistic Heavy Ion collider (RHIC). In RHIC collision optics, the tiplets at the two experimental detectors are intended to enable the collision beta function to be reduced to the design goal of [beta][sup *] = 1.0 meter in both planes, in order to minimize the spot size and maximize the luminosity. This requires running with [beta][sub max] [approx] 1400 meters in the triplet, where the beams will have their largest size, both absolutely and as a fraction of the available aperture. Hence, the ultimate performance of RHIC rests on achieving the highest possible magnetic field quality in the triplets. This paper discusses the correction of magnetic errors expected in the quadrupole bodies and ends, using both these limped correctors and also quadrupole body tuning shims.

  6. Magnetic correction of RHIC triplets

    SciTech Connect

    Wei, J.; Gupta, R.; Peggs, S.

    1993-06-01

    Triplets of large bore quadrupoles will be antisymmetrically placed on either side of all six intersection points of the Relativistic Heavy Ion collider (RHIC). In RHIC collision optics, the tiplets at the two experimental detectors are intended to enable the collision beta function to be reduced to the design goal of {beta}{sup *} = 1.0 meter in both planes, in order to minimize the spot size and maximize the luminosity. This requires running with {beta}{sub max} {approx} 1400 meters in the triplet, where the beams will have their largest size, both absolutely and as a fraction of the available aperture. Hence, the ultimate performance of RHIC rests on achieving the highest possible magnetic field quality in the triplets. This paper discusses the correction of magnetic errors expected in the quadrupole bodies and ends, using both these limped correctors and also quadrupole body tuning shims.

  7. 'Blueberry' Triplets Born in Rock

    NASA Technical Reports Server (NTRS)

    2004-01-01

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

  8. Excited states and absorption spectra of β-diketonate complexes of boron difluoride with aromatic substituents

    NASA Astrophysics Data System (ADS)

    Vovna, V. I.; Kazachek, M. V.; L'vov, I. B.

    2012-04-01

    In the approximation of the time-dependent electron density functional theory, we have studied using the quantum-chemical method the nature of excited states of boron difluoride acetylacetonate F2BAA and its substituted derivatives that contain aromatic groups with one or two benzene cycles in the β-position. Optimization of the geometry of complexes show coplanar positions of cycles for all compounds, except for that with the substituent C6H3(CH3)2. Based on the calculated transition energies and oscillator strengths, we have simulated the absorption spectra in the prevacuum range. The calculated absorption spectra have been compared with the experimental spectra in the gas phase or in solutions. We show that, in the absorption spectra of complexes that contain substituents with one benzene cycle, the first three bands are caused by the transition of π electrons of the substituent to the LUMO of the chelate cycle. In complexes with two cycles in the substituent, the number of these transitions increases to five. As the π system becomes more extended, a bathochromic shift of the first absorption band and an increase in the transition probability are observed.

  9. Bringing light into the dark triplet space of molecular systems.

    PubMed

    Ge, Jing; Zhang, Qun; Jiang, Jun; Geng, Zhigang; Jiang, Shenlong; Fan, Kaili; Guo, Zhenkun; Hu, Jiahua; Chen, Zongwei; Chen, Yang; Wang, Xiaoping; Luo, Yi

    2015-05-21

    A molecule or a molecular system always consists of excited states of different spin multiplicities. With conventional optical excitations, only the (bright) states with the same spin multiplicity of the ground state could be directly reached. How to reveal the dynamics of excited (dark) states remains the grand challenge in the topical fields of photochemistry, photophysics, and photobiology. For a singlet-triplet coupled molecular system, the (bright) singlet dynamics can be routinely examined by conventional femtosecond pump-probe spectroscopy. However, owing to the involvement of intrinsically fast decay channels such as intramolecular vibrational redistribution and internal conversion, it is very difficult, if not impossible, to single out the (dark) triplet dynamics. Herein, we develop a novel strategy that uses an ultrafast broadband white-light continuum as a excitation light source to enhance the probability of intersystem crossing, thus facilitating the population flow from the singlet space to the triplet space. With a set of femtosecond time-reversed pump-probe experiments, we report on a proof-of-concept molecular system (i.e., the malachite green molecule) that the pure triplet dynamics can be mapped out in real time through monitoring the modulated emission that occurs solely in the triplet space. Significant differences in excited-state dynamics between the singlet and triplet spaces have been observed. This newly developed approach may provide a useful tool for examining the elusive dark-state dynamics of molecular systems and also for exploring the mechanisms underlying molecular luminescence/photonics and solar light harvesting.

  10. Theoretical calculations on electronic transitions for H/sub 3/, including Rydberg and transition state spectra

    SciTech Connect

    Petsalakis, I.D.; Theodorakopoulos, G.; Wright, J.S.

    1988-12-01

    MRD-CI calculations have been carried out on the ground and excited electronic states of H/sub 3/ for D/sub 3//sub h/, D/sub infinity//sub h/, C/sub infinity//sub v/, and C/sub 2//sub v/ geometries. Dipole transition moments between the various electronic states have been also obtained at the different geometries calculated. The present work provides accurate theoretical information relevant to the transition state spectroscopy of H+H/sub 2/ along a collinear path and also along a perpendicular path. In addition, the present work is the first all-electron configuration interaction treatment of the Rydberg states of H/sub 3/, and the results are in excellent agreement with the observed spectra.

  11. Correlations between ground and excited state spectra of a quantum Dot

    PubMed

    Stewart; Sprinzak; Marcus; Duruoz; Harris

    1997-12-05

    The ground and excited state spectra of a semiconductor quantum dot with successive electron occupancy were studied with linear and nonlinear magnetoconductance measurements. A direct correlation was observed between the mth excited state of the N-electron system and the ground state of the (N + m)-electron system for m up to 4. The results are consistent with a single-particle picture in which a fixed spectrum of energy levels is successively filled, except for a notable absence of spin degeneracy. Further departures from the single-particle picture due to electron-electron interaction were also observed. Magnetoconductance fluctuations of ground states show anticrossings where wave function characteristics are exchanged between adjacent levels.

  12. Excitation spectra of circular, few-electron quantum dots

    PubMed

    Kouwenhoven; Oosterkamp; Danoesastro; Eto; Austing; Honda; Tarucha

    1997-12-05

    Studies of the ground and excited states in semiconductor quantum dots containing 1 to 12 electrons showed that the quantum numbers of the states in the excitation spectra can be identified and compared with exact calculations. A magnetic field induces transitions between the ground and excited states. These transitions were analyzed in terms of crossings between single-particle states, singlet-triplet transitions, spin polarization, and Hund's rule. These impurity-free quantum dots allow "atomic physics" experiments to be performed in magnetic field regimes not accessible for atoms.

  13. The gamma-ray blazar quest: new optical spectra, state of art and future perspectives

    NASA Astrophysics Data System (ADS)

    Massaro, F.; Álvarez Crespo, N.; D'Abrusco, R.; Landoni, M.; Masetti, N.; Ricci, F.; Milisavljevic, D.; Paggi, A.; Chavushyan, V.; Jiménez-Bailón, E.; Patiño-Álvarez, V.; Strader, J.; Chomiuk, L.; La Franca, F.; Smith, Howard A.; Tosti, G.

    2016-10-01

    We recently developed a procedure to recognize γ-ray blazar candidates within the positional uncertainty regions of the unidentified/unassociated γ-ray sources (UGSs). Such procedure was based on the discovery that Fermi blazars show peculiar infrared colors. However, to confirm the real nature of the selected candidates, optical spectroscopic data are necessary. Thus, we performed an extensive archival search for spectra available in the literature in parallel with an optical spectroscopic campaign aimed to reveal and confirm the nature of the selected γ-ray blazar candidates. Here, we first search for optical spectra of a selected sample of γ-ray blazar candidates that can be potential counterparts of UGSs using the Sloan Digital Sky Survey (SDSS DR12). This search enables us to update the archival search carried out to date. We also describe the state-of-art and the future perspectives of our campaign to discover previously unknown γ-ray blazars.

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

    PubMed

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

    2015-06-23

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

  15. Analysis of PANDA Passive Containment Cooling Steady-State Tests with the Spectra Code

    SciTech Connect

    Stempniewicz, Marek M

    2000-07-15

    Results of post test simulation of the PANDA passive containment cooling (PCC) steady-state tests (S-series tests), performed at the PANDA facility at the Paul Scherrer Institute, Switzerland, are presented. The simulation has been performed using the computer code SPECTRA, a thermal-hydraulic code, designed specifically for analyzing containment behavior of nuclear power plants.Results of the present calculations are compared to the measurement data as well as the results obtained earlier with the codes MELCOR, TRAC-BF1, and TRACG. The calculated PCC efficiencies are somewhat lower than the measured values. Similar underestimation of PCC efficiencies had been obtained in the past, with the other computer codes. To explain this difference, it is postulated that condensate coming into the tubes forms a stream of liquid in one or two tubes, leaving most of the tubes unaffected. The condensate entering the water box is assumed to fall down in the form of droplets. With these assumptions, the results calculated with SPECTRA are close to the experimental data.It is concluded that the SPECTRA code is a suitable tool for analyzing containments of advanced reactors, equipped with passive containment cooling systems.

  16. Half-metallic superconducting triplet spin valve

    NASA Astrophysics Data System (ADS)

    Halterman, Klaus; Alidoust, Mohammad

    2016-08-01

    We theoretically study a finite-size S F1N F2 spin valve, where a normal metal (N ) insert separates a thin standard ferromagnet (F1) and a thick half-metallic ferromagnet (F2). For sufficiently thin superconductor (S ) widths close to the coherence length ξ0, we find that changes to the relative magnetization orientations in the ferromagnets can result in substantial variations in the transition temperature Tc, consistent with experimental results [Singh et al., Phys. Rev. X 5, 021019 (2015), 10.1103/PhysRevX.5.021019]. Our results demonstrate that, in good agreement with the experiment, the variations are largest in the case where F2 is in a half-metallic phase and thus supports only one spin direction. To pinpoint the origins of this strong spin-valve effect, both the equal-spin f1 and opposite-spin f0 triplet correlations are calculated using a self-consistent microscopic technique. We find that when the magnetization in F1 is tilted slightly out of plane, the f1 component can be the dominant triplet component in the superconductor. The coupling between the two ferromagnets is discussed in terms of the underlying spin currents present in the system. We go further and show that the zero-energy peaks of the local density of states probed on the S side of the valve can be another signature of the presence of superconducting triplet correlations. Our findings reveal that for sufficiently thin S layers, the zero-energy peak at the S side can be larger than its counterpart in the F2 side.

  17. Investigating velocity spectra at the Hugoniot state of shock loaded heterogenous materials

    NASA Astrophysics Data System (ADS)

    LaJeunesse, Jeff; Stewart, Sarah T.; Kennedy, Greg; Thadhani, Naresh; Borg, John P.

    2017-01-01

    Particle velocity and stress profiles measured in planar impact experiments on heterogeneous materials have shown significant deviations about the idealized final shock state plateau in both experimental and simulated tests. These deviations arise from the scattering of the transmitted shock wave due to the presence of internal interfaces within heterogeneous materials. The goal of this work is to determine if the spectra of oscillatory behavior can be associated to characteristic length scales of the corresponding un-shocked heterogeneous material. Similarities between experimental and simulated particle velocity profiles from planar impacts on dry sand are compared.

  18. Long-lived, colour-triplet scalars from unnaturalness

    NASA Astrophysics Data System (ADS)

    Barnard, James; Cox, Peter; Gherghetta, Tony; Spray, Andrew

    2016-03-01

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

  19. Long-lived, colour-triplet scalars from unnaturalness

    SciTech Connect

    Barnard, James; Cox, Peter; Gherghetta, Tony; Spray, Andrew

    2016-03-01

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

  20. Long-lived, colour-triplet scalars from unnaturalness

    DOE PAGES

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

    2016-03-01

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

  1. Triplet-triplet energy transfer and protection mechanisms against singlet oxygen in photosynthesis

    NASA Astrophysics Data System (ADS)

    Kihara, Shigeharu

    In photosynthesis, (bacterio)chlorophylls ((B)Chl) play a crucial role in light harvesting and electron transport. (B)Chls, however, are known to be potentially dangerous due to the formation of the triplet excited state which forms the singlet oxygen (1O2*) when exposed to the sunlight. Singlet oxygen is highly reactive and all modern organisms incorporate special protective mechanisms to minimize the oxidative damage. One of the conventional photoprotective mechanisms used by photosynthetic organisms is by the nearby carotenoids quenching the excess energy and releasing it by heat. In this dissertation, two major aspects of this process are studied. First, based on experimental data and model calculations, the oxygen content in a functioning oxygenic photosynthetic oxygen cell was determined. These organisms perform water splitting and as a result significant amount of oxygen can be formed within the organism itself. It was found, that contrary to some published estimates, the excess oxygen concentration generated within an individual cell is extremely low -- 0.025 ... 0.25 microM, i.e. about 103-104 times lower than the oxygen concentration in air saturated water. Such low concentrations imply that the first oxygenic photosynthetic cells that evolved in oxygen-free atmosphere of the Earth ~2.8 billion years ago might have invented the water splitting machinery (photosystem II) without the need for special oxygen-protective mechanisms, and the latter mechanisms could have evolved in the next 500 million years during slow rise of oxygen in the atmosphere. This result also suggests that proteins within photosynthetic membranes are not exposed to significant O2 levels and thus can be studied in vitro under the usual O2 levels. Second, the fate of triplet excited states in the Fenna Matthew Olson (FMO) pigment-protein complex is studied by means of time-resolved nanosecond spectroscopy and exciton model simulations. For the first time, the properties of several

  2. Chl- a triplet quenching by peridinin in H-PCP and organic solvent revealed by step-scan FTIR time-resolved spectroscopy

    NASA Astrophysics Data System (ADS)

    Bonetti, C.; Alexandre, M. T. A.; Hiller, R. G.; Kennis, J. T. M.; Grondelle, R. van

    2009-02-01

    Triplet-state dynamics in Chl- a/Per mixtures in organic solvent and in native H-PCP were studied by means of step-scan FTIR spectroscopy. A single decay component of 10 μs was observed for the H-PCP triplet, the spectrum of which closely matches the 13 μs component of A-PCP [Alexandre et al., Biophysical Journal 93 (2007) 2118-2128], implying that in H-PCP, as in A-PCP, the peridinin triplet state is shared with Chl- a. In a mixture of Chl- a and Per in THF, TEET from 3Chl- a to 3Per proceeds in 3.5 μs followed by 3Per decay in 7 μs. Using a target analysis procedure, 3Chl- a and 3Per infrared difference spectra were obtained. The specific carbonyl frequencies of 3Per and 3Chl- a in THF confirm our assignment of their co-existence in the infrared spectra of H-PCP and A-PCP.

  3. Nonlinear optical spectra having characteristics of Fano interferences in coherently coupled lowest exciton biexciton states in semiconductor quantum dots

    SciTech Connect

    Gotoh, Hideki Sanada, Haruki; Yamaguchi, Hiroshi; Sogawa, Tetsuomi

    2014-10-15

    Optical nonlinear effects are examined using a two-color micro-photoluminescence (micro-PL) method in a coherently coupled exciton-biexciton system in a single quantum dot (QD). PL and photoluminescence excitation spectroscopy (PLE) are employed to measure the absorption spectra of the exciton and biexciton states. PLE for Stokes and anti-Stokes PL enables us to clarify the nonlinear optical absorption properties in the lowest exciton and biexciton states. The nonlinear absorption spectra for excitons exhibit asymmetric shapes with peak and dip structures, and provide a distinct contrast to the symmetric dip structures of conventional nonlinear spectra. Theoretical analyses with a density matrix method indicate that the nonlinear spectra are caused not by a simple coherent interaction between the exciton and biexciton states but by coupling effects among exciton, biexciton and continuum states. These results indicate that Fano quantum interference effects appear in exciton-biexciton systems at QDs and offer important insights into their physics.

  4. Intensity formulas for triplet bands

    NASA Technical Reports Server (NTRS)

    Budo, A.

    1982-01-01

    Previous work in this area is surveyed and the mathematics involved in determining the quantitative intensity measurements in triplet bands is presented. Explicit expressions for the intensity distribution in the branches of the 3 Sigma-3 Pi and 1 Sigma-3Pi bands valid for all values of the coupling constant Y of the 3 Pi terms are given. The intensity distribution calculated according to the formulas given is compared with measurements of PH, 3 Pi-3 Sigma. Good quantitative agreement is obtained.

  5. Influence of wetting state on optical reflectance spectra of Si nanopillar arrays

    NASA Astrophysics Data System (ADS)

    Gwon, Minji; Kim, Sujung; Li, Jiaqi; Xu, Xiumei; Kim, Sun-Kyung; Lee, Eunsongyi; Kim, Dong-Wook; Chen, Chang

    2015-12-01

    Finite-difference time-domain (FDTD) simulations showed that the reflectance spectra of crystalline Si nanopillar (NP) arrays with diameters of 40, 70, 100, and 130 nm differed depending on wetting state. The observed reflectance dips of the 40-nm-diameter NP array were in good agreement with those estimated from destructive interference conditions at the top and bottom of the NPs: the NP arrays were treated as a homogeneous medium with an effective permittivity according to the effective medium approximation model. In contrast, the dip positions of the FDTD-simulated spectra for 70-, 100-, and 130-nm-diameter NP arrays deviated from the results of interference calculations, particularly for short wavelengths. This suggested that Mie resonances in individual NPs significantly increased the absorption cross-section at the resonant wavelengths, which was sensitive to the refractive index of the surrounding medium (i.e., the wetting state). Optical reflectance measurements provide an easy and efficient means of inspecting the wetting behavior of non-flat surfaces.

  6. Experimental and theoretical study of the electronic states and spectra of SbNa

    NASA Astrophysics Data System (ADS)

    Setzer, K. D.; Fink, E. H.; Liebermann, H.-P.; Buenker, R. J.; Alekseyev, A. B.

    2015-12-01

    Gas-phase emission spectra of the hitherto unknown free radical SbNa were measured in the NIR region with a Fourier-transform spectrometer. The emissions were observed from a fast-flow system in which antimony vapor in argon or neon carrier gas was passed through a microwave discharge and mixed with sodium vapor in an observation tube. Seven transitions from five low-lying excited states A12, A21, A30+, A40-, and B2 to the X10+ and/or X21 components of the X3Σ- ground state have been observed and analyzed. In parallel to the experiments, relativistic configuration interaction calculations of potential energy curves, vibrational constants, bond lengths, transition moments and radiative lifetimes were carried out to aid in the analysis of the experimental data.

  7. Experimental and theoretical study of the electronic states and spectra of NaAs

    NASA Astrophysics Data System (ADS)

    Setzer, K. D.; Fink, E. H.; Alekseyev, A. B.; Liebermann, H.-P.; Buenker, R. J.

    2016-02-01

    Gas-phase emission spectra of the hitherto unknown free radical NaAs were measured in the NIR region with a Fourier-transform spectrometer. The emissions were observed from a fast-flow system in which arsenic vapor in argon carrier gas was passed through a microwave discharge and mixed with sodium vapor in an observation tube. Seven transitions from all five Ω components of the low-lying A3Π and a1Δ excited states (A12, A21, A30+, A40-, a2) to the X10+ and/or X21 components of the X3Σ- ground state have been observed and analysed. With the help of parallel relativistic configuration interaction calculations all observed spectral features could be assigned and analyzed.

  8. Dipole moment of aniline in the excited S 1 state from thermochromic effect on electronic spectra

    NASA Astrophysics Data System (ADS)

    Kawski, A.; Kukliński, B.; Bojarski, P.

    2005-11-01

    Using the thermochromic shift method of absorption and fluorescence spectra of aniline in ethyl acetate for temperature ranging from 213 to 393 K, the change of the dipole moment Δ μ = μe - μg = 0.84 D between the ground and first excited singlet state was determined based on the Bilot and Kawski theory. This is in agreement with the result obtained by Lombardi from optical Stark effect in the rotational fine structure. For the known dipole moment in the ground state μg = 1.53 D and for α/ a3 = 0.483 ( α is the polarizability and a is the Onsager interaction radius of the solute) the average value of μe = 2.37 D and a = 2.7 Å were determined. The values obtained for aniline are compared with the experimental values determined by other authors.

  9. A stability analysis of the power-law steady state of marine size spectra.

    PubMed

    Datta, Samik; Delius, Gustav W; Law, Richard; Plank, Michael J

    2011-10-01

    This paper investigates the stability of the power-law steady state often observed in marine ecosystems. Three dynamical systems are considered, describing the abundance of organisms as a function of body mass and time: a "jump-growth" equation, a first order approximation which is the widely used McKendrick-von Foerster equation, and a second order approximation which is the McKendrick-von Foerster equation with a diffusion term. All of these yield a power-law steady state. We derive, for the first time, the eigenvalue spectrum for the linearised evolution operator, under certain constraints on the parameters. This provides new knowledge of the stability properties of the power-law steady state. It is shown analytically that the steady state of the McKendrick-von Foerster equation without the diffusion term is always unstable. Furthermore, numerical plots show that eigenvalue spectra of the McKendrick-von Foerster equation with diffusion give a good approximation to those of the jump-growth equation. The steady state is more likely to be stable with a low preferred predator:prey mass ratio, a large diet breadth and a high feeding efficiency. The effects of demographic stochasticity are also investigated and it is concluded that these are likely to be small in real systems.

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

    NASA Technical Reports Server (NTRS)

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

    1993-01-01

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

  11. Product state distributions for the C + (4P)+H2(D2) reaction from chemiluminescence spectra

    NASA Astrophysics Data System (ADS)

    Kusunoki, I.; Ottinger, Ch.

    1982-02-01

    Optical emission resulting from low-energy (1-3 eVc.m.) impact of metastable C+(4P) ions on H2 and D2 molecules has been studied spectroscopically in the 2700-3900 Å range. The b 3Σ--a 3Π transition of CH+ (CD+) was resolved into numerous bands. From a spectrum simulation by computer, rotational-vibrational population distributions of the excited triplet state were obtained. In contrast to previous related studies, the vibrational excitation decreases with increasing collision energy. One-parameter surprisal fits of the vibrational (and, to a lesser extent, the rotational) population distributions are found to be unsatisfactory. The reaction is discussed in terms of changes of molecular orbital occupancy, which suggest a direct interaction mechanism. This is consistent with the observed population distributions.

  12. Theoretical and experimental study of the electronic states and spectra of KBi and KSb

    NASA Astrophysics Data System (ADS)

    Setzer, K. D.; Fink, E. H.; Alekseyev, A. B.; Liebermann, H.-P.; Buenker, R. J.

    2017-03-01

    Gas phase emission spectra of the hitherto unknown free radicals KBi and KSb were measured in the NIR range with a Fourier-transform spectrometer. The emissions were observed from a fast-flow system in which bismuth or antimony vapor in argon carrier gas was passed through a microwave discharge and mixed with potassium vapor in an observation tube. For KBi, two systems of blue-degraded bands observed in the range 5800-7700 cm-1 are assigned to the transitions A3Π (A20+) → X3Σ-(X10+, X21). Nine bands of the A20+ → X10+ and three bands of the A20+ → X21 system were measured at high spectral resolution and rotationally analysed. The rotational and vibrational analyses yielded the spectroscopic parameters of the X10+, X21, and A20+ states. For KSb, in the range of the sensitive Ge detector, only one sequence of bands was measured near 6880 cm-1. By analogy with the previously observed spectra of NaSb and NaAs these bands were identified to be the Δv = 0 sequence of the a2 → X21 transition of KSb. Some very weak bands observed at low resolution in the range 3800-5200 cm-1 are assigned to the transitions A3Π (A21) → X3Σ -(X10+, X21). To aid in the analysis of the experimental data, a series of relativistic configuration interaction calculations has been carried out to obtain potential energy curves for the low-lying states of KBi and KSb, vibrational constants, equilibrium internuclear distances, and also electric dipole transition moments connecting the states.

  13. Andreev bound states in superconductor/ferromagnet point contact Andreev reflection spectra

    NASA Astrophysics Data System (ADS)

    Yates, K. A.; Olde Olthof, L. A. B.; Vickers, M. E.; Prabhakaran, D.; Egilmez, M.; Robinson, J. W. A.; Cohen, L. F.

    2017-03-01

    As charge carriers traverse a single superconductor ferromagnet interface, they experience an additional spin-dependent phase angle that results in spin mixing and the formation of a bound state called the Andreev bound state. Here we explore whether point contact Andreev reflection can be used to detect the Andreev bound state and, within the limits of our experiment, we extract the resulting spin mixing angle. By examining spectra taken from L a1.15S r1.85M n2O7-Pb junctions, together with a compilation of literature data on highly spin polarized systems, we suggest that the existence of the Andreev bound state would resolve a number of long standing controversies in the literature of Andreev reflection, as well as defining a route to quantify the strength of spin mixing at superconductor-ferromagnet interfaces. Intriguingly, we find that for high transparency junctions, the spin mixing angle appears to take a relatively narrow range of values across all the samples studied. The ferromagnets we have chosen to study share a common property in terms of their spin arrangement, and our observations may point to the importance of this property in determining the spin mixing angle under these circumstances.

  14. [Probabilistic calculations of biomolecule charge states that generate mass spectra of multiply charged ions].

    PubMed

    Raznikova, M O; Raznikov, V V

    2015-01-01

    In this work, information relating to charge states of biomolecule ions in solution obtained using the electrospray ionization mass spectrometry of different biopolymers is analyzed. The data analyses have mainly been carried out by solving an inverse problem of calculating the probabilities of retention of protons and other charge carriers by ionogenic groups of biomolecules with known primary structures. The approach is a new one and has no known to us analogues. A program titled "Decomposition" was developed and used to analyze the charge distribution of ions of native and denatured cytochrome c mass spectra. The possibility of splitting of the charge-state distribution of albumin into normal components, which likely corresponds to various conformational states of the biomolecule, has been demonstrated. The applicability criterion for using previously described method of decomposition of multidimensional charge-state distributions with two charge carriers, e.g., a proton and a sodium ion, to characterize the spatial structure of biopolymers in solution has been formulated. In contrast to known mass-spectrometric approaches, this method does not require the use of enzymatic hydrolysis or collision-induced dissociation of the biopolymers.

  15. Proflavin binding to poly(d(A-T)) and poly(d(A-br/sup 5/U))'' triplet state and temperature-jump kinetics

    SciTech Connect

    Corin, A.F.; Jovin, T.M.

    1986-07-01

    The delayed fluorescence properties of proflavin have been exploited in studies of the excited-state binding kinetics of the dye to poly(d(A-T)) and its brominated analogue poly-d(A-br/sup 5/U)) at room temperature and pH 7. The two analyzed luminescence decay times of the DNA-dye complex are dependent on the total nucleic acid concentration. This dependence is shown to reflect a temporal coupling of the intrinsic delayed emission decay rates with the dynamic chemical kinetic binding processes in the excited state. Temperature-jump kinetic studies conducted on the brominated polymer and corresponding information on poly(d(A-T)) from a previous study provide complementary information about the ground state. The ground-state kinetic data are analyzed in terms of two alternative models incorporating series and parallel reaction schemes. A comparison of the ground- and excited-state kinetic parameters reveals that the external binding process is much stronger and the intercalation is much weaker in the excited state. That the excited-state data are only consistent with the series model suggests that delayed luminescence studies may provide a general tool for distinguishing between the two kinetic mechanisms.

  16. Indirect detection of infinite-speed MAS solid-state NMR spectra

    NASA Astrophysics Data System (ADS)

    Perras, Frédéric A.; Venkatesh, Amrit; Hanrahan, Michael P.; Goh, Tian Wei; Huang, Wenyu; Rossini, Aaron J.; Pruski, Marek

    2017-03-01

    Heavy spin-1/2 nuclides are known to possess very large chemical shift anisotropies that can challenge even the most advanced magic-angle-spinning (MAS) techniques. Wide manifolds of overlapping spinning sidebands and insufficient excitation bandwidths often obfuscate meaningful spectral information and force the use of static, low-resolution solid-state (SS)NMR methods for the characterization of materials. To address these issues, we have merged fast-magic-angle-turning (MAT) and dipolar heteronuclear multiple-quantum coherence (D-HMQC) experiments to obtain D-HMQC-MAT pulse sequences which enable the rapid acquisition of 2D SSNMR spectra that correlate isotropic 1H chemical shifts to the indirectly detected isotropic ;infinite-MAS; spectra of heavy spin-1/2 nuclides. For these nuclides, the combination of fast MAS and 1H detection provides a high sensitivity, which rivals the DNP-enhanced ultra-wideline SSNMR. The new pulse sequences were used to determine the Pt coordination environments in a complex mixture of decomposition products of transplatin and in a metal-organic framework with Pt ions coordinated to the linker ligands.

  17. Spectra of Lorentz-violating Dirac bound states in a cylindrical well

    NASA Astrophysics Data System (ADS)

    Xiao, Zhi

    2016-12-01

    In the presence of the Lorentz-violating bμ coefficient, the spectra of bound states for a Dirac particle in a cylindric well are changed. Compared to the Lorentz invariant (LI) spectrum, the Lorentz violation deviation becomes significant when eigenenergy E is sufficiently close to the critical values ±m , where m is the particle's mass. The detailed profile of the deviation depends on the observer Lorentz nature of bμ. We discussed three types of bμ configuration. When bμ=(0 ,0 ,0 ,bZ) is parallel to the well axis, the would be degenerate LI spectra split into two subspectra, reminiscent of the Zeeman splitting in the presence of a weak magnetic field. Depending on the relative sign of bZ accompanying mass m in the dispersion relation, the spectrum extends or shrinks in the allowed eigenenergy region. When bμ is a radial [bμ=(0 ,b cos ϕ ,b sin ϕ ,0 ) ] or purely timelike vector [bμ=(bT,0 →)], the spin-up and down components are coupled together, and there is no splitting. However, the monotonic increasing behavior of well depth V0 with the decrease of eigenenergy E is slightly changed when E is sufficiently close to -m .

  18. The Dependence of Quenching Rate Coefficients for Singlet and Triplet States of n2 and o2 on Vibrational and Translational Temperatures

    NASA Astrophysics Data System (ADS)

    Kirillov, Andrey

    We apply Landau-Zener and Rosen-Zener approximations to obtain analytical formulas for the calculation of quenching rate coefficients of electronically excited states of N2 and O2. This method has allowed us to estimate contributions of intramolecular and intermolecular electron energy transfer processes in the quenching. Using a modified Treanor distribution on vibrational levels for in ground state molecules we have investigated an influence of the vibrational excitation on the rate coefficients. Special attention is paid to energy transfer processes related with the afterglow in laboratory discharges. It is found that there is the influence of vibrational temperature on the coefficients. A dependence of the rate coefficients on translational temperature is studied for few states of N2 and O2. It is shown that for some states there is good agreement of results of theoretical calculations with available experimental data.

  19. Carbazole Linked NIR Aza-BODIPY Dyes as Triplet Sensitizers and Photoacoustic Contrast Agents for Deep Tissue Imaging.

    PubMed

    Sekar, Nagaiyan; D, Ramaiah; Gawale, Yogesh; N, Adarsh; J, Joseph; Pramanik, M; Kalva, S K

    2017-02-22

    Four novel N-ethylcarbazole linked aza-BODIPY dyes (8a-b and 9a-b) were synthesized and characterized. The presence of N-ethylcarbazole moiety shifts their absorption and fluorescence spectra to the near-infrared region, ca. 650-730 nm, of electromagnetic spectra. These dyes possess strong molar absorptivity in the range of 3-4 x 104 M-1cm-1 with low fluorescence quantum yields. The triplet excited state as well as singlet oxygen generation of these dyes were enhanced upon iodination at the core position. The core iodinated dyes 9a-b showed excellent triplet quantum yield of ca. 90% and 75% with singlet oxygen generation efficiency of ca. 70% and 60% when compared to the parent dyes. The derivatives 8a-b showed dual absorption profiles in contrast to the dyes 9a-b, which has the characteristic absorption band of the aza-BODIPY dyes. DFT calculations revealed the electron density is spread over the iodine and dipyrromethene plane of, 9a-b, whereas in 8a-b the electron density distributed on carbazole ring as well as dipyrromethene plane of aza-BODIPY. The uniqueness of these aza-BODIPY systems is that they exhibit efficient triplet state quantum yields, high singlet oxygen generation yields and good photostability. Further we explored the photoacoustic (PA) characteristics of these aza-BODIPY dyes, and observed efficient PA signals for 8a compared to blood serum with in vitro deep tissue imaging, thereby confirming its use as a promising photoacoustic contrast agent.

  20. OptaDOS: A tool for obtaining density of states, core-level and optical spectra from electronic structure codes

    NASA Astrophysics Data System (ADS)

    Morris, Andrew J.; Nicholls, Rebecca J.; Pickard, Chris J.; Yates, Jonathan R.

    2014-05-01

    We present OptaDOS, a program for calculating core-electron and low-loss electron energy loss spectra (EELS) and optical spectra along with total-, projected- and joint-density of electronic states (DOS) from single-particle eigenenergies and dipole transition coefficients. Energy-loss spectroscopy is an important tool for probing bonding within a material. Interpreting these spectra can be aided by first principles calculations. The spectra are generated from the eigenenergies through integration over the Brillouin zone. An important feature of this code is that this integration is performed using a choice of adaptive or linear extrapolation broadening methods which we show produces higher accuracy spectra than standard fixed-width Gaussian broadening. OptaDOS may be straightforwardly interfaced to any electronic structure code. OptaDOS is freely available under the GNU General Public licence from http://www.optados.org.

  1. Spectroscopic study on deuterated benzenes. I. Microwave spectra and molecular structure in the ground state

    SciTech Connect

    Kunishige, Sachi; Katori, Toshiharu; Baba, Masaaki; Nakajima, Masakazu; Endo, Yasuki

    2015-12-28

    We observed microwave absorption spectra of some deuterated benzenes and accurately determined the rotational constants of all H/D isotopomers in the ground vibrational state. Using synthetic analysis assuming that all bond angles are 120°, the mean bond lengths were obtained to be r{sub 0}(C–C) = 1.3971 Å and r{sub 0}(C–H) = r{sub 0}(C–D) = 1.0805 Å. It has been concluded that the effect of deuterium substitution on the molecular structure is negligibly small and that the mean bond lengths of C–H and C–D are identical unlike small aliphatic hydrocarbons, in which r{sub 0}(C–D) is about 5 mÅ shorter than r{sub 0}(C–H). It is considered that anharmonicity is very small in the C–H stretching vibration of aromatic hydrocarbons.

  2. Formation of ultracold {sup 7}Li{sup 85}Rb molecules in the lowest triplet electronic state by photoassociation and their detection by ionization spectroscopy

    SciTech Connect

    Altaf, Adeel Dutta, Sourav; Lorenz, John; Pérez-Ríos, Jesús; Chen, Yong P.; Elliott, D. S.

    2015-03-21

    We report the formation of ultracold {sup 7}Li{sup 85}Rb molecules in the a{sup 3}Σ{sup +} electronic state by photoassociation (PA) and their detection via resonantly enhanced multiphoton ionization (REMPI). With our dual-species Li and Rb magneto-optical trap apparatus, we detect PA resonances with binding energies up to ∼62 cm{sup −1} below the {sup 7}Li 2s {sup 2}S{sub 1/2} + {sup 85}Rb 5p {sup 2}P{sub 1/2} asymptote. In addition, we use REMPI spectroscopy to probe the a{sup 3}Σ{sup +} state and excited electronic 3{sup 3}Π and 4{sup 3}Σ{sup +} states and identify a{sup 3}Σ{sup +} (v″ = 7–13), 3{sup 3}Π (v{sub Π}′ = 0–10), and 4{sup 3}Σ{sup +} (v{sub Σ}′ = 0–5) vibrational levels. Our line assignments agree well with ab initio calculations. These preliminary spectroscopic studies on previously unobserved electronic states are crucial to discovering transition pathways for transferring ultracold LiRb molecules created via PA to deeply bound rovibrational levels of the electronic ground state.

  3. Spontaneous triplet, tubal ectopic gestation.

    PubMed Central

    Nwanodi, Oroma; Berry, Robert

    2006-01-01

    Only six cases of spontaneous, unilateral, triplet ectopic gestations have previously been reported. We now present a seventh case. The patient's prior obstetrical history was significant for a term stillbirth and a term cesarean section for breech. Quantitative betahCG was normal for gestational age; however, the increased trophoblastic mass of an inappropriately implanted multiple gestation may produce sufficient betahCG to mimic an intrauterine singleton gestation. Resolution was achieved via salpingostomy. This case is significant for being spontaneously conceived and not the result of assisted reproductive technologies. Furthermore, this case supports an association between prior cesarean section and ectopic gestation. Images Figure 1 PMID:16775922

  4. Hydrophobic clustering in nonnative states of a protein: Interpretation of chemical shifts in NMR spectra of denatured states of lysozyme

    SciTech Connect

    Evans, P.A.; Topping, K.D.; Woolfson, D.N.; Dobson, C.M. )

    1991-01-01

    Chemical shifts of resonances of specific protons in the 1H NMR spectrum of thermally denatured hen lysozyme have been determined by exchange correlation with assigned native state resonances in 2D NOESY spectra obtained under conditions where the two states are interconverting. There are subtle but widespread deviations of the measured shifts from the values which would be anticipated for a random coil; in the case of side chain protons these are virtually all net upfield shifts and it is shown that this may be the averaged effect of interactions with aromatic rings in a partially collapsed denatured state. In a very few cases, notably that of two sequential tryptophan residues, it is possible to interpret these effects in terms of specific, local interresidue interactions. Generally, however, there is no correlation with either native state shift perturbations or with sequence proximity to aromatic groups. Diminution of most of the residual shift perturbations on reduction of the disulfide cross-links confirms that they are not simply effects of residues adjacent in the sequence. Similar effects of chemical denaturants, with the disulfides intact, demonstrate that the shift perturbations reflect an enhanced tendency to side chain clustering in the thermally denatured state. The temperature dependences of the shift perturbations suggest that this clustering is noncooperative and is driven by small, favorable enthalpy changes. While the extent of conformational averaging is clearly much greater than that observed for a homologous protein, alpha-lactalbumin, in its partially folded molten globule state, the results clearly show that thermally denatured lysozyme differs substantially from a random coil, principally in that it is partially hydrophobically collapsed.

  5. First-principles calculation of ground and excited-state absorption spectra of ruby and alexandrite considering lattice relaxation

    NASA Astrophysics Data System (ADS)

    Watanabe, Shinta; Sasaki, Tomomi; Taniguchi, Rie; Ishii, Takugo; Ogasawara, Kazuyoshi

    2009-02-01

    We performed first-principles calculations of multiplet structures and the corresponding ground-state absorption and excited-state absorption spectra for ruby (Cr3+:α-Al2O3) and alexandrite (Cr3+:BeAl2O4) which included lattice relaxation. The lattice relaxation was estimated using the first-principles total energy and molecular-dynamics method of the CASTEP code. The multiplet structure and absorption spectra were calculated using the configuration-interaction method based on density-functional calculations. For both ruby and alexandrite, the theoretical absorption spectra, which were already in reasonable agreement with experimental spectra, were further improved by consideration of lattice relaxation. In the case of ruby, the peak positions and peak intensities were improved through the use of models with relaxations of 11 or more atoms. For alexandrite, the polarization dependence of the U band was significantly improved, even by a model with a relaxation of only seven atoms.

  6. Perturbations in the Spectra of High Rydberg States: Channel Interactions, Stark and Zeeman Effects

    NASA Astrophysics Data System (ADS)

    Haase, Christa; Schäfer, Martin; Hogan, Stephen D.; Merkt, Frédéric

    2011-06-01

    Rydberg states of principal quantum number n≫50 have been prepared by irradiation of an atomic beam of xenon with vacuum ultraviolet (VUV) radiation. Narrowband submillimeter-wave (THz) radiation was then used to record spectra of transitions from these Rydberg states to higher or lower-lying Rydberg states. The transitions were detected by selective field ionization and recording either the electrons or the ions, the latter offering the advantage of mass selection. Rydberg states of high principal quantum number are extremely sensitive to their environment, which can be exploited to characterize the experimental conditions under which the spectroscopic measurements are carried out. The high resolution achieved in the experiments (better than 100 kHz) enabled the study of the spectral lineshapes and line positions in dependence of weak electric (down to below 100μV/cm) and magnetic fields (down to a few μT), and of the density of Rydberg atoms and ions generated in the experimental volume. The experiments rely on the use of a pulsed, broadly tunable, laser-based source of THz radiation for survey scans, and of a phase- and frequency-stabilized submillimeter-wave backward-wave oscillator-based radiation source for precision measurements. To illustrate the use of these sources, we present the results of the spectroscopic investigations of the hyperfine structure of 129Xe Rydberg states in spectral regions where s-d interactions are expected to play a role. F. Merkt and A. Osterwalder Int. Rev. Phys. Chem. 21, 385, (2002). J. Liu and F. Merkt Appl. Phys. Lett. 93, 131105, (2008). M. Schäfer, M. Andrist, H. Schmutz, F. Lewen, G. Winnewisser and F. Merkt J. Phys. B: At. Mol. Opt. Phys. 39, 831, (2006).

  7. Temperature-dependent vibrational spectra of zinc(II) bis-(N,N'-diethyldithiocarbamate) in solid state and solution

    NASA Astrophysics Data System (ADS)

    Trendafilova, N.; Kellner, R.

    The IR spectra of zinc(II) bis-(N,N'-diethyldithiocarbamate) in the solid state (at 20, 80 and 120°C) as well as in solution (20°C) have been recorded and discussed as to the changes in the zinc coordination sphere that may occur upon heating and dissolution. The decreased number of bands in the high-temperature and in the solution specta as compared with the room temperature solid state spectra has been explained by removal of the intermolecular contacts upon dissolution or thermal averaging in the high temperature solid state.

  8. Excited-state Raman spectroscopy with and without actinic excitation: S{sub 1} Raman spectra of trans-azobenzene

    SciTech Connect

    Dobryakov, A. L.; Quick, M.; Ioffe, I. N.; Granovsky, A. A.; Ernsting, N. P.; Kovalenko, S. A.

    2014-05-14

    We show that femtosecond stimulated Raman spectroscopy can record excited-state spectra in the absence of actinic excitation, if the Raman pump is in resonance with an electronic transition. The approach is illustrated by recording S{sub 1} and S{sub 0} spectra of trans-azobenzene in n-hexane. The S{sub 1} spectra were also measured conventionally, upon nπ* (S{sub 0} → S{sub 1}) actinic excitation. The results are discussed and compared to earlier reports.

  9. Photobehavior of mixed nπ*/ππ* triplets: simultaneous detection of the two transients, solvent-dependent hydrogen abstraction, and reequilibration upon protein binding.

    PubMed

    Jornet, Dolors; Tormos, Rosa; Miranda, Miguel A

    2011-09-15

    In the present work, a systematic study on hydrogen abstraction by the excited triplet states of 4-methoxybenzophenone (1) and 4,4'-dimethoxybenzophenone (2) from 1,4-cyclohexadiene (3), 4-methylphenol (4), 1,2,3,4-tetrahydroquinoline (5), and 1-methyl-1,2,3,4-tetrahydroquinoline (6) in different media has been undertaken. Laser flash photolysis (LFP) revealed that in nonpolar solvents, 1 and 2 triplets have a nπ* configuration with the typical benzophenone-like T-T absorption spectrum (λ(max) ca. 525 nm). Conversely, in aqueous solution, transient absorption spectra with maxima at 450 and 680 nm, attributed to the ππ* triplet, were obtained. Quenching of 1 or 2 triplet by 3 led to ketyl radical formation with rate constants in the range of 10(6)-10(8) M(-1) s(-1), being one order of magnitude higher in acetonitrile than in aqueous media. The rate constants of quenching by 4 and 5 were similar in both polar and nonpolar solvents; the highest value was found for 6 in acetonitrile ((6.3 to 6.9) × 10(9) M(-1) s(-1)). For mechanistic insight, LFP of 1 or 2 in the presence of dimethoxybenzene as electron donor was performed. The results showed that in this case, triplet quenching is favored in aqueous solution. In addition, 2 included in human serum albumin (HSA) was submitted to LFP. The decay kinetics, monitored at 430 nm, fitted well with three lifetimes of 0.45, 1.4, and 14.4 μs assignable to 2 in bulk solution and in site II or in site I of HSA, respectively. This assignment was confirmed by using oleic acid and ibuprofen as selective displacement probes.

  10. Reinvestigation of the triplet-minus-singlet spectrum of chloroplasts

    NASA Astrophysics Data System (ADS)

    Jávorfi, T.; Garab, G.; Razi Naqvi, K.

    2000-01-01

    A comparison of the triplet-minus-singlet (TmS) absorption spectrum of spinach chloroplasts, recorded some thirty years ago, with the more recently published TmS spectrum of isolated Chl a/ b LHCII (light-harvesting complexes associated with photosystem II of higher plants) shows that the two spectra are very similar, which is to be expected, since only the carotenoid pigments contribute to each spectrum. Be that as it may, the comparison also reveals a dissimilarity: photoexcitation of the sample does, or does not, affect the absorbance in the Qy region (650-700 nm), depending on whether the sample is a suspension of chloroplasts or of isolated LHCII. The Qy-signal in the TmS spectrum of LHCII decays, it should be noted, at the same rate as the rest of the difference spectrum, and its most prominent feature is a negative peak. As the carotenoids do not absorb in the Qy region, the presence of a signal in this region calls for an explanation: van der Vos, Carbonera and Hoff, the first to find as well as fathom the phenomenon, attributed the Qy-signal to a change, in the absorption spectrum of a chlorophyll a (Chl a) molecule, brought about by the presence of triplet excitation on a neighbouring carotenoid (Car). The difference in the behaviours of chloroplasts and LHCII, if reproducible, would imply that the Car triplets which give rise to the TmS spectrum of chloroplasts do not influence the absorption spectra of their Chl a neighbours. With a view to reaching a firm conclusion about this vexed issue, spinach chloroplasts and thylakoids have been examined with the aid of the same kinetic spectrometer as that used for investigating LHCII; the TmS spectra of both chloroplasts and thylakoids contain prominent bleaching signals centred at 680 nm, and the triplet decay time in each case is comparable to that of the Chl a/ b LHCII triplets. Results pertaining to other closely related systems are recalled, and it is concluded that, so far as the overall appearance of the

  11. Lowest triplet (n,π{sup *}) state of 2-cyclohexen-1-one: Characterization by cavity ringdown spectroscopy and quantum-chemical calculations

    SciTech Connect

    McAnally, Michael O.; Zabronsky, Katherine L.; Stupca, Daniel J.; Phillipson, Kaitlyn; Pillsbury, Nathan R.; Drucker, Stephen

    2013-12-07

    The cavity ringdown (CRD) absorption spectrum of 2-cyclohexen-1-one (2CHO) was recorded over the range 401.5–410.5 nm in a room-temperature gas cell. The very weak band system (ε ⩽ 0.1 M{sup −1} cm{sup −1}) in this spectral region is due to the T{sub 1}(n, π*) ← S{sub 0} electronic transition. The 0{sub 0}{sup 0} origin band was assigned to the feature observed at 24 558.8 ± 0.3 cm{sup −1}. We have assigned 46 vibronic transitions in a region extending from −200 to +350 cm{sup −1} relative to the origin band. For the majority of these transitions, we have made corresponding assignments in the spectrum of the deuterated derivative 2CHO-2,6,6-d{sub 3}. From the assignments, we determined fundamental frequencies for several vibrational modes in the T{sub 1}(n, π{sup *}) excited state of 2CHO, including the lowest ring-twisting (99.6 cm{sup −1}) and ring-bending (262.2 cm{sup −1}) modes. These values compare to fundamentals of 122.2 cm{sup −1} and 251.9 cm{sup −1}, respectively, determined previously for the isoconfigurational S{sub 1}(n, π{sup *}) excited state of 2CHO and 99 cm{sup −1} and 248 cm{sup −1}, respectively, for the S{sub 0} ground state. With the aid of quantum-mechanical calculations, we have also ascertained descriptions for these two modes, thereby resolving ambiguities appearing in the previous literature. The ring-twisting mode (ν{sub 39}) contains a significant contribution from O=C–C=C torsion, whereas the ring-bending mode (ν{sub 38} in the ground state) involves mainly the motion of C-5 with respect to the plane containing the other heavy atoms. The CRD spectroscopic data for the T{sub 1}(n, π{sup *}) state have allowed us to benchmark several computational methods for treating excited states, including time-dependent density functional theory and an equation-of-motion coupled cluster method. In turn, the computational results provide an explanation for observed differences in the T{sub 1}(n,

  12. Generation of long-lived methylviologen radical cation in the triplet-state mediated electron transfer in a β-cyclodextrin based supramolecular triad

    NASA Astrophysics Data System (ADS)

    Rakhi, Arikkottira M.; Gopidas, Karical R.

    2015-01-01

    A novel tris(bipyridyl)ruthenium-pyrene-methylviologen supramolecular triad was assembled through inclusion complexation of adamantane-linked Ru(II)-Py dyad in MV2+-linked β-cyclodextrin. Excitation of the Ru(II) chromophore populated its 3MLCT which upon energy transfer gave 3Py, which donates an electron to MV2+ to give Ru(II)-Pyrad +-MVrad +. A second electron transfer then occurs from Ru(II) to Pyrad + to give the supramolecular Ru(III)-Py-MVrad + charge separated state. Laser flash photolysis experiments confirmed formation of MVrad + which exhibited 100 μs lifetime. Steady state irradiation of the self-assembled system in the presence of sacrificial donor also led to formation of long-lived MVrad +.

  13. Enabling the Triplet of Tetraphenylethene to Sensitize the Excited State of Europium(III) for Protein Detection and Time‐Resolved Luminescence Imaging

    PubMed Central

    Zhu, Zece; Song, Bo; Yuan, Jingli

    2016-01-01

    A tetraphenylethene (TPE) group that exhibits aggregation‐induced emission is incorporated into the ligand of a Eu(III) complex (TPEEu) to sensitize the excited state of Eu(III). In steady‐state measurements, TPEEu exhibits weak luminescence when dissolved in aqueous solutions even at a high concentration level, but emits strong fluorescence of TPE and phosphorescence of Eu(III) upon binding with bovine serum albumin. With a delay time of 0.05 ms and a gate time of 1.0 ms in time‐resolved measurements, only phosphorescent emission of Eu(III) is observed with a high on/off ratio. Moreover, this probe is successfully used in time‐resolved luminescence imaging to eliminate the background signal from biological autofluorescence without a washing process. This work provides a general strategy in designing Ln(III) complexes for detecting a broad range of biological molecules. PMID:27981006

  14. Analysis of source spectra, attenuation, and site effects from central and eastern United States earthquakes

    SciTech Connect

    Lindley, G.

    1998-02-01

    This report describes the results from three studies of source spectra, attenuation, and site effects of central and eastern United States earthquakes. In the first study source parameter estimates taken from 27 previous studies were combined to test the assumption that the earthquake stress drop is roughly a constant, independent of earthquake size. 200 estimates of stress drop and seismic moment from eastern North American earthquakes were combined. It was found that the estimated stress drop from the 27 studies increases approximately as the square-root of the seismic moment, from about 3 bars at 10{sup 20} dyne-cm to 690 bars at 10{sup 25} dyne-cm. These results do not support the assumption of a constant stress drop when estimating ground motion parameters from eastern North American earthquakes. In the second study, broadband seismograms recorded by the United States National Seismograph Network and cooperating stations have been analysed to determine Q{sub Lg} as a function of frequency in five regions: the northeastern US, southeastern US, central US, northern Basin and Range, and California and western Nevada. In the third study, using spectral analysis, estimates have been made for the anelastic attenuation of four regional phases, and estimates have been made for the source parameters of 27 earthquakes, including the M{sub b} 5.6, 14 April, 1995, West Texas earthquake.

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

    NASA Astrophysics Data System (ADS)

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

    2004-01-01

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

  16. Production of N2 Vegard-Kaplan and other triplet band emissions in the dayglow of Titan

    NASA Astrophysics Data System (ADS)

    Bhardwaj, Anil; Jain, Sonal Kumar

    2012-04-01

    Recently the Cassini Ultraviolet Imaging Spectrograph (UVIS) has revealed the presence of N2 Vegard-Kaplan (VK) band A3Σu+-X1Σg+ emissions in Titan's dayglow limb observation. We present model calculations for the production of various N2 triplet states (viz., A3Σu+,B3Πg,C3Πu,E3Σu,W3Δu, and B3Σu ) in the upper atmosphere of Titan. The Analytical Yield Spectra technique is used to calculate steady state photoelectron fluxes in Titan's atmosphere, which are in agreement with those observed by the Cassini's CAPS instrument. Considering direct electron impact excitation, inter-state cascading, and quenching effects, the population of different levels of N2 triplet states are calculated under statistical equilibrium. Densities of all vibrational levels of each triplet state and volume production rates for various triplet states are calculated in the model. Vertically integrated overhead intensities for the same date and lighting conditions as reported by the UVIS observations for N2 Vegard-Kaplan A3Σu+-X1Σg+, First Positive B3Πg-A3Σu+, Second Positive (C3Πu - B3Πg), Wu-Benesch (W3Δu - B3Πg), and Reverse First Positive bands of N2 are found to be 132, 114, 19, 22, and 22 R, respectively. Overhead intensities are calculated for each vibrational transition of all the triplet band emissions of N2, which span a wider spectrum of wavelengths from ultraviolet to infrared. The calculated limb intensities of total and prominent transitions of VK band are presented. The model limb intensity of VK emission within the 150-190 nm wavelength region is in good agreement with the Cassini UVIS observed limb profile. An assessment of the impact of solar EUV flux on the N2 triplet band emission intensity has been made by using three different solar flux models, viz., Solar EUV Experiment (SEE), SOLAR2000 (S2K) model of Tobiska (Tobiska, W.K. [2004]. Adv. Space Res. 34, 1736-1746), and HEUVAC model of Richards et al. (Richards, P.G., Woods, T.N., Peterson, W.K. [2006]. Adv

  17. The Hot Star Triplet HD 206267A

    NASA Astrophysics Data System (ADS)

    Wojdowski, P. S.; Schulz, N. S.; Ishibashi, K.; Huenemoerder, D. P.

    2002-12-01

    We have observed the triple O star system HD 206267 with Chandra HETGS for the purpose of studying the properties and dynamics of the system's stellar wind. The triple system includes a 3.7 day binary which was observed once at each of the two phases of quadrature. The spectrum contains emission lines from hydrogen and helium-like oxygen, neon, and magnesium, helium-like silicon and the iron L-shell ions XVII, XVIII, and XIX. We have fit this spectrum with a combination of emission-line spectra of the individual ions at the temperatures at which the populations of the ions peak. From this fit we derive a temperature differential emission measure distribution which is cut off at temperatures above ~10 MK. All lines are very broad with HWHM velocities of ~ 1500 - 2000 km/s. The Lyman_alpha lines from O, Ne, and Mg are blue shifted and asymmetric as would be expected from shocks within a line driven wind of considerable continuum opacity. The stellar triplet revealed the main orbital velocity of 320 km/s through shifts in the X-ray lines. So far, we have not found any indications for a colliding wind in the X-ray spectrum.

  18. Impedance spectra classification for determining the state of charge on a lithium iron phosphate cell using a support vector machine

    NASA Astrophysics Data System (ADS)

    Jansen, P.; Vergossen, D.; Renner, D.; John, W.; Götze, J.

    2015-11-01

    An alternative method for determining the state of charge (SOC) on lithium iron phosphate cells by impedance spectra classification is given. Methods based on the electric equivalent circuit diagram (ECD), such as the Kalman Filter, the extended Kalman Filter and the state space observer, for instance, have reached their limits for this cell chemistry. The new method resigns on the open circuit voltage curve and the parameters for the electric ECD. Impedance spectra classification is implemented by a Support Vector Machine (SVM). The classes for the SVM-algorithm are represented by all the impedance spectra that correspond to the SOC (the SOC classes) for defined temperature and aging states. A divide and conquer based search algorithm on a binary search tree makes it possible to grade measured impedances using the SVM method. Statistical analysis is used to verify the concept by grading every single impedance from each impedance spectrum corresponding to the SOC by class with different magnitudes of charged error.

  19. The delay time dependence of the photoelectron spectra and state populations of three-level ladder K2 molecule

    NASA Astrophysics Data System (ADS)

    Guo, Wei; Lu, Xingqiang; Wang, Xinlin

    2017-02-01

    The delay time dependence of photoelectron spectra and state populations of three-level ladder K2 molecule is investigated by pump-probe pulses via time-dependent wave packet approach. The periodical motion of the wave packet with oscillating period 500 fs results in the periodical variation of photoelectron spectra. The photoelectron spectra show Autler-Townes double splitting at zero delay time, and no splitting at positive delay time. The periodical change of state populations with delay time can be ascribed to the coupling effect between the two pulses. It is found that the selectivity of the state populations may be attained by regulating the delay time. The results can provide some important basis for realizing the optical control of molecules experimentally.

  20. Franck-Condon analysis of the S0 --> T1 absorption and phosphorescence spectra of biphenyl and bridged derivatives

    NASA Astrophysics Data System (ADS)

    Negri, Fabrizia; Zgierski, Marek Z.

    1992-11-01

    The equilibrium geometry and the vibrational force field of the ground and the lowest triplet electronic states of biphenyl and three bridged derivatives-biphenylene, fluorene and phenanthrene-are computed by using an updated version of the QCFF/PI (Quantum Chemical Force Field/π electron) Hamiltonian. The displacement parameters between T1 and S0 are obtained and used to model the S0→T1 absorption and the phosphorescence spectra. The calculated Franck-Condon envelopes are found to be in excellent agreement with the vibrational structure of the observed spectra. The common features of the phosphorescence spectra of biphenyl and fluorene are related to the same orbital nature of the lowest triplet state. The observed asymmetry between the phosphorescence and singlet-triplet absorption spectra of biphenyl is reproduced when the twisted equilibrium geometry of S0 is considered. It is shown that evidence of the nonplanarity of the ground state of biphenyl is manifested by the lower intensity of the band observed in the phosphorescence at 747 cm-1 with respect to the intensity of the same band in fluorene. The increased vibrational activity calculated in the lower frequency region for biphenylene and phenanthrene agrees with the observed spectra and reflects the different orbital nature of the lowest triplet state of the two strongly perturbed bridged derivatives with respect to biphenyl and fluorene. From the analysis of the computed vibrational frequencies, it is suggested that the false origin of the symmetry forbidden phosphorescence of biphenylene is due to the lowest out-of-plane mode of au symmetry.

  1. Evaluation of the state of active ingredients in pharmaceutical preparations using fourier transform-Raman difference spectra.

    PubMed

    Mifune, Masaki; Iwasaki, Toshinobu; Kozaki, Yukari; Tsukamoto, Ikuko; Saito, Madoka; Kitamura, Youji; Yamaguchi, Toshikazu; Saito, Yutaka

    2006-12-01

    To examine the pharmaceutical application of Fourier transform (FT)-Raman spectroscopy, the state of active pharmaceutical ingredients (APIs) in a preparation of several forms was evaluated by investigating the Raman difference spectra between the preparation and excipient. The difference spectra indicated that APIs in alacepril tablets, caffeine sustained-release granules, and quinidine sulfate granules remained unchanged after the manufacturing process. However, the state of sparfloxacin in nanoparticles changed, although it remained unchanged in tablets or powders. These results show that the FT-Raman difference spectrum is expected to be utilized in the field of quality control of crystalline pharmaceutical preparations.

  2. Solvent effects on the steady-state absorption and fluorescence spectra of uracil, thymine and 5-fluorouracil.

    PubMed

    Gustavsson, Thomas; Sarkar, Nilmoni; Bányász, Akos; Markovitsi, Dimitra; Improta, Roberto

    2007-01-01

    We report a comparison of the steady-state absorption and fluorescence spectra of three representative uracil derivatives (uracil, thymine and 5-fluorouracil) in alcoholic solutions. The present results are compared with those from our previous experimental and computational studies of the same compounds in water and acetonitrile. The effects of solvent polarity and hydrogen bonding on the spectra are discussed in the light of theoretical predictions. This comparative analysis provides a more complete picture of the solvent effects on the absorption and fluorescence properties of pyrimidine nucleobases, with special emphasis on the mechanism of the excited state deactivation.

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

    SciTech Connect

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

    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.

  4. [Raman spectra and structure analysis of 2,6-pyridine dicarboxylic acid in different states and single Bacillus spore].

    PubMed

    Huang, Rong-shao; Huang, Xi; Xu, Lan-lan; Li, Yong-qing; Huang, Shu-shi

    2011-03-01

    The Raman spectra of 2,6-pyridine dicarboxylic acid (DPA) and their calcium salts(Ca-DPA) in different states and the Ca-DPA in a single bacterial spore have been recorded by laser tweezers Raman system (LTRS) and the spectra have been assigned. Raman spectra of different states of DPA and Ca-DPA are different evidently. Analysis leading to differences in the structure of spectrum may be due to that the Raman spectra of DPA crystalline reflected more precise characteristics information compared to DPA powder, in which the laser can penetrate through DPA crystalline and the Raman scatter from the crystalline interior is greater than that from DPA powder. The second reason is that DPA powder and Ca-DPA crystalline contain water molecules, and the intermolecular hydrogen bonding in the crystals of these molecules is extensive. The presence of calcium ions would affect the pyridine ring so that both sides of the carboxyl pyridine ring have a certain geometric deformation and the hydroxy carboxylic was damaged. The DPA2-anion is principal in Ca-DPA and the DPA solution. The calcium ion affects the stability of the pyridine ring structure in the Ca-DPA solution. The result from the spectra also showed that the DPA in single spores present Ca-DPA crystal state.

  5. The biomolecule of 5-bromocytosine: FT-IR and FT-Raman spectra and DFT calculations. Identification of the tautomers in the isolated state and simulation the spectra in the solid state.

    PubMed

    Alcolea Palafox, M; Rastogi, V K; Kumar, Satendra; Joe, Hubert

    2013-07-01

    An accurate assignment of the IR spectrum in Ar matrix of 5-bromocytosine and of the IR and Raman spectra in the solid state was carried out. For this purpose Density functional calculations (DFTs) were performed to clarify wavenumber assignments of the experimental observed bands. The calculated values were scaled using scaling equations and they were compared with IR and Raman experimental data. Good reproduction of the experimental wavenumbers is obtained and the% error is very small in the majority of cases. In the isolated state all the tautomer forms of 5-bromocytosine were determined and optimized. The wavenumbers corresponding to C1 and C2b tautomers were identified and assigned in the IR experimental spectrum reported in Ar matrix. Our study confirms the existence of at least two tautomers, the amino-oxo and the amino-hydroxy in the isolated state. In the solid state the FT-IR and FT-Raman spectra of 5-bromocytosine in the powder form were recorded in the region 400-4000 cm(-1) and 50-3500 cm(-1), respectively. The unit cell found in the crystal was simulated as a tetramer form in three tautomers. Thus, it has been possible to assign all the 33 normal modes of vibration. The study indicates that the features, that are the characteristic of the vibrational spectra of cytosine, are retained by the spectra of 5-bromocytosine and it exists in the solid phase in the amino-oxo form.

  6. Influence of various functional groups on the relative stability of alkylperoxy triplet cations: A theoretical study

    NASA Astrophysics Data System (ADS)

    Smith, Kenneth J.; Meloni, Giovanni

    2015-07-01

    CBS-QB3 energy calculations show that the formation of a stable triplet cation for alkylperoxy radicals is dependent on factors other than the stability of the daughter cations exclusively. We have found that in cases where the daughter ions are not capable of stabilizing the cation through hyperconjugation, it is possible for the triplet cation to be bound. In many circumstances, CBS-QB3 calculations have found bound triplet cation states with 'negative dissociation energies.' These results are attributed to the effects that electron donating/withdrawing substituents have on the spin and charge densities of the resulting cations.

  7. Efficient Triplet Exciton Fusion in Molecularly Doped Polymer Light-Emitting Diodes.

    PubMed

    Di, Dawei; Yang, Le; Richter, Johannes M; Meraldi, Lorenzo; Altamimi, Rashid M; Alyamani, Ahmed Y; Credgington, Dan; Musselman, Kevin P; MacManus-Driscoll, Judith L; Friend, Richard H

    2017-04-01

    Solution-processed polymer organic light-emitting diodes (OLEDs) doped with triplet-triplet annihilation (TTA)-upconversion molecules, including 9,10-diphenylanthracene, perylene, rubrene and TIPS-pentacene, are reported. The fraction of triplet-generated electroluminescence approaches the theoretical limit. Record-high efficiencies in solution-processed OLEDs based on these materials are achieved. Unprecedented solid-state TTA-upconversion quantum yield of 23% (TTA-upconversion reaction efficiency of 70%) at electrical excitation well below one-sun equivalent is observed.

  8. Singlet and triplet instability theorems

    SciTech Connect

    Yamada, Tomonori; Hirata, So

    2015-09-21

    A useful definition of orbital degeneracy—form-degeneracy—is introduced, which is distinct from the usual energy-degeneracy: Two canonical spatial orbitals are form-degenerate when the energy expectation value in the restricted Hartree–Fock (RHF) wave function is unaltered upon a two-electron excitation from one of these orbitals to the other. Form-degenerate orbitals tend to have isomorphic electron densities and occur in the highest-occupied and lowest-unoccupied molecular orbitals (HOMOs and LUMOs) of strongly correlated systems. Here, we present a mathematical proof of the existence of a triplet instability in a real or complex RHF wave function of a finite system in the space of real or complex unrestricted Hartree–Fock wave functions when HOMO and LUMO are energy- or form-degenerate. We also show that a singlet instability always exists in a real RHF wave function of a finite system in the space of complex RHF wave functions, when HOMO and LUMO are form-degenerate, but have nonidentical electron densities, or are energy-degenerate. These theorems provide Hartree–Fock-theory-based explanations of Hund’s rule, a singlet instability in Jahn–Teller systems, biradicaloid electronic structures, and a triplet instability during some covalent bond breaking. They also suggest (but not guarantee) the spontaneous formation of a spin density wave (SDW) in a metallic solid. The stability theory underlying these theorems extended to a continuous orbital-energy spectrum proves the existence of an oscillating (nonspiral) SDW instability in one- and three-dimensional homogeneous electron gases, but only at low densities or for strong interactions.

  9. ANALYZING THE LOW STATE OF EF ERIDANI WITH HUBBLE SPACE TELESCOPE ULTRAVIOLET SPECTRA

    SciTech Connect

    Szkody, Paula; Mukadam, Anjum; Gaensicke, Boris T.; Campbell, Ryan K.; Harrison, Thomas E.; Holtzman, Jon; Boberg, Owen; Howell, Steve B.; Walter, Frederick M.; Henden, Arne; Dillon, William; Dealaman, Shannon; Perone, Christian S. E-mail: anjum@astro.washington.ed

    2010-06-20

    Time-resolved spectra throughout the orbit of EF Eri during its low accretion state were obtained with the solar blind channel on the Advanced Camera for Surveys on board the Hubble Space Telescope. The overall spectral distribution exhibits peaks at 1500 and 1700 A, while the UV light curves display a quasi-sinusoidal modulation over the binary orbit. Models of white dwarfs (WDs) with a hot spot and cyclotron emission were attempted to fit the spectral variations throughout the orbit. A non-magnetic WD with a temperature of {approx}10,000 K and a hot spot with a central temperature of 15,000 K generally match the broad absorptions at 1400 and 1600 A with those expected for the quasi-molecular H features H{sub 2} and H{sup +}{sub 2}. However, the flux in the core of the Ly{alpha} absorption does not go to zero, implying an additional component, and the flux variations throughout the orbit are not well matched at long wavelengths. Alternatively, a 9500 K WD with a 100 MG cyclotron component can fit the lowest (phase 0.0) fluxes, but the highest fluxes (phase 0.5) require an additional source of magnetic field or temperature. The 100 MG field required for the UV fit is much higher than that which fits the optical/IR wavelengths, which would support previous suggestions of a complex field structure in polars.

  10. Perturbations to the intersystem crossing of proflavin upon binding to DNA and poly d(A-IU) from triplet-delayed emission spectroscopy.

    PubMed Central

    Lee, W E; Galley, W C

    1988-01-01

    The steady-state prompt fluorescence, phosphorescence and delayed fluorescence spectra and triplet lifetimes of free proflavin and proflavin bound to native DNA and alternating poly d(A-IU) were obtained as a function of temperature in a buffer-glycerol solvent. The intensity of the proflavin E-type delayed fluorescence (DF) relative to both the phosphorescence (Ph) and the prompt fluorescence (F) was observed to increase with temperature, and plots of both ln (DF/Ph) and ln (DF/(F.tau T] as a function of 1/T were linear over a wide range of temperatures. Although the activation energies for the thermal repopulation of the proflavin excited singlet state from the triplet obtained from the slopes of these plots were essentially unchanged on binding, perturbations to the S1----T1 intersystem crossing rate constants extracted from the intercepts at infinite temperature were observed. The marked enhancement of the intersystem crossing that occurs with binding to the iodinated polynucleotide reflects an external heavy atom perturbation upon the intercalated dye which also induces a shortening in the triplet lifetime. With proflavin bound to DNA an enhancement to the S1----T1 intersystem crossing, though lesser in magnitude than for poly d(A-IU), is observed but with no change to the triplet lifetime. The well-studied fluorescence quenching of DNA-bound proflavin is a result of this increase in the intersystem crossing. It is proposed that these non-heavy atom enhancements in the intersystem crossing are due to distortions of the molecular plane of the bound proflavin molecule. In total these analyses provide a complete description of the excited state processes of the proflavin molecule and their variations with temperature. PMID:3224148

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

    PubMed Central

    Dimitrov, Stoichko D.; Wheeler, Scot; Niedzialek, Dorota; Schroeder, Bob C.; Utzat, Hendrik; Frost, Jarvist M.; Yao, Jizhong; Gillett, Alexander; Tuladhar, Pabitra S.; McCulloch, Iain; Nelson, Jenny; Durrant, James R.

    2015-01-01

    Electron spin is a key consideration for the function of organic semiconductors in light-emitting diodes and solar cells, as well as spintronic applications relying on organic magnetoresistance. A mechanism for triplet excited state generation in such systems is by recombination of electron-hole pairs. However, the exact charge recombination mechanism, whether geminate or nongeminate and whether it involves spin-state mixing is not well understood. In this work, the dynamics of free charge separation competing with recombination to polymer triplet states is studied in two closely related polymer-fullerene blends with differing polymer fluorination and photovoltaic performance. Using time-resolved laser spectroscopic techniques and quantum chemical calculations, we show that lower charge separation in the fluorinated system is associated with the formation of bound electron-hole pairs, which undergo spin-state mixing on the nanosecond timescale and subsequent geminate recombination to triplet excitons. We find that these bound electron-hole pairs can be dissociated by electric fields. PMID:25735188

  12. Spectra, energy levels, and energy transition of lanthanide complexes with cinnamic acid and its derivatives

    NASA Astrophysics Data System (ADS)

    Zhou, Kaining; Feng, Zhongshan; Shen, Jun; Wu, Bing; Luo, Xiaobing; Jiang, Sha; Li, Li; Zhou, Xianju

    2016-04-01

    High resolution spectra and luminescent lifetimes of 6 europium(III)-cinnamic acid complex {[Eu2L6(DMF)(H2O)]·nDMF·H2O}m (L = cinnamic acid I, 4-methyl-cinnamic acid II, 4-chloro-cinnamic acid III, 4-methoxy-cinnamic acid IV, 4-hydroxy-cinnamic acid V, 4-nitro-cinnamic acid VI; DMF = N, N-dimethylformamide, C3H7NO) were recorded from 8 K to room temperature. The energy levels of Eu3 + in these 6 complexes are obtained from the spectra analysis. It is found that the energy levels of the central Eu3 + ions are influenced by the nephelauxetic effect, while the triplet state of ligand is lowered by the p-π conjugation effect of the para-substituted functional groups. The best energy matching between the ligand triplet state and the central ion excited state is found in complex I. While the other complexes show poorer matching because the gap of 5D0 and triplet state contracts.

  13. Spectra, energy levels, and energy transition of lanthanide complexes with cinnamic acid and its derivatives.

    PubMed

    Zhou, Kaining; Feng, Zhongshan; Shen, Jun; Wu, Bing; Luo, Xiaobing; Jiang, Sha; Li, Li; Zhou, Xianju

    2016-04-05

    High resolution spectra and luminescent lifetimes of 6 europium(III)-cinnamic acid complex {[Eu2L6(DMF)(H2O)]·nDMF·H2O}m (L=cinnamic acid I, 4-methyl-cinnamic acid II, 4-chloro-cinnamic acid III, 4-methoxy-cinnamic acid IV, 4-hydroxy-cinnamic acid V, 4-nitro-cinnamic acid VI; DMF=N, N-dimethylformamide, C3H7NO) were recorded from 8 K to room temperature. The energy levels of Eu(3+) in these 6 complexes are obtained from the spectra analysis. It is found that the energy levels of the central Eu(3+) ions are influenced by the nephelauxetic effect, while the triplet state of ligand is lowered by the p-π conjugation effect of the para-substituted functional groups. The best energy matching between the ligand triplet state and the central ion excited state is found in complex I. While the other complexes show poorer matching because the gap of (5)D0 and triplet state contracts.

  14. Walking Down the Chalcogenic Group of the Periodic Table: From Singlet to Triplet Organic Emitters.

    PubMed

    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.

  15. Triplet excitons in natural photosynthetic and artificial light harvesting systems: Measurement and modeling

    NASA Astrophysics Data System (ADS)

    Hartzler, Daniel Allen

    Under full sunlight, unprotected (Bacterio)Chlorophyll ((B)Chl) molecules photodegrade in a matter of minutes. This is the result of the generation of highly reactive singlet oxygen (1O2) by energy transfer from the (B)Chl triplet state (3(B)Chl) to the oxygen ground state. Natural photosynthetic systems must protect themselves from 1O2, typically done by positioning carotenoids within a few angstroms of each (B)Chl molecule to quench 3(B)Chl states. Using phosphorescence spectroscopy and computational modeling, we investigated alternative, carotenoid independent, mechanisms which nature may employ to prevent 1O2 sensitization by lowering the energy of 3(B)Chl below that of 1O2. The two proposed triplet lowering mechanisms investigated were: triplet state lowering by strong pigment-pigment interactions (i.e. triplet exciton formation) and triplet state lowering by pigment-protein interactions. Possible natural examples employing these mechanisms are two structures found in green sulfur bacteria: the chlorosome (an antenna containing ~100000 coupled BChl c, d, or e molecules with unexpectedly high photostability) and the Fenna-Matthews-Olson (FMO) complex (an auxiliary antenna containing eight seemingly unprotected BChl a molecules). Measurements performed on linear aggregates of the dye perylene diimide (PDI) show that triplet exciton formation does reduce the triplet state energy. However, direct measurement of triplet state energies for the chlorosome and FMO complex proved experimentally difficult, thus an alternative approach was used to calculate these energies using empirical and excitonic models. Since the use of excitonic modeling requires knowledge of both the pigment site energies and the pigment-pigment interactions (i.e. couplings), work was performed to catalog the monomeric singlet and triplet state energies of all known natural (B)Chl pigments by direct measurement or computational modeling and to characterize the triplet-triplet (T-T) coupling in

  16. Cooper pairs spintronics in triplet spin valves.

    PubMed

    Romeo, F; Citro, R

    2013-11-27

    We study a spin valve with a triplet superconductor spacer intercalated between two ferromagnets with noncollinear magnetizations. We show that the magnetoresistance of the triplet spin valve depends on the relative orientations of the d vector, characterizing the superconducting order parameter, and the magnetization directions of the ferromagnetic layers. For devices characterized by a long superconductor, the effects of a polarized current sustained by Cooper pairs only are observed. In this regime, a supermagnetoresistance effect emerges, and the chiral symmetry of the order parameter of the superconducting spacer is easily recognized. Our findings open new perspectives in designing spintronics devices based on the cooperation of ferromagnetic and triplet correlations.

  17. Higgs triplets and limits from precision measurements

    SciTech Connect

    Chen, Mu-Chun; Dawson, Sally; Krupovnickas, Tadas; /Brookhaven

    2006-04-01

    In this letter, they present the results on a global fit to precision electroweak data in a Higgs triplet model. In models with a triplet Higgs boson, a consistent renormalization scheme differs from that of the Standard Model and the global fit shows that a light Higgs boson with mass of 100-200 GeV is preferred. Triplet Higgs bosons arise in many extensions of the Standard Model, including the left-right model and the Little Higgs models. The result demonstrates the importance of the scalar loops when there is a large mass splitting between the heavy scalars. It also indicates the significance of the global fit.

  18. Analyzing the Low State of EF Eridani with Hubble Space Telescope Ultraviolet Spectra

    NASA Astrophysics Data System (ADS)

    Szkody, Paula; Mukadam, Anjum; Gänsicke, Boris T.; Campbell, Ryan K.; Harrison, Thomas E.; Howell, Steve B.; Holtzman, Jon; Walter, Frederick M.; Henden, Arne; Dillon, William; Boberg, Owen; Dealaman, Shannon; Perone, Christian S.

    2010-06-01

    Time-resolved spectra throughout the orbit of EF Eri during its low accretion state were obtained with the solar blind channel on the Advanced Camera for Surveys on board the Hubble Space Telescope. The overall spectral distribution exhibits peaks at 1500 and 1700 Å, while the UV light curves display a quasi-sinusoidal modulation over the binary orbit. Models of white dwarfs (WDs) with a hot spot and cyclotron emission were attempted to fit the spectral variations throughout the orbit. A non-magnetic WD with a temperature of ~10,000 K and a hot spot with a central temperature of 15,000 K generally match the broad absorptions at 1400 and 1600 Å with those expected for the quasi-molecular H features H2 and H+ 2. However, the flux in the core of the Lyα absorption does not go to zero, implying an additional component, and the flux variations throughout the orbit are not well matched at long wavelengths. Alternatively, a 9500 K WD with a 100 MG cyclotron component can fit the lowest (phase 0.0) fluxes, but the highest fluxes (phase 0.5) require an additional source of magnetic field or temperature. The 100 MG field required for the UV fit is much higher than that which fits the optical/IR wavelengths, which would support previous suggestions of a complex field structure in polars. Based on observations made with the NASA/ESA Hubble Space Telescope, obtained at the Space Telescope Science Institute, which is operated by the Association of Universities for Research in Astronomy, Inc., under NASA contract NAS 5-26555, and with the Apache Point Observatory 3.5 m telescope which is owned and operated by the Astrophysical Research Consortium.

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

    SciTech Connect

    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.

  20. The structure definition of complementary pairs Ade-Ura in different phase states using IR spectra

    NASA Astrophysics Data System (ADS)

    Ten, G. N.; Glukhova, O. E.; Semagina, A. M.; Slepchenkov, M. M.; Baranov, V. I.

    2015-03-01

    The parameters of hydrogen bridges and oscillation spectra of complementary pairs of adenine-uracil formed by Watson- Crick and Hugstin and two reverse to them structures are calculated. Performed analysis shows that due to the characteristic oscillations of the IR spectra in the area of 1600-1800 and 2900-3500 cm-1 it is possible to identify uniquely each of the four pairs in the gas phase and aqueous solution.

  1. Importance of semicore states in GW calculations for simulating accurately the photoemission spectra of metal phthalocyanine molecules

    NASA Astrophysics Data System (ADS)

    Umari, P.; Fabris, S.

    2012-05-01

    The quasi-particle energy levels of the Zn-Phthalocyanine (ZnPc) molecule calculated with the GW approximation are shown to depend sensitively on the explicit description of the metal-center semicore states. We find that the calculated GW energy levels are in good agreement with the measured experimental photoemission spectra only when explicitly including the Zn 3s and 3p semicore states in the valence. The main origin of this effect is traced back to the exchange term in the self-energy GW approximation. Based on this finding, we propose a simplified approach for correcting GW calculations of metal phthalocyanine molecules that avoids the time-consuming explicit treatment of the metal semicore states. Our method allows for speeding up the calculations without compromising the accuracy of the computed spectra.

  2. Analysis of (030),(110), and (011) interacting states of D II 16O from hot temperature emission spectra

    NASA Astrophysics Data System (ADS)

    Starikova, Eugeniya N.; Mikhailenko, Semen N.; Mellau, Georg Ch.; Tyuterev, Vladimir G.

    2006-12-01

    This study is the continuation of our analysis of emission spectra of pure D II0. The spectra have been recorded in the 320 - 860 and 1750 - 4300 cm -1 spectral regions at different pressures and temperatures. The measurements were performed in an alumina cell with an effective length of hot gas of about 50 cm. All spectra have been recorded by using the Bruker IFS 120 spectrometer at the Physikalisch-Chemisches-Institut, Justus-Liebig-Universitat Giessen, Germany). More than 5600 lines have been assigned to the second triad {(030), (110), (011)} of interacting states of the D II 160 molecule. These transitions were assigned to 24 vibration-rotation and rotational bands. An extended set of more than 1500 experimental rovibrational levels for the (030), (110), and (011) interacting states has been obtained. The maximum values of rotational quantum numbers are J max = 30 and K a max = 21 with E max = 10568 cm -1 for the (011) state; J max = 29 and K a max = 21 with E max= 10540 cm -1 for the (030) state, and Jm 26 and Ka max 22 with Eniax 10488 cm1 for the (110) state. A comparison of the observed energy levels with the best available values from literature and with the global prediction is discussed.

  3. Determination of Peptide and Protein Ion Charge States by Fourier Transformation of Isotope-Resolved Mass Spectra

    SciTech Connect

    Tabb, Dave L; Shah, Manesh B; Strader, Michael B; Connelly, Heather M; Hettich, Robert {Bob} L; Hurst, Gregory {Greg} B

    2006-01-01

    We report an automated method for determining charge states from high-resolution mass spectra. Fourier transforms of isotope packets from high-resolution mass spectra are compared to Fourier transforms of modeled isotopic peak packets for a range of charge states. The charge state for the experimental ion packet is determined by the model isotope packet that yields the best match in the comparison of the Fourier transforms. This strategy is demonstrated for determining peptide ion charge states from 'zoom scan' data from a linear quadrupole ion trap mass spectrometer, enabling the subsequent automated identification of singly-through quadruply-charged peptide ions, while reducing the numbers of conflicting identifications from ambiguous charge state assignments. We also apply this technique to determine the charges of intact protein ions from LC-FTICR data, demonstrating that it is more sensitive under these experimental conditions than two existing algorithms. The strategy outlined in this paper should be generally applicable to mass spectra obtained from any instrument capable of isotopic resolution.

  4. DNA Triplet Repeat Expansion and Mismatch Repair

    PubMed Central

    Iyer, Ravi R.; Pluciennik, Anna; Napierala, Marek; Wells, Robert D.

    2016-01-01

    DNA mismatch repair is a conserved antimutagenic pathway that maintains genomic stability through rectification of DNA replication errors and attenuation of chromosomal rearrangements. Paradoxically, mutagenic action of mismatch repair has been implicated as a cause of triplet repeat expansions that cause neurological diseases such as Huntington disease and myotonic dystrophy. This mutagenic process requires the mismatch recognition factor MutSβ and the MutLα (and/or possibly MutLγ) endonuclease, and is thought to be triggered by the transient formation of unusual DNA structures within the expanded triplet repeat element. This review summarizes the current knowledge of DNA mismatch repair involvement in triplet repeat expansion, which encompasses in vitro biochemical findings, cellular studies, and various in vivo transgenic animal model experiments. We present current mechanistic hypotheses regarding mismatch repair protein function in mediating triplet repeat expansions and discuss potential therapeutic approaches targeting the mismatch repair pathway. PMID:25580529

  5. Single-Molecule Fluorescence Spectroscopy of Perylene Diimide Dyes in a γ-Cyclodextrin Film: Manifestation of Photoinduced H-Atom Transfer via Higher Triplet (n, π*) Excited States.

    PubMed

    Mitsui, Masaaki; Fukui, Hiroki; Takahashi, Ryoya; Takakura, Yasushi; Mizukami, Toshinari

    2017-03-02

    Supramolecular complexation of γ-cyclodextrin (γ-CD) with N,N'-bis(2,6-dimethylphenyl)perylene-3,4,9,10-tetracarboxylic diimide (DMP-PDI) or N,N'-bis(2,6-dioctyl)perylene-3,4,9,10-tetracarboxylic diimide (C8-PDI) dye in an aqueous solution and in a γ-CD solid film were investigated via ensemble and single-molecule fluorescence spectroscopy. These two perylene diimide derivatives possess almost the same electronic structure but have different terminal functional groups. This structural difference leads to formation of an inclusion complex of γ-CD with DMP-PDI but not with C8-PDI in aqueous solution. In a γ-CD solid film, the distributions of the wavelengths of emission maximum (λmax(em)) are strikingly different between these two dyes; a much narrower and blue-shifted λmax(em) distribution was observed for C8-PDI relative to DMP-PDI. This difference is attributed to the fact that the C8-PDI molecules are bound at the γ-CD/glass interface as a result of spin-coating of the sample solution, whereas the DMP-PDI molecules form 1:1 and 1:2 inclusion complexes with conformational heterogeneities in the film. In comparison to the case for C8-PDI, more frequent on-off blinking events were observed for DMP-PDI. The blinking statistics of DMP-PDI in the γ-CD film exhibit both single-exponential and nonexponential (i.e., dispersive) kinetics, revealed by robust statistical analysis. Energetic consideration with the aid of theoretical calculations suggests that the underlying photophysics most probably involves hydrogen atom transfer (HAT) between the DMP-PDI guest and γ-CD host via higher excited (n, π*) triplet states. The hypothesis of HAT in the inclusion complex reasonably explains the experimental results; however, a charge transfer hypothesis cannot explain the results. The dispersive kinetics is attributable to the effect of thermal fluctuation in the forward and backward HAT reactions.

  6. Polymer triplet energy levels need not limit photocurrent collection in organic solar cells.

    PubMed

    Schlenker, Cody W; Chen, Kung-Shih; Yip, Hin-Lap; Li, Chang-Zhi; Bradshaw, Liam R; Ochsenbein, Stefan T; Ding, Feizhi; Li, Xiaosong S; Gamelin, Daniel R; Jen, Alex K-Y; Ginger, David S

    2012-12-05

    We study charge recombination via triplet excited states in donor/acceptor organic solar cells and find that, contrary to intuition, high internal quantum efficiency (IQE) can be obtained in polymer/fullerene blend devices even when the polymer triplet state is significantly lower in energy than the intermolecular charge transfer (CT) state. Our model donor system comprises the copolymer PIDT-PhanQ: poly(indacenodithiophene-co-phenanthro[9,10-b]quinoxaline), which when blended with phenyl-C(71)-butyric acid methyl ester (PC(71)BM) is capable of achieving power conversion efficiencies of 6.0% and IQE ≈ 90%, despite the fact that the polymer triplet state lies 300 meV below the interfacial CT state. However, as we push the open circuit voltage (V(OC)) higher by tailoring the fullerene reduction potential, we observe signatures of a new recombination loss process near V(OC) = 1.0 V that we do not observe for PCBM-based devices. Using photoinduced absorption and photoluminescence spectroscopy, we show that a new recombination path opens via the fullerene triplet manifold as the energy of the lowest CT state approaches the energy of the fullerene triplet. This pathway appears active even in cases where direct recombination via the polymer triplet remains thermodynamically accessible. These results suggest that kinetics, as opposed to thermodynamics, can dominate recombination via triplet excitons in these blends and that optimization of charge separation and kinetic suppression of charge recombination may be fruitful paths for the next generation of panchromatic organic solar cell materials with high V(OC) and J(SC).

  7. Effect of nearest-neighbor ions on excited ionic states, emission spectra, and line profiles in hot and dense plasmas

    NASA Technical Reports Server (NTRS)

    Salzmann, D.; Stein, J.; Goldberg, I. B.; Pratt, R. H.

    1991-01-01

    The effect of the cylindrical symmetry imposed by the nearest-neighbor ions on the ionic levels and the emission spectra of a Li-like Kr ion immersed in hot and dense plasmas is investigated using the Stein et al. (1989) two-centered model extended to include computations of the line profiles, shifts, and widths, as well as the energy-level mixing and the forbidden transition probabilities. It is shown that the cylindrical symmetry mixes states with different orbital quantum numbers l, particularly for highly excited states, and, thereby, gives rise to forbidden transitions in the emission spectrum. Results are obtained for the variation of the ionic level shifts and mixing coefficients with the distance to the nearest neighbor. Also obtained are representative computed spectra that show the density effects on the spectral line profiles, shifts, and widths, and the forbidden components in the spectrum.

  8. Calculation of Vibrational and Electronic Excited-State Absorption Spectra of Arsenic-Water Complexes Using Density Functional Theory

    DTIC Science & Technology

    2016-06-03

    of Arsenic- Water Complexes Using Density Functional Theory June 3, 2016 Approved for public release; distribution is unlimited. L. Huang S.g...NUMBER OF PAGES 17. LIMITATION OF ABSTRACT Calculation of Vibrational and Electronic Excited-State Absorption Spectra of Arsenic- Water Complexes Using... water molecules should be associated with response features that are intermediate between that of isolated molecules and that of a bulk system. DFT and

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

    NASA Astrophysics Data System (ADS)

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

    2017-02-01

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

  10. State-by-state investigation of destructive interference in resonance Raman spectra of neutral tyrosine and the tyrosinate anion with the simplified sum-over-states approach.

    PubMed

    Cabalo, Jerry B; Saikin, Semion K; Emmons, Erik D; Rappoport, Dmitrij; Aspuru-Guzik, Alán

    2014-10-16

    UV resonance Raman scattering is uniquely sensitive to the molecular electronic structure as well as intermolecular interactions. To better understand the relationship between electronic structure and resonance Raman cross section, we carried out combined experimental and theoretical studies of neutral tyrosine and the tyrosinate anion. We studied the Raman cross sections of four vibrational modes as a function of excitation wavelength, and we analyzed them in terms of the contributions of the individual electronic states as well as of the Albrecht A and B terms. Our model, which is based on time-dependent density functional theory (TDDFT), reproduced the experimental resonance Raman spectra and Raman excitation profiles for both studied molecules with good agreement. We found that for the studied modes, the contributions of Albrecht's B terms in the Raman cross sections were important across the frequency range spanning the L(a,b) and B(a,b) electronic excitations in tyrosine and the tyrosinate anion. Furthermore, we demonstrated that interference with high-energy states had a significant impact and could not be neglected even when in resonance with a lower-energy state. The symmetry of the vibrational modes served as an indicator of the dominance of the A or B mechanisms. Excitation profiles calculated with a damping constant estimated from line widths of the electronic absorption bands had the best consistency with experimental results.

  11. Restricted active space calculations of L-edge X-ray absorption spectra: from molecular orbitals to multiplet states.

    PubMed

    Pinjari, Rahul V; Delcey, Mickaël G; Guo, Meiyuan; Odelius, Michael; Lundberg, Marcus

    2014-09-28

    The metal L-edge (2p → 3d) X-ray absorption spectra are affected by a number of different interactions: electron-electron repulsion, spin-orbit coupling, and charge transfer between metal and ligands, which makes the simulation of spectra challenging. The core restricted active space (RAS) method is an accurate and flexible approach that can be used to calculate X-ray spectra of a wide range of medium-sized systems without any symmetry constraints. Here, the applicability of the method is tested in detail by simulating three ferric (3d(5)) model systems with well-known electronic structure, viz., atomic Fe(3+), high-spin [FeCl6](3-) with ligand donor bonding, and low-spin [Fe(CN)6](3-) that also has metal backbonding. For these systems, the performance of the core RAS method, which does not require any system-dependent parameters, is comparable to that of the commonly used semi-empirical charge-transfer multiplet model. It handles orbitally degenerate ground states, accurately describes metal-ligand interactions, and includes both single and multiple excitations. The results are sensitive to the choice of orbitals in the active space and this sensitivity can be used to assign spectral features. A method has also been developed to analyze the calculated X-ray spectra using a chemically intuitive molecular orbital picture.

  12. Low frequency plasmonic state and negative permittivity spectra of coagulated Cu granular composite materials in the percolation threshold

    NASA Astrophysics Data System (ADS)

    Tsutaoka, Takanori; Kasagi, Teruhiro; Yamamoto, Shinichiro; Hatakeyama, Kenichi

    2013-05-01

    We have studied the relative complex permittivity (ɛr = ɛr'- iɛr″) of copper granular composite materials containing coagulated Cu particles in the microwave range as well as the electrical conductivity. The insulator to metal transition was observed at the percolation threshold φc = 16.0 vol. %. The enhancement of permittivity in the insulating state can be described by the Effective Cluster Model. Above the percolation threshold φc, it was found that the Cu granular composites show negative permittivity spectra below a characteristic frequency f0 indicating the low frequency plasmonic state. Characteristic frequency tends to increase with particle content.

  13. The examination of berberine excited state by laser flash photolysis

    NASA Astrophysics Data System (ADS)

    Cheng, Lingli; Wang, Mei; Zhao, Ping; Zhu, Hui; Zhu, Rongrong; Sun, Xiaoyu; Yao, Side; Wang, Shilong

    2009-07-01

    The property of the excited triplet state of berberine (BBR) was investigated by using time-resolved laser flash photolysis of 355 nm in acetonitrile. The transient absorption spectra of the excited triplet BBR were obtained in acetonitrile, which have an absorption maximum at 420 nm. And the ratio of excitation to ionization of BBR in acetonitrile solvent was calculated. The self-decay and self-quenching rate constants, and the absorption coefficient of 3BBR* were investigated and the excited state quantum yield was determined. Furthermore utilizing the benzophenone (BEN) as a triplet sensitizer, and the β-carotene (Car) as an excited energy transfer acceptor, the assignment of 3BBR* was further confirmed and the related energy transfer rate constants were also determined.

  14. Hiking on the potential energy surface of a functional tyrosinase model--implications of singlet, broken-symmetry and triplet description.

    PubMed

    Hoffmann, Alexander; Herres-Pawlis, Sonja

    2014-01-14

    The singlet, open-shell singlet and triplet potential energy surfaces (PES) for the peroxo state of a catalytic functional tyrosinase model have been investigated by density functional theory calculations. The broken-symmetry solution exhibits considerable stabilisation over the whole PES but the importance of the triplet state is unravelled as well.

  15. Renormalizing chiral nuclear forces: Triplet channels

    NASA Astrophysics Data System (ADS)

    Long, Bingwei; Yang, C.-J.

    2012-03-01

    We discuss the subleading contact interactions, or counterterms, of the triplet channels of nucleon-nucleon scattering in the framework of chiral effective field theory, with S and P waves as the examples. The triplet channels are special in that they allow the singular attraction of one-pion exchange to modify Weinberg's original power-counting (WPC) scheme. With renormalization group invariance as the constraint, our power counting for the triplet channels can be summarized as a modified version of naive dimensional analysis in which, when compared with WPC, all of the counterterms in a given partial wave (leading or subleading) are enhanced by the same amount. More specifically, this means that WPC needs no modification in 3S1-3D1 and 3P1, whereas a two-order enhancement is necessary in both 3P0 and 3P2-3F2.

  16. Renormalizing Chiral Nuclear Forces: Triplet Channels

    SciTech Connect

    Bingwei Long, Chieh-Jen Yang

    2012-03-01

    We discuss the subleading contact interactions, or counterterms, of the triplet channels of nucleon-nucleon scattering in the framework of chiral effective field theory, with S and P waves as the examples. The triplet channels are special in that it allows the singular attraction of one-pion exchange to modify Weinberg's original power counting (WPC) scheme. With renormalization group invariance as the constraint, our power counting for the triplet channels can be summarized as a modified version of naive dimensional analysis that, when compared with WPC, the subleading counterterms are enhanced as much as the leading one. More specifically, this means that WPC needs no modification in {sup 3}S{sub 1}-{sup 3}D{sub 1} and {sup 3}P{sub 1} whereas a two-order enhancement is necessary in both {sup 3}P{sub 0} and {sup 3}P{sub 2} - {sup 3}F{sub 2}.

  17. Spectral Assignments and Analysis of the Ground State of Nitromethane in High-Resolution FTIR Synchrotron Spectra

    NASA Astrophysics Data System (ADS)

    Twagirayezu, Sylvestre; Billinghurst, Brant E.; May, Tim E.; Dawadi, Mahesh B.; Perry, David S.

    2014-06-01

    The Fourier Transform infrared spectra of CH3NO2, have been recorded, in the 400-950 wn spectral region, at a resolution of 0.00096 wn, using the Far-Infrared Beamline at Canadian Light Source. The observed spectra contain four fundamental vibrations: the NO2 in-plane rock (475.2 wn), the NO2 out-of-plane rock (604.9 wn), the NO2 symmetric bend (657.1 wn), and the CN-stretch (917.2 wn). For the lowest torsional state of CN-stretch and NO2 in-plane rock, transitions involving quantum numbers, " = 0; " {≤ 50} and {_a}" {≤ 10}, have been assigned with the aid of an automated ground state combination difference program together with a traditional Loomis Wood approach Ground state combination differences derived from more than 2100 infrared transitions have been fit with the six-fold torsion-rotation program developed by Ilyushin et al. Additional sextic and octic centrifugal distortion parameters are derived for the ground vibrational state. C. F. Neese., An Interactive Loomis-Wood Package, V2.0, {56th},OSU Interanational Symposium on Molecular Spectroscopy (2001). V. V. Ilyushin, Z. Kisiel, L. Pszczolkowski, H. Mader, and J. T. Hougen, J. Mol. Spectrosc., 259, 26, (2010).

  18. Adsorption of acridine on silver electrode: SERS spectra potential dependence as a probe of adsorbate state

    NASA Astrophysics Data System (ADS)

    Solovyeva, Elena V.; Myund, Liubov A.; Dem'yanchuk, Evgeniya M.; Makarov, Artiom A.; Denisova, Anna S.

    2013-02-01

    This work investigates acridine adsorption on the silver electrode surface. The dependence of the acridine SERS spectra on the electrode potential proved to be quite different for azaheterocycle molecules, while the pH effect as expected. The changes in the acridine SERS spectrum caused by the double electric layer (DEL) rearrangement can be explained by sorption/desorption rather than the adsorbate molecule reorientation. The presence of chloride anions close to the silver surface is important not only for the SERS-active properties but for the formation of the stabilised surface complexes of the protonated acridine as well.

  19. Triplet correlation functions in liquid water

    NASA Astrophysics Data System (ADS)

    Dhabal, Debdas; Singh, Murari; Wikfeldt, Kjartan Thor; Chakravarty, Charusita

    2014-11-01

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

  20. Triplet correlation functions in liquid water

    SciTech Connect

    Dhabal, Debdas; Chakravarty, Charusita; Singh, Murari; Wikfeldt, Kjartan Thor

    2014-11-07

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

  1. Triplet excitons as sensitive spin probes for structure analysis of extended defects in microcrystalline silicon

    NASA Astrophysics Data System (ADS)

    Meier, Christoph; Teutloff, Christian; Behrends, Jan; Bittl, Robert; Astakhov, Oleksandr; Lips, Klaus

    2016-07-01

    Electrically detected magnetic resonance (EDMR) spectroscopy is employed to study the influence of triplet excitons on the photocurrent in state-of-the-art microcrystalline silicon thin-film solar cells. These triplet excitons are used as sensitive spin probes for the investigation of their electronic and nuclear environment in this mixed-phase material. According to low-temperature EDMR results obtained from solar cells with different triplet excitons reside at extended defects in the crystallites of microcrystalline silicon that give rise to shallow states in the silicon band gap. The excitons possess a rather delocalized wave function, couple to electron spins in conduction band tail states nearby, and take part in a spin-dependent recombination process. Our study shows that extended defects such as grain boundaries or stacking faults in the crystalline part of the material act as charge carrier traps that can influence the material conductivity.

  2. Ultrabright fluorescent OLEDS using triplet sinks

    SciTech Connect

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

    2013-06-04

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

  3. Mass spectra of four-quark states in the hidden charm sector

    NASA Astrophysics Data System (ADS)

    Patel, Smruti; Shah, Manan; Vinodkumar, P. C.

    2014-08-01

    Masses of the low-lying four-quark states in the hidden charm sector ( are calculated within the framework of a non-relativistic quark model. The four-body system is considered as two two-body systems such as diquark-antidiquark ( - and quark-antiquark-quark-antiquark ( - q molecular-like four-quark states. Here, the Cornell-type potential has been used for describing the two-body interactions among Q - q , - , Q - , Qq - and Q - q , with appropriate string tensions. Our present analysis suggests the following exotic states: X(3823) , Z c(3900) , X(3915) , Z c(4025) , (4040) , Z 1(4050) and X(4160) as Q - q molecular-like four-quark states, while Z c(3885) , X(3940) and Y(4140) as the diquark-antidiquark four-quark states. We have been able to assign the JPC values for many of the recently observed exotic states according to their structure. Apart from this, we have identified the charged state Z(4430) recently confirmed by LHCb as the first radial excitation of Zc(3885) with G = + 1 and Y(4360) state as the first radial excitation of Y(4008) with G = - 1 and the state as the first radial excitation of the state.

  4. Self-Consistent Constricted Variational Theory RSCF-CV(∞)-DFT and Its Restrictions To Obtain a Numerically Stable ΔSCF-DFT-like Method: Theory and Calculations for Triplet States.

    PubMed

    Park, Young Choon; Senn, Florian; Krykunov, Mykhaylo; Ziegler, Tom

    2016-11-08

    In this paper, the relaxed self-consistent field infinite order constricted variational density functional theory (RSCF-CV(∞)-DFT) for triplet calculations is presented. Here, we focus on two main features of our implementation. First, as an extension of our previous work by Krykunov and Ziegler ( J. Chem. Theory Comput. 2013 , 9 , 2761 ), the optimization of the transition matrix representing the orbital transition is implemented and applied for vertical triplet excitations. Second, restricting the transition matrix, we introduce RSCF-CV(∞)-DFT-based numerically stable ΔSCF-DFT-like methods, the most general of them being SVD-RSCF-CV(∞)-DFT. The reliability of the different methods, RSCF-CV(∞)-DFT and its restricted versions, is examined using the benchmark test set of Silva-Junior et al. ( J. Chem. Phys. 2008 , 129 , 104103 ). The obtained excitation energies validate our approach and implementation for RSCF-CV(∞)-DFT and also show that SVD-RSCF-CV(∞)-DFT mimics very well ΔSCF-DFT, as the root-mean-square deviations between these methods are less than 0.1 eV for all functionals examined.

  5. LIF dispersed emission spectra and characterization of ZnRg (Rg = Ne, Ar, Kr) ground-state potentials

    NASA Astrophysics Data System (ADS)

    Strojecki, M.; Koperski, J.

    2009-09-01

    Laser-induced fluorescence dispersed emission spectra recorded using the C1Π1(υ')→X1Σ0+ transition in ZnKr, ZnAr and ZnNe complexes are reported. The complexes were produced in a continuous free-jet beam crossed with a pulsed dye-laser beam. The spectra were recorded using a spectrograph equipped with CCD camera. The recorded profiles displayed characteristic Condon internal diffraction patterns. The patterns consisted of reflection type continuous features corresponding to bound → free transitions and bound → bound transitions. In simulation of the spectra, M-S(9.09, 7.81), M-S(10.86, 10.32) and M-S(14.49, 8.91) Maitland-Smith M-S( n0, n1) functions were found to represent the repulsive walls of the X1Σ0+-state potentials of ZnKr, ZnAr and ZnNe, respectively. The obtained results were compared with available experimental and theoretical representations of other studies.

  6. Synthetic CA II Triplet Lines

    NASA Astrophysics Data System (ADS)

    Erdelyi, M. M.; Barbuy, B.

    1990-11-01

    RESUMEN. Se hicieron calculos de sintesis del espectro en el ititervalo de longitud de onda - 8700 A, ara ? oder verificar el comporta- mien to de diferentes lineas moleculares y at5micas como funci5n de los parametros esteldres de temperatura, gravedad y metalicidad. El espec- tro sintetico ha sido generado para:(a) todas las , (b) solamente de CN, (c) solamente de TiO, y (d) solamente lineas at6micas. Abstract. Spectrum synthesis calculations are carried out in the wavelength interval X 8300 - 8700 A, in order to verify the behaviour of different molecular and atomic lines as a function of the stellar para meters temperature, gravity and metallicity. Synthetic spectra were ge nerated for: (a) all lines, (b) only CN lines, (c) only TiO lines, and (d) only atomic lines Key `td6: LINE-PROFILE - ST S-AThOSPHERES

  7. Calcium triplet metallicity calibration for stars in the Galactic bulge

    NASA Astrophysics Data System (ADS)

    Vásquez, S.; Zoccali, M.; Hill, V.; Gonzalez, O. A.; Saviane, I.; Rejkuba, M.; Battaglia, G.

    2015-08-01

    Aims: We present a new calibration of the calcium II triplet equivalent widths versus [Fe/H], constructed upon K giant stars in the Galactic bulge. This calibration will be used to derive iron abundances for the targets of the GIBS survey, and is in general especially well suited for solar and supersolar metallicity giants, which are typical of external massive galaxies. Methods: About 150 bulge K giants were observed with the GIRAFFE spectrograph at the VLT with a resolution of R ~ 20 000 and at R ~ 6000. In the first case, the spectra allowed us to directly determine the Fe abundances from several unblended Fe lines, deriving what we call here high-resolution [Fe/H] measurements. The low-resolution spectra allowed us to measure equivalent widths of the two strongest lines of the near-infrared calcium II triplet at 8542 and 8662 Å. Results: By comparing the two measurements, we derived a relation between calcium equivalent widths and [Fe/H] that is linear over the metallicity range probed here, - 1 < [Fe/H] < +0.7. By adding a small second-order correction based on literature globular cluster data, we derived the unique calibration equation [Fe/H] CaT = -3.150 + 0.432W' + 0.006W'2, with an rms dispersion of 0.197 dex, valid across the whole metallicity range -2.3 < [Fe/H] < +0.7. Based on observations taken with ESO telescopes at the La Silla Paranal Observatory under programme ID 385.B-0735(B).Full Table 2 is only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (ftp://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/580/A121

  8. Infrared and Ultraviolet Spectra of Diborane(6): B2H6 and B2D6.

    PubMed

    Peng, Yu-Chain; Chou, Sheng-Lung; Lo, Jen-Iu; Lin, Meng-Yeh; Lu, Hsiao-Chi; Cheng, Bing-Ming; Ogilvie, J F

    2016-07-21

    We recorded absorption spectra of diborane(6), B2H6 and B2D6, dispersed in solid neon near 4 K in both mid-infrared and ultraviolet regions. For gaseous B2H6 from 105 to 300 nm, we report quantitative absolute cross sections; for solid B2H6 and for B2H6 dispersed in solid neon, we measured ultraviolet absorbance with relative intensities over a wide range. To assign the mid-infrared spectra to specific isotopic variants, we applied the abundance of (11)B and (10)B in natural proportions; we undertook quantum-chemical calculations of wavenumbers associated with anharmonic vibrational modes and the intensities of the harmonic vibrational modes. To aid an interpretation of the ultraviolet spectra, we calculated the energies of electronically excited singlet and triplet states and oscillator strengths for electronic transitions from the electronic ground state.

  9. Electronic structure, excited states, and photoelectron spectra of uranium, thorium, and zirconium bis(Ketimido) complexes (C5R5)2M[-NCPh2]2 (M = Th, U, Zr; R = H, CH3).

    PubMed

    Clark, Aurora E; Martin, Richard L; Hay, P Jeffrey; Green, Jennifer C; Jantunen, Kimberly C; Kiplinger, Jaqueline L

    2005-06-23

    Organometallic actinide bis(ketimide) complexes (C5Me5)2An[-N=C(Ph)(R)]2 (where R = Ph, Me, and CH2Ph) of thorium(IV) and uranium(IV) have recently been synthesized that exhibit chemical, structural, and spectroscopic (UV-Visible, resonance-enhanced Raman) evidence for unusual actinide-ligand bonding. [Da Re et al., J. Am. Chem. Soc., 2005, 127, 682; Jantunen et al., Organometallics, 2004, 23, 4682; Morris et al., Organometallics, 2004, 23, 5142.] Similar evidence has been observed for the group 4 analogue (C5H5)2Zr[-N=CPh2]2. [Da Re et al., J. Am. Chem. Soc., 2005, 127, 682.] These compounds have important implications for the development of new heavy-element systems that possess novel electronic and magnetic properties. Here, we have investigated M-ketimido bonding (M = Th, U, Zr), as well as the spectroscopic properties of the highly colored bis-ketimido complexes, using density functional theory (DFT). Photoelectron spectroscopy (PES) has been used to experimentally elucidate the ground-state electronic structure of the thorium and uranium systems. Careful examination of the ground-state electronic structure, as well as a detailed modeling of the photoelectron spectra, reveals similar bonding interactions between the thorium and uranium compounds. Using time-dependent DFT (TDDFT), we have assigned the bands in the previously reported UV-Visible spectra for (C5Me5)2Th[-N=CPh2]2, (C5Me5)2U[-N=CPh2]2, and (C5H5)2Zr[-N=CPh2]2. The low-energy transitions are attributed to ligand-localized N p --> C=N pi excitations. These excited states may be either localized on a single ketimido unit or may be of the ligand-ligand charge-transfer type. Higher-energy transitions are cyclopentadienyl pi --> CN pi or cyclopentadienyl pi --> phenyl pi in character. The lowest-energy excitation in the (C5Me5)2U[-N=Ph2]2 compound is attributed to f-f and metal-ligand charge-transfer transitions that are not available in the thorium and zirconium analogues. Geometry optimization and

  10. EMITTING ELECTRONS SPECTRA AND ACCELERATION PROCESSES IN THE JET OF Mrk 421: FROM THE LOW STATE TO THE GIANT FLARE STATE

    SciTech Connect

    Yan Dahai; Zhang Li; Fan Zhonghui; Zeng Houdun; Yuan Qiang

    2013-03-10

    We investigate the electron energy distributions (EEDs) and the acceleration processes in the jet of Mrk 421 through fitting the spectral energy distributions (SEDs) in different active states in the frame of a one-zone synchrotron self-Compton model. After assuming two possible EEDs formed in different acceleration models: the shock-accelerated power law with exponential cut-off (PLC) EED and the stochastic-turbulence-accelerated log-parabolic (LP) EED, we fit the observed SEDs of Mrk 421 in both low and giant flare states using the Markov Chain Monte Carlo method which constrains the model parameters in a more efficient way. The results from our calculations indicate that (1) the PLC and LP models give comparably good fits for the SED in the low state, but the variations of model parameters from low state to flaring can be reasonably explained only in the case of the PLC in the low state; and (2) the LP model gives better fits compared to the PLC model for the SED in the flare state, and the intra-day/night variability observed at GeV-TeV bands can be accommodated only in the LP model. The giant flare may be attributed to the stochastic turbulence re-acceleration of the shock-accelerated electrons in the low state. Therefore, we may conclude that shock acceleration is dominant in the low state, while stochastic turbulence acceleration is dominant in the flare state. Moreover, our result shows that the extrapolated TeV spectra from the best-fit SEDs from optical through GeV with the two EEDs are different. It should be considered with caution when such extrapolated TeV spectra are used to constrain extragalactic background light models.

  11. Direct generation of photon triplets using cascaded photon-pair sources.

    PubMed

    Hübel, Hannes; Hamel, Deny R; Fedrizzi, Alessandro; Ramelow, Sven; Resch, Kevin J; Jennewein, Thomas

    2010-07-29

    Non-classical states of light, such as entangled photon pairs and number states, are essential for fundamental tests of quantum mechanics and optical quantum technologies. The most widespread technique for creating these quantum resources is spontaneous parametric down-conversion of laser light into photon pairs. Conservation of energy and momentum in this process, known as phase-matching, gives rise to strong correlations that are used to produce two-photon entanglement in various degrees of freedom. It has been a longstanding goal in quantum optics to realize a source that can produce analogous correlations in photon triplets, but of the many approaches considered, none has been technically feasible. Here we report the observation of photon triplets generated by cascaded down-conversion. Each triplet originates from a single pump photon, and therefore quantum correlations will extend over all three photons in a way not achievable with independently created photon pairs. Our photon-triplet source will allow experimental interrogation of novel quantum correlations, the generation of tripartite entanglement without post-selection and the generation of heralded entangled photon pairs suitable for linear optical quantum computing. Two of the triplet photons have a wavelength matched for optimal transmission in optical fibres, suitable for three-party quantum communication. Furthermore, our results open interesting regimes of non-linear optics, as we observe spontaneous down-conversion pumped by single photons, an interaction also highly relevant to optical quantum computing.

  12. Electronic spectra and excited-state dynamics of 4-fluoro-N,N-dimethylaniline

    NASA Astrophysics Data System (ADS)

    Fujiwara, Takashige; Reichardt, Christian; Aaron Vogt, R.; Crespo-Hernández, Carlos E.; Zgierski, Marek Z.; Lim, Edward C.

    2013-10-01

    Concerted ultrafast time-resolved spectroscopic experiments and ab initio computational (TDDFT) studies of the electronic transitions of 4-fluoro-N,N-dimethylaniline (FDMA) have been performed to investigate the mechanism of photo-induced intramolecular charge transfer (ICT). The compound FDMA shows dual fluorescence from a ππ∗ state and a closely-lying twisted intramolecular charge transfer (TICT) state in both n-hexane and acetonitrile. The very similar lifetimes observed for the two emission bands indicate that the ππ∗ and the TICT states are effectively in thermal equilibrium at room temperature.

  13. Charge-exchange X-ray emission of M82: Kα triplets of O VII, Ne IX and Mg XI

    NASA Astrophysics Data System (ADS)

    Liu, Jiren; Mao, Shude; Wang, Q. Daniel

    2011-07-01

    Starburst galaxies are primary feedback sources of mechanical energy and metals, which are generally measured from associated X-ray emission lines, assuming that they are from the thermal emission of the outflowing hot gas. Such line emission, however, can also arise from the charge-exchange X-ray emission (CXE) between highly ionized ions and neutral species. To understand the feedback of energy and metals, it is crucial to determine the origin of the X-ray emission lines and to distinguish the contributions from the CXE and the thermal emission. The origin of the lines can be diagnosed by the Kα triplets of He-like ions, because the CXE favours the intercombination and forbidden lines, while the thermal emission favours the resonance line. We analyse the triplets of O VII, Ne IX and Mg XI observed in the XMM-Newton reflection grating spectra of the starburst galaxy M82. The flux contribution of the CXE is 90, 50 and 30 per cent to the O VII, Ne IX and Mg XI triplets, respectively. Averaged over all the three triplets, the contribution of the CXE is ˜50 per cent of the total observed triplet flux. To correctly understand the hot outflow of starburst galaxies, it is necessary to include the CXE. Based on the measured CXE fluxes of the O VII, Ne IX and Mg XI triplets, we estimate the relative abundances of O, Ne and Mg of the outflow and find they are similar to the solar ratios.

  14. Solvent Effects on the Electronic Absorption and Fluorescence Spectra of HNP: Estimation of Ground and Excited State Dipole Moments.

    PubMed

    Desai, Vani R; Hunagund, Shirajahammad M; Basanagouda, Mahantesha; Kadadevarmath, Jagadish S; Sidarai, Ashok H

    2016-07-01

    We report the effect of solvents on absorption and fluorescence spectra of biologically active 3(2H)-pyridazinone namely 5-(2-hydroxy-naphthalen-1-yl)-2-phenyl-2H-pyridazin-3-one (HNP) in different solvents at room temperature. The ground and the excited state dipole moments of HNP molecule was estimated from Lippert's, Bakshiev's and Kawski-Chamma-Viallet's equations using the solvatochromic shift method. The ground state dipole moment (μ g ) was also estimated by Guggenheim and Higasi method using the dielectric constant and refractive index of solute at different concentrations, the μ g value obtained from these two methods are comparable to the μ g value obtained by the solvatochromic shift method. The excited state dipole moment (μ e ) is greater than the ground state dipole moment (μ g ), which indicates that the excited state is more polar than the ground state. Further, we have evaluated the change in dipole moment (Δμ) from the solvatochromic shift method and on the basis of molecular-microscopic solvent polarity parameter[Formula: see text], later on the values were compared.

  15. Precursor charge state prediction for electron transfer dissociation tandem mass spectra.

    PubMed

    Sharma, Vagisha; Eng, Jimmy K; Feldman, Sergey; von Haller, Priska D; MacCoss, Michael J; Noble, William S

    2010-10-01

    Electron-transfer dissociation (ETD) induces fragmentation along the peptide backbone by transferring an electron from a radical anion to a protonated peptide. In contrast with collision-induced dissociation, side chains and modifications such as phosphorylation are left intact through the ETD process. Because the precursor charge state is an important input to MS/MS sequence database search tools, the ability to accurately determine the precursor charge is helpful for the identification process. Furthermore, because ETD can be applied to large, highly charged peptides, the need for accurate precursor charge state determination is magnified. Otherwise, each spectrum must be searched repeatedly using a large range of possible precursor charge states. To address this problem, we have developed an ETD charge state prediction tool based on support vector machine classifiers that is demonstrated to exhibit superior classification accuracy while minimizing the overall number of predicted charge states. The tool is freely available, open source, cross platform compatible, and demonstrated to perform well when compared with an existing charge state prediction tool. The program is available from http://code.google.com/p/etdz/.

  16. Photochemistry of furyl- and thienyldiazomethanes: spectroscopic characterization of triplet 3-thienylcarbene.

    PubMed

    Pharr, Caroline R; Kopff, Laura A; Bennett, Brian; Reid, Scott A; McMahon, Robert J

    2012-04-11

    Photolysis (λ > 543 nm) of 3-thienyldiazomethane (1), matrix isolated in Ar or N(2) at 10 K, yields triplet 3-thienylcarbene (13) and α-thial-methylenecyclopropene (9). Carbene 13 was characterized by IR, UV/vis, and EPR spectroscopy. The conformational isomers of 3-thienylcarbene (s-E and s-Z) exhibit an unusually large difference in zero-field splitting parameters in the triplet EPR spectrum (|D/hc| = 0.508 cm(-1), |E/hc| = 0.0554 cm(-1); |D/hc| = 0.579 cm(-1), |E/hc| = 0.0315 cm(-1)). Natural Bond Orbital (NBO) calculations reveal substantially differing spin densities in the 3-thienyl ring at the positions adjacent to the carbene center, which is one factor contributing to the large difference in D values. NBO calculations also reveal a stabilizing interaction between the sp orbital of the carbene carbon in the s-Z rotamer of 13 and the antibonding σ orbital between sulfur and the neighboring carbon-an interaction that is not observed in the s-E rotamer of 13. In contrast to the EPR spectra, the electronic absorption spectra of the rotamers of triplet 3-thienylcarbene (13) are indistinguishable under our experimental conditions. The carbene exhibits a weak electronic absorption in the visible spectrum (λ(max) = 467 nm) that is characteristic of triplet arylcarbenes. Although studies of 2-thienyldiazomethane (2), 3-furyldiazomethane (3), or 2-furyldiazomethane (4) provided further insight into the photochemical interconversions among C(5)H(4)S or C(5)H(4)O isomers, these studies did not lead to the spectroscopic detection of the corresponding triplet carbenes (2-thienylcarbene (11), 3-furylcarbene (23), or 2-furylcarbene (22), respectively).

  17. Sensitive marker bands for the detection of spin states of heme in surface-enhanced resonance Raman scattering spectra of metmyoglobin.

    PubMed

    Kitahama, Yasutaka; Egashira, Masatoshi; Suzuki, Toshiaki; Tanabe, Ichiro; Ozaki, Yukihiro

    2014-12-21

    Surface-enhanced resonance Raman scattering (SERRS) spectra of myoglobin (Mb) with various ligands were measured. In the resonance Raman scattering (RRS) spectra, peaks at around 1610 and 1640 cm(-1) have so far been used to discriminate between the heme iron in a high or low spin state. In the SERRS spectra, however, the spin state cannot be distinguished by the corresponding peaks. Alternatively, the intensity ratio of the SERRS peak at 1560 cm(-1) to that at 1620 cm(-1) was applied to detect the spin states sensitively (1.5 × 10(5) times compared with the RRS); namely, a high ratio was obtained from met-Mb in the high spin state at pH ≤ 7 except for in a strong acid solution. The different marker bands between the SERRS and RRS spectra may be due to the enhancement order from the surface selection rule.

  18. H-, He-like recombination spectra - II. l-changing collisions for He Rydberg states

    NASA Astrophysics Data System (ADS)

    Guzmán, F.; Badnell, N. R.; Williams, R. J. R.; van Hoof, P. A. M.; Chatzikos, M.; Ferland, G. J.

    2017-01-01

    Cosmological models can be constrained by determining primordial abundances. Accurate predictions of the He I spectrum are needed to determine the primordial helium abundance to a precision of <1 per cent in order to constrain big bang nucleosynthesis models. Theoretical line emissivities at least this accurate are needed if this precision is to be achieved. In the first paper of this series, which focused on H I, we showed that differences in l-changing collisional rate coefficients predicted by three different theories can translate into 10 per cent changes in predictions for H I spectra. Here, we consider the more complicated case of He atoms, where low-l subshells are not energy degenerate. A criterion for deciding when the energy separation between l subshells is small enough to apply energy-degenerate collisional theories is given. Moreover, for certain conditions, the Bethe approximation originally proposed by Pengelly & Seaton is not sufficiently accurate. We introduce a simple modification of this theory which leads to rate coefficients which agree well with those obtained from pure quantal calculations using the approach of Vrinceanu et al. We show that the l-changing rate coefficients from the different theoretical approaches lead to differences of ˜10 per cent in He I emissivities in simulations of H II regions using spectral code CLOUDY.

  19. Electronic spectra of azaindole and its excited state mixing: A symmetry-adapted cluster configuration interaction study

    NASA Astrophysics Data System (ADS)

    Arulmozhiraja, Sundaram; Coote, Michelle L.; Hasegawa, Jun-ya

    2015-11-01

    Electronic structures of azaindole were studied using symmetry-adapted cluster configuration interaction theory utilizing Dunning's cc-pVTZ basis set augmented with appropriate Rydberg spd functions on carbon and nitrogen atoms. The results obtained in the present study show good agreement with the available experimental values. Importantly, and contrary to previous theoretical studies, the excitation energy calculated for the important n-π∗ state agrees well with the experimental value. A recent study by Pratt and co-workers concluded that significant mixing of π-π∗ and n-π∗ states leads to major change in the magnitude and direction of the dipole moment of the upper state vibrational level in the 0,0 + 280 cm-1 band in the S1←S0 transition when compared to that of the zero-point level of the S1 state. The present study, however, shows that all the four lowest lying excited states, 1Lb π-π∗, 1La π-π∗, n-π∗, and π-σ∗, cross each other in one way or another, and hence, significant state mixing between them is likely. The upper state vibrational level in the 0,0 + 280 cm-1 band in the S1←S0 transition benefits from this four-state mixing and this can explain the change in magnitude and direction of the dipole moment of the S1 excited vibrational level. This multistate mixing, and especially the involvement of π-σ∗ state in mixing, could also provide a route for hydrogen atom detachment reactions. The electronic spectra of benzimidazole, a closely related system, were also investigated in the present study.

  20. Electronic spectra of azaindole and its excited state mixing: A symmetry-adapted cluster configuration interaction study

    SciTech Connect

    Arulmozhiraja, Sundaram Coote, Michelle L.; Hasegawa, Jun-ya

    2015-11-28

    Electronic structures of azaindole were studied using symmetry-adapted cluster configuration interaction theory utilizing Dunning’s cc-pVTZ basis set augmented with appropriate Rydberg spd functions on carbon and nitrogen atoms. The results obtained in the present study show good agreement with the available experimental values. Importantly, and contrary to previous theoretical studies, the excitation energy calculated for the important n–π{sup ∗} state agrees well with the experimental value. A recent study by Pratt and co-workers concluded that significant mixing of π-π{sup ∗} and n-π{sup ∗} states leads to major change in the magnitude and direction of the dipole moment of the upper state vibrational level in the 0,0 + 280 cm{sup −1} band in the S{sub 1}←S{sub 0} transition when compared to that of the zero-point level of the S{sub 1} state. The present study, however, shows that all the four lowest lying excited states, {sup 1}L{sub b} π-π{sup ∗}, {sup 1}L{sub a} π-π{sup ∗}, n-π{sup ∗}, and π-σ{sup ∗}, cross each other in one way or another, and hence, significant state mixing between them is likely. The upper state vibrational level in the 0,0 + 280 cm{sup −1} band in the S{sub 1}←S{sub 0} transition benefits from this four-state mixing and this can explain the change in magnitude and direction of the dipole moment of the S{sub 1} excited vibrational level. This multistate mixing, and especially the involvement of π-σ{sup ∗} state in mixing, could also provide a route for hydrogen atom detachment reactions. The electronic spectra of benzimidazole, a closely related system, were also investigated in the present study.

  1. Mass Ordering of Spectra from Fragmentation of Saturated Gluon States in High-Multiplicity Proton-Proton Collisions

    NASA Astrophysics Data System (ADS)

    Schenke, Björn; Schlichting, Sören; Tribedy, Prithwish; Venugopalan, Raju

    2016-10-01

    The mass ordering of mean transverse momentum ⟨pT⟩ and of the Fourier harmonic coefficient v2(pT) of azimuthally anisotropic particle distributions in high energy hadron collisions is often interpreted as evidence for the hydrodynamic flow of the matter produced. We investigate an alternative initial state interpretation of this pattern in high-multiplicity proton-proton collisions at the LHC. The QCD Yang-Mills equations describing the dynamics of saturated gluons are solved numerically with initial conditions obtained from the color-glass-condensate-based impact-parameter-dependent glasma model. The gluons are subsequently fragmented into various hadron species employing the well established Lund string fragmentation algorithm of the pythia event generator. We find that this initial state approach reproduces characteristic features of bulk spectra, in particular, the particle mass dependence of ⟨pT⟩ and v2(pT).

  2. How disorder controls the kinetics of triplet charge recombination in semiconducting organic polymer photovoltaics.

    PubMed

    Bittner, Eric R; Lankevich, Vladimir; Gélinas, Simon; Rao, Akshay; Ginger, David A; Friend, Richard H

    2014-10-14

    Recent experiments by Rao et al. (Nature, 2013, 500, 435-439) indicate that recombination of triplet charge-separated states is suppressed in organic polymer-fullerene based bulk-heterojunction (BHJ) photovoltaic cells exhibiting a high degree of crystallinity in the fullerene phase relative to systems with more disorder. In this paper, we use a series of Frenkel-exciton lattice models to rationalize these results in terms of wave-function localization, interface geometry, and density of states. In one-dimensional co-linear and co-facial models of the interface, increasing local energetic disorder in one phase localizes the interfacial triplet charge-transfer ((3)CT) states and increases the rate at which these states relax to form lower-energy triplet excitons. In two dimensional BHJ models, energetic disorder within the fullerene phase plays little role in further localizing states pinned to the interface. However, inhomogeneous broadening introduces strong coupling between the interfacial (3)CT and nearby fullerene triplet excitons and can enhance the decay of these states in systems with higher degrees of energetic disorder.

  3. Coherent transient in dressed-state and transient spectra of Autler-Townes doublet

    SciTech Connect

    Zhang Lianshui; Feng Xiaomin; Fu Guangsheng; Li Xiaowei; Han Li; Manson, Neil B.; Wei Changjiang

    2004-12-01

    In this paper we present a theoretical study of the time-dependent probe response in the presence of a strong pump field in a three-level pump-probe configuration. Two situations are investigated: a cw pump with a pulsed probe field and a pulsed pump with a cw probe field. The results are explained as dressed-state nutation and nutation by dynamic Stark switching. Dressed-state quantum beats are also an important feature for both situations. Furthermore, when a 90 deg. phase shift after a {pi}/2 period is introduced in the pulsed probe field, there is a spin locking in the dressed-state transition. Our results give a satisfactory theoretical account of a previous experimental observation [Wei et al., Phys. Rev. Lett. 74, 1083 (1995)].

  4. Excitation spectra of unconventional FQHE states in the SLL from Light Scattering Experiments

    NASA Astrophysics Data System (ADS)

    Wurstbauer, Ursula; Levy, Antonio; Pinczuk, Aron; Watson, John; Gardner, Geoff; Manfra, Michael; West, Ken; Pfeiffer, Loren

    The fascinating interaction physics in the second Landau level (SLL) supports the emergence of exotic quantum phases and unconventional possibly FQHE states such as e.g. at ν = 5/2 and 2 +1/3 and the weaker state at ν = 2 +3/8 and 2 +2/5. We observe clear signatures for gapped collective excitations in inelastic light scattering experiments just for these `magic' filling factors and only for low temperatures substantiating access to the physics of the incompressible quantum fluids. The lowest excitation feature in the spectrum at 2 +1/3 occurs at around 70 μeV. The analysis of spectral lineshapes suggests magnetoroton features that are characteristic of 2D neutral excitations in a perpendicular magnetic field. The striking polarization dependence observable in light scattering experiments in the SLL are consistent with nematic FQHE states. Supported by award NSF-DMR-1306976.

  5. Photophysics of Soret-Excited Tetrapyrroles in Solution. IV. Radiationless Decay and Triplet-Triplet Annihilation Investigated Using Tetraphenylporphinato Sn(IV)

    NASA Astrophysics Data System (ADS)

    Maiti, Manisankar; Danger, Brook R.; Steer, Ronald P.

    2009-09-01

    The S2 population decay rates and triplet-triplet annihilation efficiencies of Sn(IV)Cl2TPP have been measured in fluid solutions using its weak S2-S0 fluorescence as a metric. A detailed description of the excited-state photophysics of Sn(IV)Cl2TPP has allowed comparisons to be made between this rigid, D4h axially coordinated molecule and axially uncoordinated tetrapyrroles of greater flexibility and lower symmetry. S2-S1 internal conversion is the major S2 population decay path for Sn(IV)Cl2TPP as it is for the S2 states of all other d0 and d10 metalated tetrapyrroles. The S2 state of Sn(IV)Cl2TPP exhibits S2-S1 relaxation rates that follow the energy gap law of radiationless transition theory and are only slightly faster than those exhibited by MgTPP and the weak coupling limit. Differences in S2-S1 radiationless decay rates among the series MTPP (M = Mg, Zn, Cd, SnCl2) cannot be traced to differences in the displacements of the S2 and S1 potential surfaces. Instead, the most likely source of the large differences in S2-S1 radiationless decay rates between CdTPP and Sn(IV)Cl2TPP is the lower symmetry of the former (near C4v), which permits a much larger number of vibrations to participate in S2-S1 vibronic coupling. Triplet-triplet annihilation of the type 2T1 → S2 + S0 has been observed in Sn(IV)Cl2TPP for the first time, but is of substantially lower efficiency than seen in ZnTPP in noncoordinating solvents because of its shorter triplet lifetime and the shielding effects of its axial Cl ligands, which tend to block the short-range interaction needed for Dexter energy transfer.

  6. Electronic spectra and excited state dynamics of pentafluorophenol: Effects of low-lying πσ∗ states

    NASA Astrophysics Data System (ADS)

    Karmakar, Shreetama; Mukhopadhyay, Deb Pratim; Chakraborty, Tapas

    2015-05-01

    Multiple fluorine atom substitution effect on photophysics of an aromatic chromophore has been investigated using phenol as the reference system. It has been noticed that the discrete vibronic structure of the S1←S0 absorption system of phenol vapor is completely washed out for pentafluorophenol (PFP), and the latter also shows very large Stokes shift in the fluorescence spectrum. For excitations beyond S1 origin, the emission yield of PFP is reduced sharply with increase in excess vibronic energy. However, in a collisional environment like liquid hydrocarbon, the underlying dynamical process that drives the non-radiative decay is hindered drastically. Electronic structure theory predicts a number of low-lying dark electronic states of πσ∗ character in the vicinity of the lowest valence ππ∗ state of this molecule. Tentatively, we have attributed the excitation energy dependent non-radiative decay of the molecule observed only in the gas phase to an interplay between the lowest ππ∗ and a nearby dissociative πσ∗ state. Measurements in different liquids reveal that some of the dark excited states light up with appreciable intensity only in protic liquids like methanol and water due to hydrogen bonding between solute and solvents. Electronic structure theory methods indeed predict that for PFP-(H2O)n clusters (n = 1-11), intensities of a number of πσ∗ states are enhanced with increase in cluster size. In contrast with emitting behavior of the molecule in the gas phase and solutions of nonpolar and polar aprotic liquids, the fluorescence is completely switched off in polar protic liquids. This behavior is a chemically significant manifestation of perfluoro effect, because a very opposite effect occurs in the case of unsubstituted phenol for which fluorescence yield undergoes a very large enhancement in protic liquids. Several dynamical mechanisms have been suggested to interpret the observed photophysical behavior.

  7. Photophysical properties and thermochromic shifts of electronic spectra of Nile Red in selected solvents. Excited states dipole moments

    NASA Astrophysics Data System (ADS)

    Kawski, A.; Kukliński, B.; Bojarski, P.

    2009-05-01

    Photophysical parameters, the rate constants for radiative ( kF) and nonradiative ( kIC) for Nile Red (NR) in aprotic polar solvents incapable of hydrogen bonding with NR have been determined. No regular polarity dependence on kIC were observed in contrast to other authors. The effect of temperature on absorption and fluorescence spectra of NR in two selected solvents: ethyl acetate and 1,2-dichloroethane was studied and the electric dipole moment in the excited state S 1 was determined using the Bilot and Kawski theory [L. Bilot, A. Kawski, Z. Naturforsch. 17a (1962) 621, L. Bilot, A. Kawski, Z. Naturforsch. 18a (1963) 10, 256]. For the previously obtained dipole moment in the ground state μg = 8.2 D [A. Kawski, P. Bojarski, B. Kukliński, Chem. Phys. Lett. 463 (2008) 410] the change from thermochromic measurements upon excitation of NR is equal to Δ μ = μe - μg = 1.75 ± 0.5 D and is in good agreement with the value Δ μ = 1.8 ± 1 D from solvatochromic method. A comparison of the obtained Δ μ value with those of other authors is given and discussed. It has been concluded that the difference between the excited μe and ground μg state dipole moments for NR is too small to create a TICT state.

  8. Singlet-to-Triplet Excitations in the Unconventional Spin-Peierls System TiOBr

    SciTech Connect

    Clancy, James P; Gaulin, Bruce D.; Adams, Carl P; Granroth, Garrett E; Kolesnikov, Alexander I; Sherline, Todd E; Chou, F. C.

    2011-01-01

    We have performed time-of-flight neutron scattering measurements on powder samples of the unconventional spin-Peierls compound TiOBr using the fine-resolution Fermi chopper spectrometer (SEQUOIA) at the SNS. These measurements reveal two branches of magnetic excitations within the commensurate and incommensurate spin-Peierls phases, which we associate with n = 1 and n = 2 triplet excitations out of the singlet ground state. These measurements represent the first direct measure of the singlet-triplet energy gap in TiOBr, which is found to have a value of Eg 21 meV.

  9. Singlet-Triplet Excitations in the Unconventional Spin-Peierls TiOBr Compound

    NASA Astrophysics Data System (ADS)

    Clancy, J. P.; Gaulin, B. D.; Adams, C. P.; Granroth, G. E.; Kolesnikov, A. I.; Sherline, T. E.; Chou, F. C.

    2011-03-01

    We have performed time-of-flight neutron scattering measurements on powder samples of the unconventional spin-Peierls compound TiOBr using the fine-resolution Fermi chopper spectrometer (SEQUOIA) at the Spallation Neutron Source at Oak Ridge National Laboratory. These measurements reveal two branches of magnetic excitations within the commensurate and incommensurate spin-Peierls phases, which we associate with n=1 and n=2 triplet excitations out of the singlet ground state. These results represent the first direct measurement of the singlet-triplet energy gap in TiOBr, which has a value of Eg=21.2±1.0meV.

  10. Detuning-dependent Mollow triplet of a coherently-driven single quantum dot.

    PubMed

    Ulhaq, Ata; Weiler, Stefanie; Roy, Chiranjeeb; Ulrich, Sven Marcus; Jetter, Michael; Hughes, Stephen; Michler, Peter

    2013-02-25

    We present both experimental and theoretical investigations of a laser-driven quantum dot (QD) in the dressed-state regime of resonance fluorescence. We explore the role of phonon scattering and pure dephasing on the detuning-dependence of the Mollow triplet and show that the triplet sidebands may spectrally broaden or narrow with increasing detuning. Based on a polaron master equation approach, which includes electron-phonon interaction nonperturbatively, we derive a fully analytical expression for the spectrum. With respect to detuning dependence, we identify a crossover between the regimes of spectral sideband narrowing or broadening. We also predict regimes of phonon-induced squeezing and anti-squeezing of the spectral resonances. A comparison of the theoretical predictions to detailed experimental studies on the laser detuning-dependence of Mollow triplet resonance emission from single In(Ga)As QDs reveals excellent agreement.

  11. (1)H NMR spectra dataset and solid-state NMR data of cowpea (Vigna unguiculata).

    PubMed

    Alves Filho, Elenilson G; Silva, Lorena M A; Teofilo, Elizita M; Larsen, Flemming H; de Brito, Edy S

    2017-04-01

    In this article the NMR data from chemical shifts, coupling constants, and structures of all the characterized compounds were provided, beyond a complementary PCA evaluation for the corresponding manuscript (E.G. Alves Filho, L.M.A. Silva, E.M. Teofilo, F.H. Larsen, E.S. de Brito, 2017) [3]. In addition, a complementary assessment from solid-state NMR data was provided. For further chemometric analysis, numerical matrices from the raw (1)H NMR data were made available in Microsoft Excel workbook format (.xls).

  12. Possible spin-triplet superconducting phase in the La0.7Sr0.3MnO3/YBa2Cu3O7/La0.7Sr0.3MnO3 trilayer

    NASA Astrophysics Data System (ADS)

    Dybko, K.; Werner-Malento, K.; Aleshkevych, P.; Wojcik, M.; Sawicki, M.; Przyslupski, P.

    2009-10-01

    We report on results of conductance spectroscopy measurements in the current-in-plane (CIP) and current-perpendicular-to-plane (CPP) geometries ([001] and [100] directions respectively) of La0.7Sr0.3MnO3/YBa2Cu3O7/La0.7Sr0.3MnO3 (LSMO/YBCO/LSMO) nonsymmetric trilayer structures in order to search for signature of the formation of spin-triplet phase. This trilayer shows an enhancement of the superconducting transition temperature in magnetic field parallel to the plane. We argue that this enhancement is a result of the formation of spin-triplet phase. The differential conductance (dI/dV) spectra show fully developed zero-bias conductance peaks (ZBCP). The ZBCP measured in CIP geometry demonstrates a sharp shape. This could be attributed to a spin-triplet state arising from the proximity effect at the interface of the half-metal with the d -wave superconductor, similar as was predicted theoretically for the p -wave superconductor and observed experimentally in p -wave Sr2RuO4 superconductor. The measurements of the dI/dV in CPP geometry reveal a V shape similar as was experimentally observed in YBCO superconductor and predicted theoretically for superconductor with a dx2-y2 pairing symmetry of the order parameter.

  13. BVRI SURFACE PHOTOMETRY OF ISOLATED GALAXY TRIPLETS

    SciTech Connect

    Hernandez-Toledo, H. M.; Mendez-Hernandez, H.; Aceves, H.; OlguIn, L. E-mail: hmendez@astroscu.unam.mx E-mail: lorenzo@astro.uson.mx

    2011-03-15

    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 {approx}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 {epsilon}{sub max} {approx} 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{sub H} , velocity dispersion {sigma}, dimensionless crossing time H{sub 0{tau}c}, and virial mass M{sub 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

  14. Dressing effects in the attosecond transient absorption spectra of doubly excited states in helium

    NASA Astrophysics Data System (ADS)

    Argenti, L.; Jiménez-Galán, Á.; Marante, C.; Ott, C.; Pfeifer, T.; Martín, F.

    2015-06-01

    Strong-field manipulation of autoionizing states is a crucial aspect of electronic quantum control. Recent measurements of the attosecond transient absorption spectrum (ATAS) of helium dressed by a few-cycle visible pulse [C. Ott et al., Nature (London) 516, 374 (2014), 10.1038/nature14026] provide evidence of the inversion of Fano profiles. With the support of accurate ab initio calculations that reproduce the results of the latter experiment, here we investigate the new physics that arise from ATAS when the laser intensity is increased. In particular, we show that (i) previously unnoticed signatures of the dark 2 p21S doubly excited state are observed in the experimental spectrum, (ii) inversion of Fano profiles is predicted to be periodic in the laser intensity, and (iii) the ac Stark shift of the higher terms in the s p2,n + autoionizing series exceeds the ponderomotive energy, which is the result of a genuine two-electron contribution to the polarization of the excited atom.

  15. Higher energy states in the CO dimer: millimeter-wave spectra and rovibrational calculations.

    PubMed

    Surin, Leonid A; Fourzikov, Dmitri N; Giesen, Thomas F; Schlemmer, Stephan; Winnewisser, Gisbert; Panfilov, Victor A; Dumesh, Boris S; Vissers, Gé W M; van der Avoird, Ad

    2007-12-13

    New extensive millimeter-wave measurements of the 12C16O dimer have been made, and more than 300 new spectral transitions have been observed in the frequency range 81-135 GHz. A joint analysis of these and previous millimeter-wave data yielded the precise location of 33 new energy levels of A+ symmetry and 20 levels of A- symmetry. These energy levels are located at 8-18 cm(-1) above the zero-point level. Some of them belong to already known stacks, and others make up 9 new stacks of the dimer. Newly determined stacks have K=0, 1, and, for the first time, 2, where K is the projection of the total angular momentum on the intermolecular axis. The energy levels from accompanying rovibrational calculations with the use of a recently developed hybrid CCSD(T)/DFT-SAPT potential are in very good agreement with experiment. Analysis of the calculated wave functions revealed that two new stacks of A+ symmetry with K=2 correspond to overall rotation of the dimer while the other newly observed stacks belong to the geared bend overtone modes. The ground vibrational states of the two "isomers" found are more or less localized at the two minima in the potential surface, whereas all the geared bend excited states show a considerable amount of delocalization.

  16. Electronic spectra and excited state dynamics of pentafluorophenol: Effects of low-lying πσ{sup ∗} states

    SciTech Connect

    Karmakar, Shreetama; Mukhopadhyay, Deb Pratim; Chakraborty, Tapas

    2015-05-14

    Multiple fluorine atom substitution effect on photophysics of an aromatic chromophore has been investigated using phenol as the reference system. It has been noticed that the discrete vibronic structure of the S{sub 1}←S{sub 0} absorption system of phenol vapor is completely washed out for pentafluorophenol (PFP), and the latter also shows very large Stokes shift in the fluorescence spectrum. For excitations beyond S{sub 1} origin, the emission yield of PFP is reduced sharply with increase in excess vibronic energy. However, in a collisional environment like liquid hydrocarbon, the underlying dynamical process that drives the non-radiative decay is hindered drastically. Electronic structure theory predicts a number of low-lying dark electronic states of πσ{sup ∗} character in the vicinity of the lowest valence ππ{sup ∗} state of this molecule. Tentatively, we have attributed the excitation energy dependent non-radiative decay of the molecule observed only in the gas phase to an interplay between the lowest ππ{sup ∗} and a nearby dissociative πσ{sup ∗} state. Measurements in different liquids reveal that some of the dark excited states light up with appreciable intensity only in protic liquids like methanol and water due to hydrogen bonding between solute and solvents. Electronic structure theory methods indeed predict that for PFP-(H{sub 2}O){sub n} clusters (n = 1-11), intensities of a number of πσ{sup ∗} states are enhanced with increase in cluster size. In contrast with emitting behavior of the molecule in the gas phase and solutions of nonpolar and polar aprotic liquids, the fluorescence is completely switched off in polar protic liquids. This behavior is a chemically significant manifestation of perfluoro effect, because a very opposite effect occurs in the case of unsubstituted phenol for which fluorescence yield undergoes a very large enhancement in protic liquids. Several dynamical mechanisms have been suggested to interpret the

  17. Exchange-only optimized effective potential calculation of excited state spectra for He and Be atoms.

    SciTech Connect

    Desjarlais, Michael Paul; Muller, Richard Partain

    2006-02-01

    The optimized effective potential (OEP) method allows orbital-dependent functionals to be used in density functional theory (DFT), which, in particular, allows exact exchange formulations of the exchange energy to be used in DFT calculations. Because the exact exchange is inherently self-interaction correcting, the resulting OEP calculations have been found to yield superior band-gaps for condensed-phase systems. Here we apply these methods to the isolated atoms He and Be, and compare to high quality experiments and calculations to demonstrate that the orbital energies accurately reproduce the excited state spectrum for these species. These results suggest that coupling the exchange-only OEP calculations with proper (orbital-dependent or other) correlation functions might allow quantitative accuracy from DFT calculations.

  18. Hindered and modulated rotational states and spectra of adsorbed diatomic molecules

    SciTech Connect

    Shih, Y.T.; Chuu, D.S.; Mei, W.N.

    1996-10-01

    Both vertical and horizontal adsorption configurations of a diatomic molecule were modeled as the rigid rotor with which the spatial motion was confined by a finite conical well. In addition to the polar hindering potential, a sinusoidal azimuthal modulation, which bears the local symmetry of the adsorption site, was incorporated. Eigenfunctions for different models were expressed analytically in terms of the hypergeometric functions, and eigenvalues were solved numerically. We found that the rotational energy levels exhibit oscillatory behavior when plotted as functions of the hindrance angle. This particular phenomenon was interpreted as the occurrence of resonance transmission of the rotor wave function at certain hindrance condition. We also found that the rotational levels were grouped into bands when the azimuthal modulation strength was increased. The solutions were used to calculate the rotational-state distribution of desorbed molecules, and agreement with the previous experiment was obtained. {copyright} {ital 1996 The American Physical Society.}

  19. Rich structure in the correlation matrix spectra in non-equilibrium steady states.

    PubMed

    Biswas, Soham; Leyvraz, Francois; Monroy Castillero, Paulino; Seligman, Thomas H

    2017-01-17

    It has been shown that, if a model displays long-range (power-law) spatial correlations, its equal-time correlation matrix will also have a power law tail in the distribution of its high-lying eigenvalues. The purpose of this paper is to show that the converse is generally incorrect: a power-law tail in the high-lying eigenvalues of the correlation matrix may exist even in the absence of equal-time power law correlations in the initial model. We may therefore view the study of the eigenvalue distribution of the correlation matrix as a more powerful tool than the study of spatial Correlations, one which may in fact uncover structure, that would otherwise not be apparent. Specifically, we show that in the Totally Asymmetric Simple Exclusion Process, whereas there are no clearly visible correlations in the steady state, the eigenvalues of its correlation matrix exhibit a rich structure which we describe in detail.

  20. Rich structure in the correlation matrix spectra in non-equilibrium steady states

    PubMed Central

    Biswas, Soham; Leyvraz, Francois; Monroy Castillero, Paulino; Seligman, Thomas H.

    2017-01-01

    It has been shown that, if a model displays long-range (power-law) spatial correlations, its equal-time correlation matrix will also have a power law tail in the distribution of its high-lying eigenvalues. The purpose of this paper is to show that the converse is generally incorrect: a power-law tail in the high-lying eigenvalues of the correlation matrix may exist even in the absence of equal-time power law correlations in the initial model. We may therefore view the study of the eigenvalue distribution of the correlation matrix as a more powerful tool than the study of spatial Correlations, one which may in fact uncover structure, that would otherwise not be apparent. Specifically, we show that in the Totally Asymmetric Simple Exclusion Process, whereas there are no clearly visible correlations in the steady state, the eigenvalues of its correlation matrix exhibit a rich structure which we describe in detail. PMID:28094322

  1. Rich structure in the correlation matrix spectra in non-equilibrium steady states

    NASA Astrophysics Data System (ADS)

    Biswas, Soham; Leyvraz, Francois; Monroy Castillero, Paulino; Seligman, Thomas H.

    2017-01-01

    It has been shown that, if a model displays long-range (power-law) spatial correlations, its equal-time correlation matrix will also have a power law tail in the distribution of its high-lying eigenvalues. The purpose of this paper is to show that the converse is generally incorrect: a power-law tail in the high-lying eigenvalues of the correlation matrix may exist even in the absence of equal-time power law correlations in the initial model. We may therefore view the study of the eigenvalue distribution of the correlation matrix as a more powerful tool than the study of spatial Correlations, one which may in fact uncover structure, that would otherwise not be apparent. Specifically, we show that in the Totally Asymmetric Simple Exclusion Process, whereas there are no clearly visible correlations in the steady state, the eigenvalues of its correlation matrix exhibit a rich structure which we describe in detail.

  2. Twin and Triplet Drugs in Opioid Research

    NASA Astrophysics Data System (ADS)

    Fujii, Hideaki

    Twin and triplet drugs are defined as compounds that contain respectively two and three pharmacophore components exerting pharmacological effects in a molecule. The twin drug bearing the same pharmacophores is a "symmetrical twin drug", whereas that possessing different pharmacophores is a "nonsymmetrical twin drug." In general, the symmetrical twin drug is expected to produce more potent and/or selective pharmacological effects, whereas the nonsymmetrical twin drug is anticipated to show both pharmacological activities stemming from the individual pharmacophores (dual action). On the other hand, nonsymmetrical triplet drugs, which have two of the same pharmacophores and one different moiety, are expected to elicit both increased pharmacological action and dual action. The two identical portions could bind the same receptor sites simultaneously while the third portion could bind a different receptor site or enzyme. This review will mainly focus on the twin and triplet drugs with an evaluation of their in vivo pharmacological effects, and will also include a description of their pharmacology and synthesis.

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

    PubMed

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

    2017-03-29

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

  4. Rotational Spectra of Urea in its Ground and First Excited Vibrational States

    NASA Astrophysics Data System (ADS)

    Thomas, Jessica; Medvedev, Ivan; Kisiel, Zbigniew

    2014-06-01

    Urea is an important terrestrial bio-molecule, which has been tentatively detected in the interstellar medium. To match the much improved range and sensitivities of modern sub-millimeter telescopes a broad laboratory assay of rotational transitions needs to be recorded in order to aid in the definitive identification of this molecule. This paper focuses on the spectroscopic assignment of the rotational transitions of urea in the 207-500 GHz range which belong to its ground and first excited vibrational states. Remijan, A.J., L.E. Snyder, B.A. McGuire, H.-L. Kuo, L.W. Looney, D.N. Friedel, G.Y. Golubiatnikov, F.J. Lovas, V.V. Ilyushin, E.A. Alekseev, S.F. Dyubko, B.J. McCall, and J.M. Hollis, Observational Results of a Multi-Telescope Campaign in Search of Interstellar Urea [NH22CO]. The Astrophysical Journal, 2014. 783(2): p. 77

  5. 1H NMR z-spectra of acetate methyl in stretched hydrogels: Quantum-mechanical description and Markov chain Monte Carlo relaxation-parameter estimation

    NASA Astrophysics Data System (ADS)

    Shishmarev, Dmitry; Chapman, Bogdan E.; Naumann, Christoph; Mamone, Salvatore; Kuchel, Philip W.

    2015-01-01

    The 1H NMR signal of the methyl group of sodium acetate is shown to be a triplet in the anisotropic environment of stretched gelatin gel. The multiplet structure of the signal is due to the intra-methyl residual dipolar couplings. The relaxation properties of the spin system were probed by recording steady-state irradiation envelopes ('z-spectra'). A quantum-mechanical model based on irreducible spherical tensors formed by the three magnetically equivalent spins of the methyl group was used to simulate and fit experimental z-spectra. The multiple parameter values of the relaxation model were estimated by using a Bayesian-based Markov chain Monte Carlo algorithm.

  6. Determination of the Effective Ground State Potential Energy Function of Ozone from High-Resolution Infrared Spectra.

    PubMed

    Tyuterev; Tashkun; Jensen; Barbe; Cours

    1999-11-01

    The effective ground state potential energy function of the ozone molecule near the C(2v) equilibrium configuration was obtained in a least-squares fit to the largest sample of experimental, high-resolution vibration-rotation data used for this purpose so far. The fitting is based on variational calculations carried out with the extended Morse Oscillator Rigid Bender Internal Dynamics model. The potential function is expanded in Morse-type functions of the stretching variables and in cosine of the bending angle. The present calculation produces results in significantly better agreement with experiment than previous determinations of the potential energy surface, and the energies predicted with the new surface are sufficiently accurate to be useful for the assignment of new high-resolution spectra. The rms (root-mean-square) deviation of the fit of rovibrational data up to J = 5 is 0.02 cm(-1). For the set of all 60 band centers of the (16)O(3) molecule included in the Atlas of Ozone Line Parameters, the rms deviation is 0.025 cm(-1), and for all band centers determined so far from high-resolution spectra, including those recently observed and assigned in Reims corresponding to highly excited stretching and bending vibrations (v(1) + v(2) + v(3) = 6), the rms deviation is 0.1 cm(-1). The "dark states" that produce resonance perturbations in the observed bands are described with experimental accuracy up to the (v(1)v(2)v(3)) = (080) state. Extrapolation tests demonstrate the predictive power of the potential function obtained: rotational extrapolation up to J = 10 for the 11 lowest vibrational states results in an rms deviation of 0.06cm(-1). Also, vibrational energies measured by low-resolution Raman spectroscopy (which were not included in the input data for the fit) are calculated within the experimental accuracy (rms = 1.6 cm(-1)) of the experimental values up to the dissociation limit. The statistical analysis suggests that the accuracy of the equilibrium

  7. Hydride stretch infrared spectra in the excited electronic states of indole and its derivatives: Direct evidence for the 1πσ* state

    NASA Astrophysics Data System (ADS)

    Dian, Brian C.; Longarte, Asier; Zwier, Timothy S.

    2003-02-01

    The hydride stretch infrared spectra of indole, indole-H2O, 3-methyl indole, 3-methyl indole-H2O, the main conformer of tryptamine (TRA), two conformers of N-acetyl tryptophan amide (NATA), and three conformers of N-acetyl tryptophan methyl amide (NATMA), have been recorded in the electronically excited singlet states using excited-state fluorescence-dip infrared spectroscopy. NATA and NATMA are methyl-capped dipeptides of tryptophan that have conformational flexibility and exhibit sensitivity in their electronic spectra to the conformation of the dipeptide backbone. In the indole monomer, the indole NH stretch fundamental at the S1 origin is shifted from its ground-state value (3525 cm-1) to 3478 cm-1. The corresponding band in the indole-H2O complex appears at 3387 cm-1, shifted by a similar amount from its ground-state position (3436 cm-1). Higher vibronic levels within 1500 cm-1 of the S1 origin, which have been identified previously [B. J. Fender et al., Chem. Phys. Lett. 239, 31 (1995)] as being 1Lb or 1La in character, all show similar excited state indole NH stretch absorptions. The corresponding spectra in 3-methyl indole, 3-methyl indole-H2O, TRA, and in the C5 conformers of NATA and NATMA all are missing the indole NH stretch absorption. In its place, a broad background absorption appears, spread over the entire 2800-3800 cm-1 region. In these molecules, other CH stretch or amide NH stretch absorptions remain sharp, appearing in their expected frequency ranges. Finally, the C7 conformations of NATA and NATMA, which possess an intramolecular hydrogen bond in the dipeptide backbone, have all infrared transitions washed out, replaced by a stronger broad background absorption. The entire data set can be explained by the presence of an excited 1πσ* state which is dissociative along the indole NH stretch coordinate, as recently predicted by Sobolewski and Domcke [Chem. Phys. Lett. 315, 293 (1999)]. In the weak coupling case (indole, indole-H2O), the gap

  8. Intra-molecular Triplet Energy Transfer is a General Approach to Improve Organic Fluorophore Photostability

    PubMed Central

    Zheng, Qinsi; Jockusch, Steffen; Rodríguez-Calero, Gabriel G.; Zhou, Zhou; Zhao, Hong; Altman, Roger B.; Abruña, Héctor D.; Blanchard, Scott C.

    2015-01-01

    Bright, long-lasting and non-phototoxic organic fluorophores are essential to the continued advancement of biological imaging. Traditional approaches towards achieving photostability, such as the removal of molecular oxygen and the use of small-molecule additives in solution, suffer from potentially toxic side effects, particularly in the context of living cells. The direct conjugation of small-molecule triplet state quenchers, such as cyclooctatetraene (COT), to organic fluorophores has the potential to bypass these issues by restoring reactive fluorophore triplet states to the ground state through intra-molecular triplet energy transfer. Such methods have enabled marked improvement in cyanine fluorophore photostability spanning the visible spectrum. However, the generality of this strategy to chemically and structurally diverse fluorophore species has yet to be examined. Here, we show that the proximal linkage of COT increases the photon yield of a diverse range of organic fluorophores widely used in biological imaging applications, demonstrating that the intra-molecular triplet energy transfer mechanism is a potentially general approach for improving organic fluorophore performance and photostability. PMID:26700693

  9. Triplet-triplet annihilation upconversion followed by FRET for the red light activation of a photodissociative ruthenium complex in liposomes.

    PubMed

    Askes, Sven H C; Kloz, Miroslav; Bruylants, Gilles; Kennis, John T M; Bonnet, Sylvestre

    2015-11-07

    Upconversion is a promising way to trigger high-energy photochemistry with low-energy photons. However, combining upconversion schemes with non-radiative energy transfer is challenging because bringing several photochemically active components in close proximity results in complex multi-component systems where quenching processes may deactivate the whole assembly. In this work, PEGylated liposomes were prepared that contained three photoactive components: a porphyrin dye absorbing red light, a perylene moiety emitting in the blue, and a light-activatable ruthenium prodrug sensitive to blue light. Time-dependent spectroscopic studies demonstrate that singlet perylene excited states are non-radiatively transferred to the nearby ruthenium complex by Förster resonance energy transfer (FRET). Under red-light irradiation of the three-component membranes, triplet-triplet annihilation upconversion (TTA-UC) occurs followed by FRET, which results in a more efficient activation of the ruthenium prodrug compared to a physical mixture of two-component upconverting liposomes and liposomes containing only the ruthenium complex. This work represents a rare example where TTA-UC and Förster resonance energy transfer are combined to achieve prodrug activation in the phototherapeutic window.

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

    NASA Astrophysics Data System (ADS)

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

    2017-04-01

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

  11. Integrals over the triplet distribution function without the triplet distribution function

    NASA Astrophysics Data System (ADS)

    Lado, F.

    While the triplet distribution function of disordered systems appears in a wide variety of problems in statistical mechanics, it does so always under an integral sign. In this paper, we propose a new method of evaluating such integrals that involves only pair functions throughout and avoids altogether the need for any explicit representation of the little-known triplet function. The procedure is based on an extension of integral equation theory of classical fluids. Numerical illustrations of the method are given for integrals that arise in the calculation of moments of a local field distribution.

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

    PubMed

    Hirai, Katsuyuki; Bessho, Kana; Tsujita, Kosaku; Kitagawa, Toshikazu

    2016-11-15

    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-diiodophenyl)diazomethane (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.

  13. Contribution of satellite lines to temperature diagnostics with He-like triplet lines in photoionized plasma

    NASA Astrophysics Data System (ADS)

    Wang, Feilu; Han, Bo; Salzmann, David; Zhao, Gang

    2017-04-01

    In the present paper, the He α triplet line ratios (resonance, intercombination, and forbidden lines) are computed for photoionized plasmas, when the contributions of nearby satellite lines are taken into account. The computations have been carried out with our radiative-collisional code, RCF, which is based on the flexible atomic code. The calculations of these line ratios have been done for three materials, namely, silicon, magnesium, and neon. Our calculations are used to derive the plasma temperatures for several astronomical objects, where the spectra are emitted from photoionizing plasmas. It is shown that the incorporation of the satellite lines from doubly excited Li-like ions into the He α triplet lines is necessary to obtain reliable temperature diagnostics for these astrophysical objects.

  14. Rotationally resolved photoelectron spectra in resonance enhanced multiphoton ionization of HCl via the F 1Δ2 Rydberg state

    NASA Astrophysics Data System (ADS)

    Wang, Kwanghsi; McKoy, V.

    1991-12-01

    Results of studies of rotational ion distributions in the X 2Π3/2 and X 2Π1/2 spin-orbit states of HCl+ resulting from (2+1') resonance enhanced multiphoton ionization (REMPI) via the S(0) branch of the F 1Δ2 Rydberg state are reported and compared with measured threshold-field-ionization zero-kinetic-energy spectra reported recently [K. S. Haber, Y. Jiang, G. Bryant, H. Lefebvre-Brion, and E. R. Grant, Phys. Rev. A (in press)]. These results show comparable intensities for J+=3/2 of the X 2Π3/2 ion and J+=1/2 of the X 2Π1/2 ion. Both transitions require an angular momentum change of ΔN=-1 upon photoionization. To provide further insight into the near-threshold dynamics of this process, we also show rotationally resolved photoelectron angular distributions, alignment of the ion rotational levels, and rotational distributions for the parity components of the ion rotational levels. About 18% population is predicted to occur in the (+) parity component, which would arise from odd partial-wave contributions to the photoelectron matrix element. This behavior is similar to that in (2+1) REMPI via the S(2) branch of the F 1Δ2 state of HBr and was shown to arise from significant l mixing in the electronic continuum due to the nonspherical molecular ion potential. Rotational ion distributions resulting from (2+1) REMPI via the S(10) branch of the F 1Δ2 state are also shown.

  15. The TDF System for Thermonuclear Plasma Reaction Rates, Mean Energies and Two-Body Final State Particle Spectra

    SciTech Connect

    Warshaw, S I

    2001-07-11

    The rate of thermonuclear reactions in hot plasmas as a function of local plasma temperature determines the way in which thermonuclear ignition and burning proceeds in the plasma. The conventional model approach to calculating these rates is to assume that the reacting nuclei in the plasma are in Maxwellian equilibrium at some well-defined plasma temperature, over which the statistical average of the reaction rate quantity {sigma}v is calculated, where {sigma} is the cross-section for the reaction to proceed at the relative velocity v between the reacting particles. This approach is well-understood and is the basis for much nuclear fusion and astrophysical nuclear reaction rate data. The Thermonuclear Data File (TDF) system developed at the Lawrence Livermore National Laboratory (Warshaw 1991), which is the topic of this report, contains data on the Maxwellian-averaged thermonuclear reaction rates for various light nuclear reactions and the correspondingly Maxwellian-averaged energy spectra of the particles in the final state of those reactions as well. This spectral information closely models the output particle and energy distributions in a burning plasma, and therefore leads to more accurate computational treatments of thermonuclear burn, output particle energy deposition and diagnostics, in various contexts. In this report we review and derive the theoretical basis for calculating Maxwellian-averaged thermonuclear reaction rates, mean particle energies, and output particle spectral energy distributions for these reactions in the TDF system. The treatment of the kinematics is non-relativistic. The current version of the TDF system provides exit particle energy spectrum distributions for two-body final state reactions only. In a future report we will discuss and describe how output particle energy spectra for three- and four-body final states can be developed for the TDF system. We also include in this report a description of the algorithmic implementation of the

  16. Excited S 1 state dipole moments of nitrobenzene and p-nitroaniline from thermochromic effect on electronic absorption spectra

    NASA Astrophysics Data System (ADS)

    Kawski, A.; Kukliński, B.; Bojarski, P.

    2006-11-01

    The effect of temperature on the absorption spectra of nitrobenzene (NB) and p-nitroaniline (NA) in 1,2-dichloroethane was studied for temperature ranging from 295 K to 378 K and from 296 K to 408 K, respectively. With temperature increase the absorption bands of both compounds are blue shifted, which is caused by the decrease of permittivity ɛ and refractive index n. From the band shifts and by using the Bilot and Kawski theory [ L. Bilot, A. Kawski, Z. Naturforsch. 17a (1962) 621] the dipole moments in the excited singlet state μe = 6.59 D of NB and μe = 13.35 D of NA were determined. The influence of polarizability α, the Onsager cavity radius a and dipole moment in the ground state μg on the determined values of μe are discussed. A comparison of the obtained μe values with those of other authors is given. In the case of p-NA a strong intramolecular charge transfer (ICT) was confirmed.

  17. Excited state dipole moments of N, N-dimethylaniline from thermochromic effect on electronic absorption and fluorescence spectra

    NASA Astrophysics Data System (ADS)

    Kawski, A.; Kukliński, B.; Bojarski, P.

    2006-01-01

    The effect of temperature on absorption and fluorescence spectra of N, N-dimethylaniline (DMA) in ethyl acetate has been studied for temperature ranging from 293 to 388 K. The permittivity ɛ and refractive index n of the solvent decrease with temperature increase and the absorption and fluorescence bands are blue shifted (so-called "thermochromic shift"). Based on this phenomenon, the dipole moment μe in the excited singlet state and the Onsager interaction radius a for DMA were determined using the Bilot and Kawski theory [L. Bilot, A. Kawski, Z. Naturforsch. 17a (1962) 621; 18a (1963) 10, 256]. For the known dipole moment in the ground state μg = 1.61 D and for α/ a3 = 0.54 ( α is the polarizability of the solute) the average value of μe = 3.55 D and a = 3.1 Å were determined. The obtained values for DMA are compared with the experimental values determined by other authors.

  18. A versatile detector system to measure the change states, mass compositions and energy spectra of interplanetary and magnetosphere ions

    NASA Technical Reports Server (NTRS)

    Gloeckler, G.

    1977-01-01

    An instrument is described for measuring the mass and charge state composition as well as the energy spectra and angular distributions of 0.5 to 350 kev/charge ions in interplanetary space and in magnetospheres of planets such as Jupiter and earth. Electrostatic deflection combined with a time-of-flight and energy measurement allows three-parameter analysis of output signals from which the mass, charge states, and energy are determined. Post-acceleration by 30 kV extends the energy range of the detector system into the solar wind and magnetosphere plasma regime. Isotopes of H and He are easily resolved as are individual elements up to Ne and the dominant elements up to and including Fe. This instrument has an extremely large dynamic range in intensity and is sensitive to rare elements even in the presence of high intensity radiation, and is adapted for interplanetary, deep-space, and out-of-the-ecliptic missions, as well as for flights on spacecraft orbiting Jupiter and earth.

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

    SciTech Connect

    Wu, Wei

    2014-06-14

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

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

    PubMed

    Wu, Wei

    2014-06-14

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

  1. Ultrafast electronic and vibrational dynamics in brominated aluminum corroles: Energy relaxation and triplet formation

    PubMed Central

    Stensitzki, T.; Yang, Y.; Berg, A.; Mahammed, A.; Gross, Z.; Heyne, K.

    2016-01-01

    We combined femtosecond (fs) VIS pump–IR probe spectroscopy with fs VIS pump–supercontinuum probe spectroscopy to characterize the photoreaction of the hexacoordinated Al(tpfc-Br8)(py)2 in a comprehensive way. Upon fs excitation at ∼400 nm in the Soret band, the excitation energy relaxes with a time constant of (250 ± 80) fs to the S2 and S1 electronic excited states. This is evident from the rise time of the stimulated emission signal in the visible spectral range. On the same time scale, narrowing of broad infrared signals in the C=C stretching region around 1500 cm−1 is observed. Energy redistribution processes are visible in the vibrational and electronic dynamics with time constants between ∼2 ps and ∼20 ps. Triplet formation is detected with a time constant of (95 ± 3) ps. This is tracked by the complete loss of stimulated emission. Electronic transition of the emerging triplet absorption band overlaps considerably with the singlet excited state absorption. In contrast, two well separated vibrational marker bands for triplet formation were identified at 1477 cm−1 and at 1508 cm−1. These marker bands allow a precise identification of triplet dynamics in corrole systems. PMID:27226980

  2. Quasiparticle energies, excitons, and optical spectra of few-layer black phosphorus

    NASA Astrophysics Data System (ADS)

    Tran, Vy; Fei, Ruixiang; Yang, Li

    2015-12-01

    We report first-principles GW-Bethe-Salpeter-equation (BSE) studies of excited-state properties of few-layer black phosphorus (BP) (phosphorene). With improved GW computational methods, we obtained converged quasiparticle band gaps and optical absorption spectra by the single-shot (G0W0) procedure. Moreover, we reveal fine structures of anisotropic excitons, including the series of one-dimensional like wave functions, spin singlet-triplet splitting, and electron-hole binding energy spectra by solving BSE. An effective-mass model is employed to describe these electron-hole pairs, shedding light on estimating the exciton binding energy of anisotropic two-dimensional semiconductors without expensive ab initio simulations. Finally, the anisotropic optical response of BP is explained by using optical selection rules based on the projected single-particle density of states at band edges.

  3. Rydberg-blockade effects in Autler-Townes spectra of ultracold strontium

    NASA Astrophysics Data System (ADS)

    DeSalvo, B. J.; Aman, J. A.; Gaul, C.; Pohl, T.; Yoshida, S.; Burgdörfer, J.; Hazzard, K. R. A.; Dunning, F. B.; Killian, T. C.

    2016-02-01

    We present a combined experimental and theoretical study of the effects of Rydberg interactions on Autler-Townes spectra of ultracold gases of atomic strontium. Realizing two-photon Rydberg excitation via a long-lived triplet state allows us to probe the regime where Rydberg state decay presents the dominant decoherence mechanism. The effects of Rydberg interactions are observed in shifts, asymmetries, and broadening of the measured atom-loss spectra. The experiment is analyzed within a one-body density-matrix approach, accounting for interaction-induced level shifts and dephasing through nonlinear terms that approximately incorporate correlations due to the Rydberg blockade. This description yields good agreement with our experimental observations for short excitation times. For longer excitation times, the loss spectrum is altered qualitatively, suggesting additional dephasing mechanisms beyond the standard blockade mechanism based on pure van der Waals interactions.

  4. Triplet excimer formation of dibromocarbazole chromophores in methacrylate copolymer films measured by time-resolved phosphorescence and transient absorption spectroscopy

    SciTech Connect

    Ito, Shinzaburo; Yamamoto, Masahide ); Liebe, W.R.; Burkhart, R.D. ); Wada, Yoshio )

    1994-08-04

    Time-resolved phosphorescence and transient absorption spectroscopy have been carried out for studying the triplet states of the 3,6-dibromocarbazole (DBCz) chromophore in a solid matrix of methacrylate copolymer. poly[2-(3,6-dibromo-9-carbazoyl)ethyl methacrylate-co-methyl methacrylate]. The sample film containing 10% DBCz units showed critical behavior in the time-resolved phosphorescence spectra which altered the shape from the monomer state [sup 3]M* to two kinds of excimer states: E1 and E2 (460 and 510 nm at the maximum intensity, respectively). These excimeric species have identical profiles with those reported for poly(3,6-dibromo-9-vinylcarbazole), although the polymer structures are totally different. This result shows that the DBCz chromophores tend to take some preferential geometry which results in the formation of two distinct excimer sites in the polymer film. The spectral alteration with time was drastically accelerated by thermal activation in the temperature range 25-77 K. Iterative trapping and detrapping processes determine the rate of relaxation to the deeper traps, E1 and E2. 15 refs., 8 figs., 1 tab.

  5. Far infrared spectra of solid state L-serine, L-threonine, L-cysteine, and L-methionine in different protonation states.

    PubMed

    Gaillard, Thomas; Trivella, Aurélien; Stote, Roland H; Hellwig, Petra

    2015-01-01

    In this study, experimental far infrared measurements of L-serine, L-threonine, L-cysteine, and L-methionine are presented showing the spectra for the 1.0-13.0 pH range. In parallel, solid state DFT calculations were performed on the amino acid zwitterions in the crystalline form. We focused on the lowest frequency far infrared normal modes, which required the most precision and convergence of the calculations. Analysis of the computational results, which included the potential energy distribution of the vibrational modes, permitted a detailed and almost complete assignment of the experimental spectrum. In addition to characteristic signals of the two main acid-base couples, CO2H/CO2(-) and NH3(+)/NH2, specific side chain contributions for these amino acids, including CCO and CCS vibrational modes were analyzed. This study is in line with the growing application of FIR measurements to biomolecules.

  6. Assessment of Functionals for TD-DFT Calculations of Singlet-Triplet Transitions.

    PubMed

    Jacquemin, Denis; Perpète, Eric A; Ciofini, Ilaria; Adamo, Carlo

    2010-05-11

    The calculation of transition energies for electronically excited states remains a challenge in quantum chemistry, for which time-dependent density functional theory (TD-DFT) is often viewed as a balanced (computational effort/obtained accuracy) technique. In this study, we benchmark 34 DFT functionals in the specific framework of TD-DFT calculations for singlet-triplet transitions. The results are compared to accurate wave function data reported for the same set of 63 excited-states, and it turns out that, within the selected TD-DFT framework, BMK and M06-2X emerge as the most efficient hybrids. This investigation clearly illustrates that the conclusions drawn for singlet excited states do not necessarily hold for triplet states, even for similar molecular structures.

  7. Anharmonic Franck-Condon simulation of the absorption and fluorescence spectra for the low-lying S1 and S2 excited states of pyridine.

    PubMed

    Wang, Huan; Zhu, Chaoyuan; Yu, Jian-Guo; Lin, Sheng Hsien

    2009-12-31

    Anharmonic effects of the absorption and fluorescence spectra of pyridine molecule are studied and analyzed for the two-low lying singlet excited states S(1)((1)B(1)) and S(2)((1)B(2)). The complete active space self-consistent field (CASSCF) method is utilized to compute equilibrium geometries and all 27 vibrational normal-mode frequencies for the ground state and the two excited states. The present calculations show that the frequency differences between the ground and two excited states are small for the ten totally symmetric vibrational modes so that the displaced oscillator approximation can be used for spectrum simulations. The Franck-Condon factors within harmonic approximation basically grasp the main features of molecular spectra, but simulated 0-0 transition energy position and spectrum band shapes are not satisfactorily good for S(1)((1)B(1)) absorption and fluorescence spectra in comparison with experiment observation. As the first-order anharmonic correction added to Franck-Condon factors, both spectrum positions and band shapes can be simultaneously improved for both absorption and fluorescence spectra. It is concluded that the present anharmonic correction produces a significant dynamic shifts for spectrum positions and improves spectrum band shapes as well. The detailed structures of absorption spectrum of S(2)((1)B(2)) state observed from experiment can be also reproduced with anharmonic Franck-Condon simulation, and these were not shown in the harmonic Franck-Condon simulation with either distorted or Duschinsky effects in the literature.

  8. Tetralogy of Fallot in monozygotic triplets

    SciTech Connect

    Victorica, B.E.; Kumar, A.; Zori, R.T.

    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.

  9. Isolation of proximity-induced triplet pairing channel in a superconductor/ferromagnet spin valve

    NASA Astrophysics Data System (ADS)

    Leksin, P. V.; Garif'yanov, N. N.; Kamashev, A. A.; Validov, A. A.; Fominov, Ya. V.; Schumann, J.; Kataev, V.; Thomas, J.; Büchner, B.; Garifullin, I. A.

    2016-03-01

    We have studied the proximity-induced superconducting triplet pairing in CoOx/Py1/Cu/Py2/Cu/Pb spin-valve structure (where Py = Ni0.81Fe0.19 ). By optimizing the parameters of this structure we found a triplet channel assisted full switching between the normal and superconducting states. To observe an "isolated" triplet spin-valve effect we exploited the oscillatory feature of the magnitude of the ordinary spin-valve effect Δ Tc in the dependence of the Py2-layer thickness dP y 2. We determined the value of dP y 2 at which Δ Tc caused by the ordinary spin-valve effect (the difference in the superconducting transition temperature Tc between the antiparallel and parallel mutual orientation of magnetizations of the Py1 and Py2 layers) is suppressed. For such a sample a "pure" triplet spin-valve effect which causes the minimum in Tc at the orthogonal configuration of magnetizations has been observed.

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

    NASA Astrophysics Data System (ADS)

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

    2002-05-01

    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.

  11. Field-induced transition from chiral spin-triplet to mixed-parity Fulde-Ferrell-Larkin-Ovchinnikov superconductivity

    NASA Astrophysics Data System (ADS)

    Romano, Alfonso; Cuoco, Mario; Noce, Canio; Gentile, Paola; Annunziata, Gaetano

    2010-02-01

    We analyze the response to a magnetic field of a two-dimensional spin-triplet superconductor with chiral order parameter when triplet pairing is closely competing with the singlet one. The study is performed via numerical solution of the Bogoliubov-de Gennes equations, assuming that the translational symmetry is broken in one direction by the presence of an interface beyond which superconducting pairing is not effective. We show that as the intensity of the magnetic field is increased above a threshold value, the system undergoes a transition to a spatially inhomogeneous state of the Fulde-Ferrell-Larkin-Ovchinnikov (FFLO) type where chirality disappears and a singlet-triplet mixing takes place along the direction perpendicular to the interface. Subdominant singlet components are found to accompany the triplet dominant ones in both phases. They develop close to the interface at low fields, then turning continuously into oscillating long-range ones as the field is increased. A similar behavior is found for the magnetization. It nucleates at the interface in the chiral phase, then acquiring in the FFLO phase an oscillatory behavior reaching its maximum amplitude at the sites where the dominant triplet component has a node. At these sites, the local spin-resolved density of states exhibits strong resonances, associated with the formation of Andreev bound states, which tend to broaden and decay in intensity as increasingly high magnetic fields are considered.

  12. Room temperature and low-temperature absorption and emission spectra of some polypyridylruthenium(II) 3.2.1 complexes

    NASA Astrophysics Data System (ADS)

    Silva, M. I.; Burrows, H. D.; Formosinho, S. J.; Miguel, M. da G.

    2001-05-01

    Electronic absorption and luminescence spectra are reported for a series of complexes of type [Ru(tpy)(L-L)(py)] 2+, where tpy and py are 2,2',2″-terpyridine and pyridine, and L-L represents the bidentate ligands bipyridyl, 4,4'-dimethylbipyridyl, 4-nitrobipyridyl, oxalate and acetylacetonate. The effect of solvent polarity and temperature on their spectral and light emission properties is studied. Energies are reported for the lowest-energy 3MLCT ∗ excited state, and on the basis of these it is suggested that the complexes may make good triplet energy acceptors for use in organic and polymeric light emitting devices.

  13. Regioselectivity and competition of the Paternò-Büchi reaction and triplet-triplet energy transfer between triplet benzophenones and pyrimidines: control by triplet energy levels.

    PubMed

    Liu, Xiu-Ling; Wang, Jian-Bo; Tong, Yao; Song, Qin-Hua

    2013-09-23

    The photochemical reaction of a pyrimidine and a ketone occurs either as a Paternò-Büchi (PB) reaction or as energy transfer (ET) from the triplet ketone to the pyrimidine. It is rare for the two types of reactions to occur concurrently, and their competitive mechanism remains unknown. In this work, two classes of products, regioisomeric oxetane(s) (2, 3) from a PB reaction and three isomeric dimers of 5-fluoro-1,3-dimethyl uracil (FDMU) (4-6) from a photosensitized dimerization of FDMU, are obtained through the UV irradiation of FDMU with various benzophenones (BPs). The ratio of the two products (oxetanes to dimers) reveals that the two competitive reactions depend strongly on the triplet energy levels (ET ) of the BPs. The BPs with higher ET values lead to higher proportions of dimers, whereas those with lower ET values give higher proportions of oxetane(s), with the generation of just two regioisomeric oxetanes for the BP with the lowest ET of the eight BPs investigated. The ratio of the two oxetanes (2:3) decreases with the BP ET value. The competitive mechanism for the two types of photochemical reactions is demonstrated through quenching experiments and investigation of temperature effects. Kinetic analysis shows that the rate constants of the two [2+2] photocycloadditions are comparable. Furthermore, in combination with the results of previous studies, we have gained insight into the dependence of the photochemical type and the regioselectivity in the PB reaction on the triplet energy gaps (ΔE) between the pyrimidines and ketones. For ketones with higher ET values than the pyrimidines, the photochemical reaction is a photosensitized dimerization of the pyrimidine. In the opposite case, a PB reaction occurs, and the lower the ET of the ketones, the lower the ratio of oxetanes (2:3). When the ET of values of the ketones are close to those of the pyrimidines, the two reactions occur concurrently, and the higher the ET of the ketones, the higher the

  14. Excitation dynamics in Phycoerythrin 545: modeling of steady-state spectra and transient absorption with modified Redfield theory.

    PubMed

    Novoderezhkin, Vladimir I; Doust, Alexander B; Curutchet, Carles; Scholes, Gregory D; van Grondelle, Rienk

    2010-07-21

    We model the spectra and excitation dynamics in the phycobiliprotein antenna complex PE545 isolated from the unicellular photosynthetic cryptophyte algae Rhodomonas CS24. The excitonic couplings between the eight bilins are calculated using the CIS/6-31G method. The site energies are extracted from a simultaneous fit of the absorption, circular dichroism, fluorescence, and excitation anisotropy spectra together with the transient absorption kinetics using the modified Redfield approach. Quantitative fit of the data enables us to assign the eight exciton components of the spectra and build up the energy transfer picture including pathways and timescales of energy relaxation, thus allowing a visualization of excitation dynamics within the complex.

  15. Triplet extinction coefficients of some laser dyes. II

    SciTech Connect

    Pavlopoulos, T.G.; Golich, D.J.

    1990-01-01

    We measured the triplet extinction coefficients over the laser action spectral region of DODC, DMC, Sulforhodamine B, Rhodamine 575, Coumarin 523, Coumarin 521, Coumarin 504, Coumarin 498, Coumarin 490, LD466, bis-MSB, and BBO. We employed the different lines from an argon and a krypton ion cw laser for excitation. McClure's method was again employed to measure the triplet extinction coefficients. We provide a simplified derivation of McClure's equation. The triplet extinction coefficient of Rhodamine 575 was also measured by using the depletion method and improving it by reconstructing for true triplet-triplet (T-T) absorption. The ET value obtained is in good agreement with the one obtained by McClure's method.

  16. Three-Triplet Model with Double SU(3) Symmetry

    DOE R&D Accomplishments Database

    Han, M. Y.; Nambu, Y.

    1965-01-01

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

  17. Ordering of PCDTBT revealed by time-resolved electron paramagnetic resonance spectroscopy of its triplet excitons.

    PubMed

    Biskup, Till; Sommer, Michael; Rein, Stephan; Meyer, Deborah L; Kohlstädt, Markus; Würfel, Uli; Weber, Stefan

    2015-06-22

    Time-resolved electron paramagnetic resonance (TREPR) spectroscopy is shown to be a powerful tool to characterize triplet excitons of conjugated polymers. The resulting spectra are highly sensitive to the orientation of the molecule. In thin films cast on PET film, the molecules' orientation with respect to the surface plane can be determined, providing access to sample morphology on a microscopic scale. Surprisingly, the conjugated polymer investigated here, a promising material for organic photovoltaics, exhibits ordering even in bulk samples. Orientation effects may significantly influence the efficiency of solar cells, thus rendering proper control of sample morphology highly important.

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

    PubMed

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

    2014-02-01

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

  19. Formation of Schiff-base for photoreaction mechanism of red shift of GFP spectra.

    PubMed

    Koseki, Jun; Kita, Yukiumi; Tachikawa, Masanori

    2010-04-01

    We have proposed the formation of Schiff-base between R96 and chromophore (CRO) to elucidate the reaction mechanism for the irreversible red shift of green fluorescent protein (GFP) spectra under the absence of oxygen. The difference between absorption energies of reactant and product for our GFP models with CIS(D)/6-31G* level is 0.21eV, which is in reasonable agreement with the corresponding experimental value of 0.25eV. We have suggested the irreversible photoreaction mechanism, where the CRO excited from ground (S(0)) state to first excited singlet (S(1)) state immediately turns to the first excited triplet (T(1)) state, and the nucleophilic addition reaction occurs on the T(1) state.

  20. Correlation and relativistic effects in 2p photoelectron spectra of sodium atoms from the initial state 2{p}^{6}3p

    NASA Astrophysics Data System (ADS)

    Liu, Xiaobin; Shi, Yinglong; Xing, Yongzhong; Lu, Feiping; Chen, Zhanbin

    2017-02-01

    We investigate the 2p photoelectron spectra of sodium atoms with the initial state 2{p}63p at a photon energy of 54 eV. The analysis is performed based on the multi-configuration Dirac–Fock method. Special attention is given to the influences of correlation and relativistic effects on the spectra structures. To explore the nature and importance of such influences, calculations were performed based on detailed analyses of the thresholds, relative intensities and corresponding data calculated in the nonrelativistic limit.

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

    PubMed

    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.

  2. Epigenetics and Triplet-Repeat Neurological Diseases.

    PubMed

    Nageshwaran, Sathiji; Festenstein, Richard

    2015-01-01

    The term "junk DNA" has been reconsidered following the delineation of the functional significance of repetitive DNA regions. Typically associated with centromeres and telomeres, DNA repeats are found in nearly all organisms throughout their genomes. Repetitive regions are frequently heterochromatinized resulting in silencing of intrinsic and nearby genes. However, this is not a uniform rule, with several genes known to require such an environment to permit transcription. Repetitive regions frequently exist as dinucleotide, trinucleotide, and tetranucleotide repeats. The association between repetitive regions and disease was emphasized following the discovery of abnormal trinucleotide repeats underlying spinal and bulbar muscular atrophy (Kennedy's disease) and fragile X syndrome of mental retardation (FRAXA) in 1991. In this review, we provide a brief overview of epigenetic mechanisms and then focus on several diseases caused by DNA triplet-repeat expansions, which exhibit diverse epigenetic effects. It is clear that the emerging field of epigenetics is already generating novel potential therapeutic avenues for this group of largely incurable diseases.

  3. The superconducting spin valve and triplet superconductivity

    NASA Astrophysics Data System (ADS)

    Garifullin, I. A.; Leksin, P. V.; Garif`yanov, N. N.; Kamashev, A. A.; Fominov, Ya. V.; Schumann, J.; Krupskaya, Y.; Kataev, V.; Schmidt, O. G.; Büchner, B.

    2015-01-01

    A review of our recent results on the spin valve effect is presented. We have used a theoretically proposed spin switch design F1/F2/S comprising a ferromagnetic bilayer (F1/F2) as a ferromagnetic component, and an ordinary superconductor (S) as the second interface component. Based on it we have prepared and studied in detail a set of multilayers CoOx/Fe1/Cu/Fe2/S (S=In or Pb). In these heterostructures we have realized for the first time a full spin switch effect for the superconducting current, have observed its sign-changing oscillating behavior as a function of the Fe2-layer thickness and finally have obtained direct evidence for the long-range triplet superconductivity arising due to noncollinearity of the magnetizations of the Fe1 and Fe2 layers.

  4. Facile Co-Assembly of a Dipeptide-Based Organogel toward Efficient Triplet-Triplet Annihilation Photonic Upconversion.

    PubMed

    Liu, Xingcen; Fei, Jinbo; Zhu, Pengli; Li, Junbai

    2016-10-06

    By one-step molecular co-assembly, a diphenylalanine-based photonic upconversion organogel was constructed within 20 seconds. Impressively, such an assembled system exhibits green-to-blue triplet-triplet annihilation upconversion with a relative quantum yield of 12 % even under ambient conditions.

  5. Triplet excitation dynamics of two keto-carotenoids in n-hexane and in methanol as studied by ns flash photolysis spectroscopy

    NASA Astrophysics Data System (ADS)

    Li, Li; Hu, Feng; Chang, Yu-Qiang; Zhou, Yan; Wang, Peng; Zhang, Jian-Ping

    2015-07-01

    Siphonaxanthin and siphonein are two keto-carotenoids. Upon anthracene-sensitizing, triplet excitation dynamics of these two carotenoids were studied in n-hexane and in methanol, respectively, by ns flash photolysis spectroscopy. In n-hexane, bleaching of the ground state absorption (GSB) and the excitation triplet (3Car*) absorption were observed. In methanol, upon the decay of the 3Car*, the cation dehydrodimer of carotenoid, #[Car]2+, generated by the same rate, while an additional GSB generated synchronously, a polar solvent assisted and anthracene-sensitized mechanism was addressed based on the discussion. The environment-sensitive triplet excitation dynamics imply their potential role in photo-protection in vivo.

  6. A blocked diketo form of avobenzone: photostability, photosensitizing properties and triplet quenching by a triazine-derived UVB-filter.

    PubMed

    Paris, Cecilia; Lhiaubet-Vallet, Virginie; Jiménez, Oscar; Trullas, Carles; Miranda, Miguel Angel

    2009-01-01

    Novel sunscreens are required providing active protection in the UVA and UVB regions. On the other hand, there is an increasing concern about the photosafety of UV filters, as some of them are not sufficiently photostable. Avobenzone is one of the most frequently employed sunscreen ingredients, but it has been reported to partially decompose after irradiation. In the present work, photophysical and photochemical studies on a methylated avobenzone-derivative have shown that the diketo form is responsible for photodegradation. A transient absorption was observed at 380 nm after laser flash photolysis excitation at 308 nm. It was assigned to the triplet excited state of the diketo form, as inferred from quenching by oxygen and beta-carotene. This transient also interacted with key building blocks of biomolecules by triplet-triplet energy transfer (in the case of thymidine) or electron transfer processes (for 2'-deoxyguanosine, tryptophan and tyrosine). Irradiation of the avobenzone derivative in the presence of a triazine UV-B filter (E-35852) diminished the undesirable effects of the compound by an efficient quenching of the triplet excited state. Thus, sunscreen formulations including triplet quenchers could provide effective protection from the potential phototoxic and photoallergic effects derived from poor photostability of avobenzone.

  7. Two-photon absorption spectra of a near-infrared 2-azaazulene polymethine dye: solvation and ground-state symmetry breaking.

    PubMed

    Hu, Honghua; Przhonska, Olga V; Terenziani, Francesca; Painelli, Anna; Fishman, Dmitry; Ensley, Trenton R; Reichert, Matthew; Webster, Scott; Bricks, Julia L; Kachkovski, Alexey D; Hagan, David J; Van Stryland, Eric W

    2013-05-28

    Polymethine dyes (PDs) with absorption bands in the near-infrared region undergo symmetry breaking in polar solvents. To investigate how symmetry breaking affects nonlinear optical responses of PDs, an extensive and challenging experimental characterization of a cationic 2-azaazulene polymethine dye, including linear absorption, fluorescence, two-photon absorption and excited-state absorption, has been performed in two solvents with different polarity. Based on this extensive set of experimental data, a three-electronic-state model, accounting for the coupling of electronic degrees of freedom to molecular vibrations and polar solvation, has been reliably parameterized and validated for this dye, fully rationalizing optical spectra in terms of spectral position, intensities and bandshapes. In low-polarity solvents where the dye is mainly in its symmetric form, a nominally forbidden two-photon absorption band is observed, due to a vibronic activation mechanism. Inhomogeneous broadening plays a major role in polar solvents: absorption spectra represent the weighted sum of contributions from states with a variable amount of symmetry breaking, leading to a complex evolution of linear and nonlinear optical spectra with solvent polarity. In more polar solvents, the dominant role of the asymmetric form leads to the activation of two-photon absorption as a result of the symmetry lowering. The subtle interplay between the two mechanisms for two-photon absorption activation, vibronic coupling and polar solvation, can be fully accounted for within the proposed microscopic model allowing a detailed interpretation of the optical spectra of PDs.

  8. Least-squares self-coherency analysis of superconducting gravimeter records in search for the Slichter triplet

    NASA Astrophysics Data System (ADS)

    Pagiatakis, Spiros D.; Yin, Hui; El-Gelil, Mahmoud Abd

    2007-02-01

    We develop a new approach for the spectral analysis of the superconducting gravimeter data to search for the spheroidal oscillation 1S1 of the Earth solid inner core. The new method, which we call least- squares ( LS) self- coherency analysis, is based on the product of the least-squares spectra of segments of the time series under consideration. The statistical foundation of this method is presented in the new least- squares product spectrum theorem that establishes rigorously confidence levels for detecting significant peaks. We apply this approach along with a number of other innovative ideas to a 6-year long gravity series collected at the Canadian Superconducting Gravimeter Installation (CSGI) in Cantley, Canada, by splitting it into 72 statistically independent monthly records. Each monthly record is analysed spectrally and all monthly LS spectra are multiplied to construct the self- coherency spectrum of the 6-year gravity series. The self-coherency spectrum is then used to detect significant peaks in the band 3-7 h at various significant levels with the aim to identify a triplet of periods associated with the rotational/ellipsoidal splitting of 1S1 (Slichter triplet). From all the Slichter periods predicted by various researchers so far, Smylie's triplet appears to be the most supported one, albeit very weakly, both, before and after the atmospheric pressure effect is removed from the series. Using the viscous splitting law [Smylie, D.E., 1992. The inner core translational triplet and the density near Earth's center. Science 255, 1678-1682] as guide, we can also see one interesting and statistically significant triplet with periods A = {4.261 h, 4.516 h, 4.872 h}, which changes slightly to A' = {4.269 h, 4.516 h, 4.889 h} after the atmospheric pressure correction is applied to the gravity series.

  9. Rotationally resolved S1<-- S0 electronic spectra of fluorene, carbazole, and dibenzofuran: evidence for Herzberg-Teller coupling with the S2 state.

    PubMed

    Yi, John T; Alvarez-Valtierra, Leonardo; Pratt, David W

    2006-06-28

    Rotationally resolved fluorescence excitation spectra of the S1 <-- S0 origin bands and higher vibronic bands of fluorene (FLU), carbazole (CAR), and dibenzofuran (DBF) have been observed and assigned. Analyses of these data show that replacement of the CH2 group in FLU with a NH group in CAR and an O atom in DBF produces only localized changes in structure, in the ground state. But the three molecules exhibit different changes in geometry when they are excited by light. The S1 states of the three molecules also are electronically very different. The S1 <-- S0 transition moments of CAR and DBF are parallel to the C2 symmetry axis whereas the corresponding transition moment in FLU is perpendicular to this axis. Herzberg-Teller coupling involving the S2 state also has been observed in the spectra of higher vibronic bands of CAR and DBF. Possible reasons for these behaviors are discussed.

  10. Rotationally resolved S1<--S0 electronic spectra of fluorene, carbazole, and dibenzofuran: Evidence for Herzberg-Teller coupling with the S2 state

    NASA Astrophysics Data System (ADS)

    Yi, John T.; Alvarez-Valtierra, Leonardo; Pratt, David W.

    2006-06-01

    Rotationally resolved fluorescence excitation spectra of the S1←S0 origin bands and higher vibronic bands of fluorene (FLU), carbazole (CAR), and dibenzofuran (DBF) have been observed and assigned. Analyses of these data show that replacement of the CH2 group in FLU with a NH group in CAR and an O atom in DBF produces only localized changes in structure, in the ground state. But the three molecules exhibit different changes in geometry when they are excited by light. The S1 states of the three molecules also are electronically very different. The S1←S0 transition moments of CAR and DBF are parallel to the C2 symmetry axis whereas the corresponding transition moment in FLU is perpendicular to this axis. Herzberg-Teller coupling involving the S2 state also has been observed in the spectra of higher vibronic bands of CAR and DBF. Possible reasons for these behaviors are discussed.

  11. Benzophenone Ultrafast Triplet Population: Revisiting the Kinetic Model by Surface-Hopping Dynamics

    PubMed Central

    2016-01-01

    The photochemistry of benzophenone, a paradigmatic organic molecule for photosensitization, was investigated by means of surface-hopping ab initio molecular dynamics. Different mechanisms were found to be relevant within the first 600 fs after excitation; the long-debated direct (S1 → T1) and indirect (S1 → T2 → T1) mechanisms for population of the low-lying triplet state are both possible, with the latter being prevalent. Moreover, we established the existence of a kinetic equilibrium between the two triplet states, never observed before. This fact implies that a significant fraction of the overall population resides in T2, eventually allowing one to revisit the usual spectroscopic assignment proposed by transient absorption spectroscopy. This finding is of particular interest for photocatalysis as well as for DNA damages studies because both T1 and T2 channels are, in principle, available for benzophenone-mediated photoinduced energy transfer toward DNA. PMID:26821061

  12. Experimental investigation of the role of the triplet pairing in the superconducting spin-valve effect

    NASA Astrophysics Data System (ADS)

    Leksin, P. V.; Kamashev, A. A.; Garif'yanov, N. N.; Validov, A. A.; Fominov, Ya. V.; Schumann, J.; Kataev, V. E.; Büchner, B.; Garifullin, I. A.

    2016-11-01

    An important role of the morphology of a superconducting layer in the superconducting spin-valve effect has been established. The triplet pairing induced by the superconductor/ferromagnet proximity effect has been experimentally investigated for samples CoO x /Py1/Cu/Py2/Cu/Pb (where Py = Ni0.81Fe0.19) with a smooth superconducting layer. The optimization of the parameters of this structure has demonstrated a complete switching between the normal and superconducting states with a change in the relative orientation of magnetizations of the ferromagnetic layers from the antiparallel to orthogonal orientation. A pure triplet contribution has been observed for the sample with a permalloy layer thickness at which the superconducting spin-valve effect vanishes. A direct comparison of the experimental data with the theoretical calculation of the temperature of the transition to the superconducting state has been performed for the first time.

  13. Singlet-triplet energy gaps for diradicals from fractional-spin density-functional theory.

    PubMed

    Ess, Daniel H; Johnson, Erin R; Hu, Xiangqian; Yang, Weitao

    2011-01-13

    Open-shell singlet diradicals are difficult to model accurately within conventional Kohn-Sham (KS) density-functional theory (DFT). These methods are hampered by spin contamination because the KS determinant wave function is neither a pure spin state nor an eigenfunction of the S(2) operator. Here we present a theoretical foray for using single-reference closed-shell ground states to describe diradicals by fractional-spin DFT (FS-DFT). This approach allows direct, self-consistent calculation of electronic properties using the electron density corresponding to the proper spin eigenfunction. The resulting FS-DFT approach is benchmarked against diradical singlet-triplet gaps for atoms and small molecules. We have also applied FS-DFT to the singlet-triplet gaps of hydrocarbon polyacenes.

  14. Singlet-Triplet Energy Gaps for Diradicals from Fractional-Spin Density-Functional Theory

    SciTech Connect

    Ess, Daniel H.; Johnson, E. R.; Hu, Xiangqian; Yang, W. T.

    2010-12-09

    Open-shell singlet diradicals are difficult to model accurately within conventional Kohn-Sham (KS) density-functional theory (DFT). These methods are hampered by spin contamination because the KS determinant wave function is neither a pure spin state nor an eigenfunction of the S2 operator. Here we present a theoretical foray for using single-reference closed-shell ground states to describe diradicals by fractional-spin DFT (FS-DFT). This approach allows direct, self-consistent calculation of electronic properties using the electron density corresponding to the proper spin eigenfunction. The resulting FS-DFT approach is benchmarked against diradical singlet-triplet gaps for atoms and small molecules. We have also applied FS-DFT to the singlet-triplet gaps of hydrocarbon polyacenes.

  15. Triplet p-wave pairing correlation in low-doped zigzag graphene nanoribbons

    NASA Astrophysics Data System (ADS)

    Ma, Tianxing; Yang, Fan; Huang, Zhongbing; Lin, Hai-Qing

    2017-02-01

    We reveal an edge spin triplet p–wave superconducting pairing correlation in slightly doped zigzag graphene nanoribbons. By employing a method that combines random-phase approximation, the finite-temperature determinant quantum Monte Carlo approach, and the ground-state constrained-path quantum Monte Carlo method, it is shown that such a spin-triplet pairing is mediated by the ferromagnetic fluctuations caused by the flat band at the edge. The spin susceptibility and effective pairing interactions at the edge strongly increase as the on-site Coulomb interaction increases, indicating the importance of electron-electron correlations. It is also found that the doping-dependent ground-state p-wave pairing correlation bears some similarity to the famous superconducting dome in the phase diagram of a high-temperature superconductor, while the spin correlation at the edge is weakened as the system is doped away from half filling.

  16. Triplet p-wave pairing correlation in low-doped zigzag graphene nanoribbons

    PubMed Central

    Ma, Tianxing; Yang, Fan; Huang, Zhongbing; Lin, Hai-Qing

    2017-01-01

    We reveal an edge spin triplet p–wave superconducting pairing correlation in slightly doped zigzag graphene nanoribbons. By employing a method that combines random-phase approximation, the finite-temperature determinant quantum Monte Carlo approach, and the ground-state constrained-path quantum Monte Carlo method, it is shown that such a spin-triplet pairing is mediated by the ferromagnetic fluctuations caused by the flat band at the edge. The spin susceptibility and effective pairing interactions at the edge strongly increase as the on-site Coulomb interaction increases, indicating the importance of electron-electron correlations. It is also found that the doping-dependent ground-state p-wave pairing correlation bears some similarity to the famous superconducting dome in the phase diagram of a high-temperature superconductor, while the spin correlation at the edge is weakened as the system is doped away from half filling. PMID:28186185

  17. Physical properties and spectra of IO, IO- and HOI studied by ab initio methods.

    PubMed

    Minaev, Boris; Loboda, Oleksandr; Vahtras, Olav; Agren, Hans; Bilan, Elena

    2002-03-15

    Structure and properties of the IO, IO- and HOI species, which are of potential importance for the ozone destruction catalytic cycle in the troposphere, have been calculated together with the EPR, NMR and UV-visible spectra by ab initio methodology with account of spin-orbit coupling (SOC) effects. Multi-configuration self-consistent field calculations with linear and quadratic response techniques and the multi-reference configuration interaction method have been employed. Photodissociation of these species, crucial for the catalytic ozone-destruction cycle, is critically reviewed and analyzed. Calculations predict that the singlet-triplet (S-T) transition to the lowest triplet state (X1 A' --> 3A'') should be responsible for the weak long-wavelength tail absorption (approximately 450-560 nm) and photodissociation of the HOI molecule. The second, more intense, band around 400 nm is produced by two overlapping S-S and S-T transitions. In order to check this assignment of the HOI photodissociation the isoelectronic IO- anion and IO radical have been studied by the same methods. Comparison with the EPR spectrum of the IO radical indicates that the methods are reliable which gives credit to the accuracy of the HOI spectral interpretation. NMR spectra of HOI and IO- molecules and some other properties are calculated for the first time.

  18. The Moving Lines on Electron Spectra as Charge Reflexes on Non-equilibrium States of Nanostructured Surfaces

    NASA Astrophysics Data System (ADS)

    Mishchuk, Oleg A.

    2016-04-01

    The experimental results present the phenomenon of moving lines on electron spectra which are linked spatially and in time with the localization and durability of the processes of new surface producing in folds and grain boundaries. This effect was also realized for a thin-layer composite "organic on metal films on dielectric substrate" in modeling non-equilibrium conditions which are created by the intensive electron beam pulse impact. It was found that the nature of the inceptive adsorption layer, in addition to the metal film, determines the initial positions of moving lines on the spectra. The main accents in these investigations were in observations of appearance of the moving lines, dynamics of their displacements on the spectra, final stages when these lines vanished, and finding the general regularities between the spontaneous and induced events.

  19. The Moving Lines on Electron Spectra as Charge Reflexes on Non-equilibrium States of Nanostructured Surfaces.

    PubMed

    Mishchuk, Oleg A

    2016-12-01

    The experimental results present the phenomenon of moving lines on electron spectra which are linked spatially and in time with the localization and durability of the processes of new surface producing in folds and grain boundaries. This effect was also realized for a thin-layer composite "organic on metal films on dielectric substrate" in modeling non-equilibrium conditions which are created by the intensive electron beam pulse impact. It was found that the nature of the inceptive adsorption layer, in addition to the metal film, determines the initial positions of moving lines on the spectra. The main accents in these investigations were in observations of appearance of the moving lines, dynamics of their displacements on the spectra, final stages when these lines vanished, and finding the general regularities between the spontaneous and induced events.

  20. Discordant sex in one of three monozygotic triplets.

    PubMed Central

    Dallapiccola, B; Stomeo, C; Ferranti, G; Di Lecce, A; Purpura, M

    1985-01-01

    A case is reported of monozygotic triplets, discordant for phenotypic sex, in which the female presented at birth with the features of Turner's syndrome. Chromosomal analyses showed homogeneous 46,XY karyotypes in the lymphocytes of the three sibs, while a 45,X non-mosaic chromosome constitution was detected in skin fibroblasts of the female triplet. It is suggested that mitotic non-disjunction or anaphase lag occurring early during embryonic development accounted for the occurrence of monosomy X in one cell line of the affected triplet. Previous observations of monozygotic twin pairs discordant for chromosome constitutions are reviewed. Images PMID:3856681

  1. Comparative assessment of density functional methods for evaluating essential parameters to simulate SERS spectra within the excited state energy gradient approximation

    NASA Astrophysics Data System (ADS)

    Mohammadpour, Mozhdeh; Jamshidi, Zahra

    2016-05-01

    The prospect of challenges in reproducing and interpretation of resonance Raman properties of molecules interacting with metal clusters has prompted the present research initiative. Resonance Raman spectra based on the time-dependent gradient approximation are examined in the framework of density functional theory using different methods for representing the exchange-correlation functional. In this work the performance of different XC functionals in the prediction of ground state properties, excitation state energies, and gradients are compared and discussed. Resonance Raman properties based on time-dependent gradient approximation for the strongly low-lying charge transfer states are calculated and compared for different methods. We draw the following conclusions: (1) for calculating the binding energy and ground state geometry, dispersion-corrected functionals give the best performance in comparison to ab initio calculations, (2) GGA and meta GGA functionals give good accuracy in calculating vibrational frequencies, (3) excited state energies determined by hybrid and range-separated hybrid functionals are in good agreement with EOM-CCSD calculations, and (4) in calculating resonance Raman properties GGA functionals give good and reasonable performance in comparison to the experiment; however, calculating the excited state gradient by using the hybrid functional on the hessian of GGA improves the results of the hybrid functional significantly. Finally, we conclude that the agreement of charge-transfer surface enhanced resonance Raman spectra with experiment is improved significantly by using the excited state gradient approximation.

  2. Collisionally-Mediated Singlet-Triplet Crossing in ˜{a}1A1 CH_2 Revisited: (010) Coupling

    NASA Astrophysics Data System (ADS)

    Le, Anh T.; Hall, Gregory; Sears, Trevor

    2014-06-01

    Methylene, CH2, possesses a ground ˜{X}3B1 ground electronic state and an excited ˜{a}1A1 state only 3150cm-1 higher in energy. The collision-induced singlet-triplet crossing in the gaseous mixtures is important in determining overall reaction rates and chemical behavior. Accidental near-degeneracies between rotational levels of the singlet state and the vibrationally excited triplet state result in a few gateway rotational levels that mediate collision-induced intersystem crossing. The mixed states can be recognized and quantified by deperturbation, knowing the zero-order singlet and triplet energy levels. Hyperfine structure can be used as alternative indicator of singlet-triplet mixing. Non-zero mixing will induce hyperfine splittings intermediate between the unresolved hyperfine structure of pure singlet and the resolvable (≈50MHz) splittings of pure triplet, arising from the (I\\cdotS) interaction in the ortho states, where nuclear spin I=1. Collision-induced intersystem crossing rates from the (010) state are comparable to those for (000), yet the identities and characters of the presumed gateway states are unknown. A new spectrometer is under construction to investigate triplet mixing rotational levels of ˜{a}1A1(010) by sub-Doppler measurements of perturbation-induced hyperfine splittings. Their observation will permit the identification of gateway states and quantification of the degree of triplet contamination of the singlet wavefunction. Progress in the measurements and the analysis of rotational energy transfer in (010) will be reported. Acknowledgments: Work at Brookhaven National Laboratory was carried out under Contract No. DE-AC02-98CH10886 with the U.S. Department of Energy and supported by its Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences. C.-H. Chang, G. E. Hall, T. J. Sears, J. Chem. Phys 133, 144310(2010) G. E. Hall, A. V. Komissarov, and T. J. Sears, J. Phys. Chem. A 108 7922-7927 (2004)

  3. Ultrafast interfacial charge separation processes from the singlet and triplet MLCT states of Ru(bpy)2(dcbpy) adsorbed on nanocrystalline SnO2 under negative applied bias

    NASA Astrophysics Data System (ADS)

    Iwai, Shinichiro; Hara, Kohjiro; Murata, Shigeo; Katoh, Ryuzi; Sugihara, Hideki; Arakawa, Hironori

    2000-08-01

    We have observed the stimulated emission from the 1MLCT state of Ru(bpy)2(dcbpy) adsorbed on SnO2 nanocrystal by femtosecond pump-probe spectroscopy under applied bias (Vex) for the first time. The luminescence from the 3MLCT state has been also observed by picosecond time-resolved measurement. Observed lifetimes of the stimulated emission and the luminescence are 70 fs and 130 ps, respectively, at zero applied voltage. Both these lifetimes continuously increase with increasing negative bias and reach 320 fs (stimulated emission) and 6 ns (luminescence) at Vex=-0.7 V. The change in the lifetime of luminescence and of stimulated emission under negative applied bias is considered to be due to the change in the interfacial CS rate, although the possibility of the bias dependent desorption of the dye cannot be completely excluded. We analyzed the result by assuming that the changes in the lifetimes of the stimulated emission and the luminescence are due to the change in the interfacial CS rate constant. This analysis shows that interfacial CS occurs from both the 1MLCT and 3MLCT states. The competition between CS and intersystem crossing (ISC) from 1MLCT occurs in ˜100 fs time region. Assuming there is no nonradiative relaxation pathways from 1MLCT except for CS and for ISC, the rate constant of ISC was estimated to be 1/(320 fs). The ratio of the numbers of electrons injected from the 1MLCT and the 3MLCT states was 0.76:0.22. This means that unnegligible number of electrons are injected to SnO2 from the 1MLCT state.

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

    SciTech Connect

    Corona, Maria; Garay-Palmett, Karina; U'Ren, Alfred B.

    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.

  5. Theory of Triplet Excitation Transfer in the Donor-Oxygen-Acceptor System: Application to Cytochrome b6f

    PubMed Central

    Petrov, Elmar G.; Robert, Bruno; Lin, Sheng Hsien; Valkunas, Leonas

    2015-01-01

    Theoretical consideration is presented of the triplet excitation dynamics in donor-acceptor systems in conditions where the transfer is mediated by an oxygen molecule. It is demonstrated that oxygen may be involved in both real and virtual intramolecular triplet-singlet conversions in the course of the process under consideration. Expressions describing a superexchange donor-acceptor coupling owing to a participation of the bridging twofold degenerate oxygen’s virtual singlet state are derived and the transfer kinetics including the sequential (hopping) and coherent (distant) routes are analyzed. Applicability of this theoretical description to the pigment-protein complex cytochrome b6f, by considering the triplet excitation transfer from the chlorophyll a molecule to distant β-carotene, is discussed. PMID:26488665

  6. Magnetically tunable singlet-triplet spin qubit in a four-electron InGaAs coupled quantum dot

    NASA Astrophysics Data System (ADS)

    Weiss, K. M.; Miguel-Sanchez, J.; Elzerman, J. M.

    2013-11-01

    A pair of self-assembled InGaAs quantum dots filled with two electrons can act as a singlet-triplet spin qubit that is robust against nuclear spin fluctuations as well as charge noise. This results in a T2* coherence time two orders of magnitude longer than that of a single electron, provided the qubit is operated at a particular ``sweet spot'' in gate voltage. However, at this fixed operating point the ground-state splitting can no longer be tuned into resonance with e.g. another qubit, limiting the options for coupling multiple qubits. Here, we propose using a four-electron coupled quantum dot to implement a singlet-triplet qubit that features a magnetically tunable level splitting. As a first step towards full experimental realization of this qubit design, we use optical spectroscopy to demonstrate the tunability of the four-electron singlet-triplet splitting in a moderate magnetic field.

  7. Estimation of ground and excited state dipole moment of laser dyes C504T and C521T using solvatochromic shifts of absorption and fluorescence spectra

    NASA Astrophysics Data System (ADS)

    Basavaraja, Jana; Suresh Kumar, H. M.; Inamdar, S. R.; Wari, M. N.

    2016-02-01

    The absorption and fluorescence spectra of laser dyes: coumarin 504T (C504T) and coumarin 521T (C521T) have been recorded at room temperature in a series of non-polar and polar solvents. The spectra of these dyes showed bathochromic shift with increasing in solvent polarity indicating the involvement of π → π* transition. Kamlet-Taft and Catalan solvent parameters were used to analyze the effect of solvents on C504T and C521T molecules. The study reveals that both general solute-solvent interactions and specific interactions are operative in these two systems. The ground state dipole moment was estimated using Guggenheim's method and also by quantum mechanical calculations. The solvatochromic data were used to determine the excited state dipole moment (μe). It is observed that dipole moment value of excited state (μe) is higher than that of the ground state in both the laser dyes indicating that these dyes are more polar in nature in the excited state than in the ground state.

  8. Estimation of ground and excited state dipole moment of laser dyes C504T and C521T using solvatochromic shifts of absorption and fluorescence spectra.

    PubMed

    Basavaraja, Jana; Kumar, H M Suresh; Inamdar, S R; Wari, M N

    2016-02-05

    The absorption and fluorescence spectra of laser dyes: coumarin 504T (C504T) and coumarin 521T (C521T) have been recorded at room temperature in a series of non-polar and polar solvents. The spectra of these dyes showed bathochromic shift with increasing in solvent polarity indicating the involvement of π→π⁎ transition. Kamlet-Taft and Catalan solvent parameters were used to analyze the effect of solvents on C504T and C521T molecules. The study reveals that both general solute-solvent interactions and specific interactions are operative in these two systems. The ground state dipole moment was estimated using Guggenheim's method and also by quantum mechanical calculations. The solvatochromic data were used to determine the excited state dipole moment (μ(e)). It is observed that dipole moment value of excited state (μ(e)) is higher than that of the ground state in both the laser dyes indicating that these dyes are more polar in nature in the excited state than in the ground state.

  9. Epigenetics and Triplet-Repeat Neurological Diseases

    PubMed Central

    Nageshwaran, Sathiji; Festenstein, Richard

    2015-01-01

    The term “junk DNA” has been reconsidered following the delineation of the functional significance of repetitive DNA regions. Typically associated with centromeres and telomeres, DNA repeats are found in nearly all organisms throughout their genomes. Repetitive regions are frequently heterochromatinized resulting in silencing of intrinsic and nearby genes. However, this is not a uniform rule, with several genes known to require such an environment to permit transcription. Repetitive regions frequently exist as dinucleotide, trinucleotide, and tetranucleotide repeats. The association between repetitive regions and disease was emphasized following the discovery of abnormal trinucleotide repeats underlying spinal and bulbar muscular atrophy (Kennedy’s disease) and fragile X syndrome of mental retardation (FRAXA) in 1991. In this review, we provide a brief overview of epigenetic mechanisms and then focus on several diseases caused by DNA triplet-repeat expansions, which exhibit diverse epigenetic effects. It is clear that the emerging field of epigenetics is already generating novel potential therapeutic avenues for this group of largely incurable diseases. PMID:26733936

  10. Triplet pairing in pure neutron matter

    NASA Astrophysics Data System (ADS)

    Srinivas, Sarath; Ramanan, S.

    2016-12-01

    We study the zero-temperature BCS gaps for the triplet channel in pure neutron matter using similarity renormalization group (SRG) evolved interactions. We use the dependence of the results on the SRG resolution scale as a tool to analyze medium and many-body corrections. In particular, we study the effects of including the three-body interactions at leading order, which appear at next-to-next-to leading order (N2LO) in the chiral effective field theory (EFT), as well as that of the first-order self-energy corrections on the zero-temperature gap. In addition we also extract the transition temperature as a function of densities and verify the BCS scaling of the zero-temperature gaps to the transition temperature. We observe that the self-energy effects are very crucial in order to reduce the SRG resolution scale dependence of the results, while the three-body effects at the leading order do not change the two-body resolution scale dependence. On the other hand, the results depend strongly on the three-body cutoff, emphasizing the importance of the missing higher-order three-body effects. We also observe that self-energy effects reduce the overall gap as well as shift the gap closure to lower densities.

  11. Triplet pairing in pure neutron matter

    NASA Astrophysics Data System (ADS)

    Srinivas, Sarath; Ramanan, Sunethra

    2016-09-01

    We study the zero temperature BCS gaps for the triplet channel in pure neutron matter using Similarity Renormalization Group (SRG) evolved interactions. We use the dependence of the results on the SRG resolution scale, as a tool to analyze medium and many-body corrections. In particular, we study the effects of including the three-body interactions at leading order, which appear at N2LO in the Chiral EFT, as well as that of the first-order self-energy corrections on the zero temperature gap. In addition we also extract the transition temperature as a function of densities and verify the BCS scaling of the zero temperature gaps to the transition temperature. We observe that the self-energy effects are very crucial in order to reduce the resolution scale dependence of the results, while the three-body effects at the leading order do not change the two-body resolution scale depdendence. On the other hand, the results depend strongly on the three-body cut-off, emphasizing the importance of the missing higher-order three-body effects. We also observe that self-energy effects reduce the overall gap as well as shift the gap closure to lower densities.

  12. Computational Kinetics by Variational Transition-State Theory with Semiclassical Multidimensional Tunneling: Direct Dynamics Rate Constants for the Abstraction of H from CH3OH by Triplet Oxygen Atoms.

    PubMed

    Meana-Pañeda, Rubén; Xu, Xuefei; Ma, He; Truhlar, Donald G

    2017-03-02

    Rate constants and the product branching ratio for hydrogen abstraction from CH3OH by O((3)P) were computed with multistructural variational transition-state theory including microcanonically optimized multidimensional tunneling. Benchmark calculations of the forward and reverse classical barrier heights and the reaction energetics have been carried out by using coupled cluster theory and multireference calculations to select the most reliable density functional method for direct dynamics computations of the rate constants. The dynamics calculations included the anharmonicity of the zero-point energies and partition functions, with specific-reaction-parameter scaling factors for reactants and transition states, and multistructural torsional anharmonicity was included for the torsion around the C-O bond in methanol and in the transition states. The resulting rate constants are presented over a wider range than they are available from experiment, but in the temperature range where experiments are available, they agree well with experimental values, which is encouraging for their reliability over the wider temperature range and for future computations of oxygen atom reaction rates. In contrast to a previous computational prediction, the branching ratio predicted by the present work shows that the formation of CH2OH + OH is the dominant channel over the whole range of temperature from 250 to 2000 K.

  13. Scalar triplet on a domain wall: an exact solution

    NASA Astrophysics Data System (ADS)

    Gani, Vakhid A.; Lizunova, Mariya A.; Radomskiy, Roman V.

    2016-04-01

    We study a model with a real scalar Higgs field and a scalar triplet field that allows existence of a topological defect — a domain wall. The wall breaks the global O(3) symmetry of the model, which gives rise to non-Abelian orientational degrees of freedom. We found an exact analytic solution that describes a domain wall with a localized configuration of the triplet field on it. This solution enables one to calculate contributions to the action from the orientational and translational degrees of freedom of the triplet field. We also study the linear stability of the domain wall with the triplet field switched off. We obtain that degrees of freedom localized on the wall can appear or do not appear depending on the parameters of the model.

  14. Magnetoelectric Andreev Effect due to Proximity-Induced Nonunitary Triplet Superconductivity in Helical Metals

    NASA Astrophysics Data System (ADS)

    Tkachov, G.

    2017-01-01

    Noncentrosymmetric superconductors exhibit the magnetoelectric effect, which manifests itself in the appearance of the magnetic spin polarization in response to a dissipationless electric current (supercurrent). While much attention has been dedicated to the thermodynamic version of this phenomenon (Edelstein effect), nonequilibrium transport magnetoelectric effects have not been explored yet. We propose the magnetoelectric Andreev effect (MAE), which consists in the generation of spin-polarized triplet Andreev conductance by an electric supercurrent. The MAE stems from the spin polarization of the Cooper-pair condensate due to a supercurrent-induced nonunitary triplet pairing. We propose the realization of such a nonunitary pairing and MAE in superconducting proximity structures based on two-dimensional helical metals—strongly spin-orbit-coupled electronic systems with the Dirac spectrum such as the topological surface states. Our results uncover an unexplored route towards electrically controlled superconducting spintronics and are a smoking gun for induced unconventional superconductivity in spin-orbit-coupled materials.

  15. Triplet pairing and possible weak topological superconductivity in BiS2-based superconductors

    NASA Astrophysics Data System (ADS)

    Yang, Yang; Wang, Wan-Sheng; Xiang, Yuan-Yuan; Li, Zheng-Zao; Wang, Qiang-Hua

    2013-09-01

    We show that the newly discovered BiS2-based superconductors may have a dominant triplet pairing component in addition to a subdominant singlet component arising from the spin-orbital coupling. The pairing respects time-reversal symmetry. The dominant triplet gap causes gap sign changes between the spin-split Fermi pockets. Within a pocket, the gap function respects dx2-y2*-wave symmetry where the asterisk indicates joint spin-lattice rotations. Below the Lifshitz filling level, the gap is nodeless, and the superconducting state is weak topological. Above the Lifshitz points, the gap becomes nodal. The superconducting pairing and the time-reversal symmetry result from the strong spin-orbital coupling and the ferromagneticlike spin fluctuations. The dx2-y2*-wave gap structure follows from the coexisting antiferromagnetic spin fluctuations. The relevance to experiments is discussed.

  16. Triplet FFLO superconductivity in the doped Kitaev-Heisenberg honeycomb model

    NASA Astrophysics Data System (ADS)

    Liu, Tianhan; Repellin, Cécile; Douçot, Benoît; Regnault, Nicolas; Le Hur, Karyn

    2016-11-01

    We provide analytical and numerical evidence of spin-triplet Fulde-Ferrell-Larkin-Ovchinnikov (FFLO) superconductivity in the itinerant Kitaev-Heisenberg model (antiferromagnetic Kitaev coupling and ferromagnetic Heisenberg coupling) on the honeycomb lattice around quarter filling. The strong spin-orbit coupling in our model leads to the emergence of six inversion symmetry centers for the Fermi surface at nonzero momenta in the first Brillouin zone. We show how the Cooper pairs condense into these nontrivial momenta, causing spatial modulation of the superconducting order parameter. Applying a Ginzburg-Landau expansion analysis, we find that the superconductivity has three separated degenerate ground states with three different spin-triplet pairings. Exact diagonalizations on finite clusters support this picture while ruling out a spin (charge) density wave.

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

    SciTech Connect

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

    1994-08-04

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

  18. Triplet superconductivity in 3D Dirac semi-metal due to exchange interaction.

    PubMed

    Rosenstein, Baruch; Shapiro, B Ya; Li, Dingping; Shapiro, I

    2015-01-21

    Conventional phonon-electron interaction induces either triplet or one of two (degenerate) singlet pairing states in time reversal and inversion invariant 3D Dirac semi-metal. Investigation of the order parameters and energies of these states at zero temperature in a wide range of values of chemical potential μ, the effective electron-electron coupling constant λ and Debye energy TD demonstrates that when the exchange interaction is neglected the singlet always prevails, however, in significant portions of the (μ, λ, TD) parameter space the energy difference is very small. This means that interactions that are small, but discriminate between the spin singlet and the spin triplet, are important in order to determine the nature of the superconducting order there. The best candidate for such an interaction in the materials under consideration is the exchange (the Stoner term) characterized by constant λex. We show that at values of λex, much smaller than ones creating Stoner instability to ferromagnetism λex ∼ 1, the triplet pairing becomes energetically favored over the singlet ones. The 3D quantum critical point at μ = 0 is considered in detail. This can be realized experimentally in optically trapped cold atom systems.

  19. Infrared, Raman, and ultraviolet absorption spectra and theoretical calculations and structure of 2,6-difluoropyridine in its ground and excited electronic states.

    PubMed

    Sheu, Hong-Li; Kim, Sunghwan; Laane, Jaan

    2013-12-19

    The infrared and Raman spectra of 2,6-difluoropyridine (26DFPy) along with ab initio and DFT computations have been used to assign the vibrations of the molecule in its S0 electronic ground state and to calculate its structure. The ultraviolet absorption spectrum showed the electronic transition to the S1(π,π*) state to be at 37,820.2 cm(-1). With the aid of ab initio computations the vibrational frequencies for this excited state were also determined. TD-B3LYP and CASSCF computations for the excited states were carried out to calculate the structures for the S1(π,π*) and S2(n,π*) excited states. The CASSCF results predict that the S1(π,π*) state is planar and that the S2(n,π*) state has a barrier to planarity of 256 cm(-1). The TD-B3LYP computations predict a barrier of 124 cm(-1) for the S1(π,π*) state, but the experimental results support the planar structure. Hypothetical models for the ring-puckering potential energy function were calculated for both electronic excited states to show the predicted quantum states. The changes in the vibrational frequencies in the two excited states reflect the weaker π bonding within the pyridine ring.

  20. Phonon density of states of Sn in textured SnO under high pressure: Comparison of nuclear inelastic x-ray scattering spectra to a shell model

    NASA Astrophysics Data System (ADS)

    Giefers, H.; Koval, S.; Wortmann, G.; Sturhahn, W.; Alp, E. E.; Hu, M. Y.

    2006-09-01

    The local phonon density of states (DOS) at the Sn site in tin monoxide (SnO) is studied at pressures up to 8GPa with Sn119 nuclear resonant inelastic x-ray scattering (NRIXS) of synchrotron radiation at 23.88keV . The preferred orientation (texture) of the SnO crystallites in the investigated samples is used to measure NRIXS spectra preferentially parallel and almost perpendicular to the c axis of tetragonal SnO . A subtraction method is applied to these NRIXS spectra to produce projected local Sn DOS spectra as seen parallel and perpendicular to the c axis of SnO . These experimentally obtained local Sn DOS spectra, both in the polycrystalline case as well as projected parallel and perpendicular to the c axis, are compared with corresponding theoretical phonon DOS spectra, derived from dispersion relations calculated with a recently developed shell model. Comparison between the experimental projected Sn DOS spectra and the corresponding theoretical DOS spectra enables us to follow the pressure-induced shifts of several acoustic and optic phonon modes. While the principal spectral features of the experimental and theoretical phonon DOS agree well at energies above 10meV , the pressure behavior of the low-energy part of the DOS is not well reproduced by the theoretical calculations. In fact, they exhibit, in contrast to the experimental data, a dramatic softening of two low-energy modes, their energies approaching zero around 2.5GPa , clearly indicating the limitations of the applied shell model. These difficulties are obviously connected with the complex Sn-O and Sn-Sn bindings within and between the Sn-O-Sn layers in the litharge structure of SnO . We derived from the experimental and theoretical DOS spectra a variety of elastic and thermodynamic parameters of the Sn sublattice, such as the Lamb-Mössbauer factor, the mean force constant, and Debye temperatures, as well as the vibrational contributions to the Helmholtz free energy, specific heat, entropy, and

  1. On the He/plus/ triplet line intensities.

    NASA Technical Reports Server (NTRS)

    Daltabuit, E.; Cox, D. P.

    1972-01-01

    Check of the adequacy of theoretical calculations of helium-triplet line strengths, including collisional enhancement, by comparing theoretical prediction with astronomical observations. It is shown that the observations of Peimbert and Torres-Peimbert (1971) and of Peimbert and Costero (1969) fit the theoretical predictions rather well, placing planetary nebulae and H II regions in separate density and temperature ranges. It appears that the theory of helium-triplet line strengths agrees with present observations.

  2. Acardius in a triplet pregnancy: cytogenetic and morphological profile.

    PubMed

    Bolaji, I I; Mortimer, G; Meehan, F P; England, S; Greally, M

    1992-01-01

    We describe a rare case of acardius in a triplet pregnancy terminated by Caesarean Section at 32 weeks gestation. Morphological and chromosomal abnormalities of the fetus as well as structural abnormalities of the placenta are presented. Cytogenetic analysis and examination of the single disc triplet placenta provide evidence for the two major theories of pathogenesis of acardius, the twin reversed arterial perfusion (TRAP) sequence and the genetic theory, which we believe are not necessarily mutually exclusive.

  3. Thickness dependence of the triplet spin-valve effect in superconductor–ferromagnet–ferromagnet heterostructures

    PubMed Central

    Zdravkov, Vladimir I; Kehrle, Jan-Michael; Obermeier, Günter; Ullrich, Aladin; Morari, Roman; Krug von Nidda, Hans-Albrecht; Müller, Claus; Kupriyanov, Mikhail Yu; Sidorenko, Anatolie S; Horn, Siegfried; Deminov, Rafael G; Tagirov, Lenar R; Tidecks, Reinhard

    2016-01-01

    Summary Background: In nanoscale layered S/F1/N/F2/AF heterostructures, the generation of a long-range, odd-in-frequency spin-projection one triplet component of superconductivity, arising at non-collinear alignment of the magnetizations of F1 and F2, exhausts the singlet state. This yields the possibility of a global minimum of the superconducting transition temperature T c, i.e., a superconducting triplet spin-valve effect, around mutually perpendicular alignment. Results: The superconducting triplet spin valve is realized with S = Nb a singlet superconductor, F1 = Cu41Ni59 and F2 = Co ferromagnetic metals, AF = CoOx an antiferromagnetic oxide, and N = nc-Nb a normal conducting (nc) non-magnetic metal, which serves to decouple F1 and F2. The non-collinear alignment of the magnetizations is obtained by applying an external magnetic field parallel to the layers of the heterostructure and exploiting the intrinsic perpendicular easy-axis of the magnetization of the Cu41Ni59 thin film in conjunction with the exchange bias between CoOx and Co. The magnetic configurations are confirmed by superconducting quantum interference device (SQUID) magnetic moment measurements. The triplet spin-valve effect has been investigated for different layer thicknesses, d F1, of F1 and was found to decay with increasing d F1. The data is described by an empirical model and, moreover, by calculations using the microscopic theory. Conclusion: The long-range triplet component of superconducting pairing is generated from the singlet component mainly at the N/F2 interface, where the amplitude of the singlet component is suppressed exponentially with increasing distance d F1. The decay length of the empirical model is found to be comparable to twice the electron mean free path of F1 and, thus, to the decay length of the singlet component in F1. Moreover, the obtained data is in qualitative agreement with the microscopic theory, which, however, predicts a (not investigated) breakdown of the

  4. Perinatal and Neonatal Outcomes of Triplet Gestations Based on Chorionicity

    PubMed Central

    Downing, Maureen; Sulo, Suela; Parilla, Barbara V.

    2017-01-01

    Objective To compare perinatal and neonatal outcomes of dichorionic (DC) and monochorionic (MC) with trichorionic (TC) triplet gestations. Methods A retrospective cohort study of DC + MC versus TC triplet gestations delivered at a tertiary care hospital from 2009 to 2015. The results include 42 sets of triplets (TC, n = 26; DC + MC, n = 16). Maternal demographics and pregnancy data were compared. Neonatal outcomes were assessed using composite morbidity and mortality. Results Maternal baseline characteristics including age, mode of conception, race, parity, body mass index, and previous preterm delivery were statistically comparable. Comparison of prenatal management and complications yielded no significant differences in terms of presence of shortened cervix, cerclage placement, use of tocolytics, intrauterine growth restriction, premature rupture of membranes, pregnancy-induced hypertension, or gestational diabetes. However, evaluation of composite morbidity and mortality (RDS, IVH, NEC, IUGR, and death) illustrated that all infants born from DC + MC triplet gestations suffered some morbidity or mortality compared with TC pregnancies (p < 0.01). Conclusion DC + MC triplet gestations are at an increased risk of neonatal morbidity and mortality compared with TC triplet gestations. PMID:28367358

  5. Short-Range Characterization of the MeAr (Me=Zn, Cd) Ground-State Potentials from Fluorescence Spectra

    NASA Astrophysics Data System (ADS)

    Koperski, J.; Czajkowski, M.

    2002-04-01

    First-time observed D1(1Π)v‧=10→X0+(1Σ) fluorescence in ZnAr, and A0+(3Π)v‧=4→X0+ and D1(1Π)v‧=7,8→X0+ fluorescence in CdAr van der Waals (vdW) molecules were produced in a continuous supersonic molecular beam crossed with a pulsed dye-laser beam, following excitation of single vibronic levels. The dispersed fluorescence spectra displayed characteristic Condon internal diffraction (CID) patterns consisting of bound-free, reflection type, continuous spectra, and, in certain cases, bound-bound discrete features. An analysis of the A0+→X0+ and D1→X0+ bound-bound spectra indicates that Morse functions are adequate representations of the X0+ potential energy (PE) curves below their dissociation limits. In simulation of the A0+→X0+ and D1→X0+ bound-free spectra, the Morse, Lennard-Jones L-J(n-6), and Maitland-Smith M-S(n0,n1) functions were tested, and the respective M-S(11.3, 9.0) and M-S(10.6, 7.0) potentials were found to be good representations for the repulsive walls of the X0+ PE curves of ZnAr and CdAr, respectively, over the short range, R=2.45-4.38 Å (ZnAr) and R=2.85-4.31 Å (CdAr), of internuclear separations.

  6. The origin of the absorption spectra of porphyrin N- and dithiaporphyrin S-oxides in their neutral and protonated states.

    PubMed

    Bruhn, Torsten; Brückner, Christian

    2015-02-07

    meso-Tetraphenylporphyrin N-oxide (1) and meso-tetraphenyl-21,23-dithiaporphyrin S-oxide (3) possess optical spectra that are distinctly different from their parent porphyrins, meso-tetraphenylporphyrin (2) and meso-tetraphenyl-21,23-dithiaporphyrin (4), respectively. The hyperporphyrin spectra were reproduced and classified using TD CAM-B3LYP and SCS-CC2 computational methods. Calculations revealed the electronic and conformational influences of the N- and S-oxide functionalities. While the N-oxide under acidic conditions forms a dication with a UV-vis spectrum that is nearly indistinguishable from that of the diprotonated parent porphyrin, the diprotonated S-oxide possesses a much different UV-vis spectrum from diprotonated parent dithiaporphyrin. A computational study of the protonation events revealed the site and degree of protonation and rationalized the regular and hyperporphyrin UV-vis spectra of the neutral and protonated species, respectively. The study illuminates the electronic effects of the relatively rare modification of the inner porphyrin heteroatoms. It also illustrates a case in which TD CAM-B3LYP reaches its limits to make reliable predictions about the optical properties of a porphyrinoid, making the use of higher methods essential.

  7. Broadband up-conversion at subsolar irradiance: triplet-triplet annihilation boosted by fluorescent semiconductor nanocrystals.

    PubMed

    Monguzzi, A; Braga, D; Gandini, M; Holmberg, V C; Kim, D K; Sahu, A; Norris, D J; Meinardi, F

    2014-11-12

    Conventional solar cells exhibit limited efficiencies in part due to their inability to absorb the entire solar spectrum. Sub-band-gap photons are typically lost but could be captured if a material that performs up-conversion, which shifts photon energies higher, is coupled to the device. Recently, molecular chromophores that undergo triplet-triplet annihilation (TTA) have shown promise for efficient up-conversion at low irradiance, suitable for some types of solar cells. However, the molecular systems that have shown the highest up-conversion efficiency to date are ill suited to broadband light harvesting, reducing their applicability. Here we overcome this limitation by combining an organic TTA system with highly fluorescent CdSe semiconductor nanocrystals. Because of their broadband absorption and spectrally narrow, size-tunable fluorescence, the nanocrystals absorb the radiation lost by the TTA chromophores, returning this energy to the up-converter. The resulting nanocrystal-boosted system shows a doubled light-harvesting ability, which allows a green-to-blue conversion efficiency of ∼12.5% under 0.5 suns of incoherent excitation. This record efficiency at subsolar irradiance demonstrates that boosting the TTA by light-emitting nanocrystals can potentially provide a general route for up-conversion for different photovoltaic and photocatalytic applications.

  8. Improving triplet-triplet-annihilation based upconversion systems by tuning their topological structure

    SciTech Connect

    Zimmermann, Jochen Wellens, Thomas; Buchleitner, Andreas; Mulet, Roberto; Scholes, Gregory D.

    2014-11-14

    Materials capable to perform upconversion of light transform the photon spectrum and can be used to increase the efficiency of solar cells by upconverting sub-bandgap photons, increasing the density of photons able to generate an electron-hole pair in the cell. Incoherent solar radiation suffices to activate upconverters based on sensitized triplet-triplet annihilation, which makes them particularly suited for this task. This process requires two molecular species, sensitizers absorbing low energy photons, and emitters generating higher frequency photons. Successful implementations exist in solutions and solids. However, solid upconverters exhibit lower efficiency than those in solution, which poses a serious problem for real applications. In the present work, we suggest a new strategy to increase the efficiency of sensitized upconverters that exploits the solid nature of the material. We show that an upconversion model system with molecules distributed as clusters outperforms a system with a random distribution of molecules, as used in current upconverters. Our simulations reveal a high potential for improvement of upconverter systems by exploring different structural configurations of the molecules. The implementation of advanced structures can push the performance of solid upconverters further towards the theoretical limit and a step closer to technological application of low power upconversion.

  9. Imaging the radical channel in acetaldehyde photodissociation: Competing mechanisms at energies close to the triplet exit barrier

    SciTech Connect

    Amaral, G. A.; Arregui, A.; Rodriguez, J. D.; Banares, L.; Rubio-Lago, L.

    2010-08-14

    The photodissociation of acetaldehyde in the radical channel has been studied at wavelengths between 315 and 325 nm using the velocity-map imaging technique. Upon one-photon absorption at 315 nm, the molecule is excited to the first singlet excited state S{sub 1}, which, in turn, undergoes intersystem crossing to the first excited triplet state T{sub 1}. On the triplet surface, the molecule dissociates into CH{sub 3} and HCO radicals with large kinetic energy release (KER), in accordance with the well characterized exit barrier on T{sub 1}. However, at longer wavelengths (>320 nm), which correspond to excitation energies just below the triplet barrier, a sudden change in KER is observed. At these photolysis wavelengths, there is not enough energy to surpass the exit barrier on the triplet state, which leaves the possibility of unimolecular dissociation on S{sub 0} after internal conversion from S{sub 1}. We have characterized the fragments' KER at these wavelengths, as well as determined the energy partitioning for the radical fragments. A new accurate estimate of the barrier height on T{sub 1} is presented.

  10. Impact of environmentally induced fluctuations on quantum mechanically mixed electronic and vibrational pigment states in photosynthetic energy transfer and 2D electronic spectra

    NASA Astrophysics Data System (ADS)

    Fujihashi, Yuta; Fleming, Graham R.; Ishizaki, Akihito

    2015-06-01

    Recently, nuclear vibrational contribution signatures in two-dimensional (2D) electronic spectroscopy have attracted considerable interest, in particular as regards interpretation of the oscillatory transients observed in light-harvesting complexes. These transients have dephasing times that persist for much longer than theoretically predicted electronic coherence lifetime. As a plausible explanation for this long-lived spectral beating in 2D electronic spectra, quantum-mechanically mixed electronic and vibrational states (vibronic excitons) were proposed by Christensson et al. [J. Phys. Chem. B 116, 7449 (2012)] and have since been explored. In this work, we address a dimer which produces little beating of electronic origin in the absence of vibronic contributions, and examine the impact of protein-induced fluctuations upon electronic-vibrational quantum mixtures by calculating the electronic energy transfer dynamics and 2D electronic spectra in a numerically accurate manner. It is found that, at cryogenic temperatures, the electronic-vibrational quantum mixtures are rather robust, even under the influence of the fluctuations and despite the small Huang-Rhys factors of the Franck-Condon active vibrational modes. This results in long-lasting beating behavior of vibrational origin in the 2D electronic spectra. At physiological temperatures, however, the fluctuations eradicate the mixing, and hence, the beating in the 2D spectra disappears. Further, it is demonstrated that such electronic-vibrational quantum mixtures do not necessarily play a significant role in electronic energy transfer dynamics, despite contributing to the enhancement of long-lived quantum beating in 2D electronic spectra, contrary to speculations in recent publications.

  11. Impact of environmentally induced fluctuations on quantum mechanically mixed electronic and vibrational pigment states in photosynthetic energy transfer and 2D electronic spectra

    SciTech Connect

    Fujihashi, Yuta; Ishizaki, Akihito; Fleming, Graham R.

    2015-06-07

    Recently, nuclear vibrational contribution signatures in two-dimensional (2D) electronic spectroscopy have attracted considerable interest, in particular as regards interpretation of the oscillatory transients observed in light-harvesting complexes. These transients have dephasing times that persist for much longer than theoretically predicted electronic coherence lifetime. As a plausible explanation for this long-lived spectral beating in 2D electronic spectra, quantum-mechanically mixed electronic and vibrational states (vibronic excitons) were proposed by Christensson et al. [J. Phys. Chem. B 116, 7449 (2012)] and have since been explored. In this work, we address a dimer which produces little beating of electronic origin in the absence of vibronic contributions, and examine the impact of protein-induced fluctuations upon electronic-vibrational quantum mixtures by calculating the electronic energy transfer dynamics and 2D electronic spectra in a numerically accurate manner. It is found that, at cryogenic temperatures, the electronic-vibrational quantum mixtures are rather robust, even under the influence of the fluctuations and despite the small Huang-Rhys factors of the Franck-Condon active vibrational modes. This results in long-lasting beating behavior of vibrational origin in the 2D electronic spectra. At physiological temperatures, however, the fluctuations eradicate the mixing, and hence, the beating in the 2D spectra disappears. Further, it is demonstrated that such electronic-vibrational quantum mixtures do not necessarily play a significant role in electronic energy transfer dynamics, despite contributing to the enhancement of long-lived quantum beating in 2D electronic spectra, contrary to speculations in recent publications.

  12. Impact of environmentally induced fluctuations on quantum mechanically mixed electronic and vibrational pigment states in photosynthetic energy transfer and 2D electronic spectra.

    PubMed

    Fujihashi, Yuta; Fleming, Graham R; Ishizaki, Akihito

    2015-06-07

    Recently, nuclear vibrational contribution signatures in two-dimensional (2D) electronic spectroscopy have attracted considerable interest, in particular as regards interpretation of the oscillatory transients observed in light-harvesting complexes. These transients have dephasing times that persist for much longer than theoretically predicted electronic coherence lifetime. As a plausible explanation for this long-lived spectral beating in 2D electronic spectra, quantum-mechanically mixed electronic and vibrational states (vibronic excitons) were proposed by Christensson et al. [J. Phys. Chem. B 116, 7449 (2012)] and have since been explored. In this work, we address a dimer which produces little beating of electronic origin in the absence of vibronic contributions, and examine the impact of protein-induced fluctuations upon electronic-vibrational quantum mixtures by calculating the electronic energy transfer dynamics and 2D electronic spectra in a numerically accurate manner. It is found that, at cryogenic temperatures, the electronic-vibrational quantum mixtures are rather robust, even under the influence of the fluctuations and despite the small Huang-Rhys factors of the Franck-Condon active vibrational modes. This results in long-lasting beating behavior of vibrational origin in the 2D electronic spectra. At physiological temperatures, however, the fluctuations eradicate the mixing, and hence, the beating in the 2D spectra disappears. Further, it is demonstrated that such electronic-vibrational quantum mixtures do not necessarily play a significant role in electronic energy transfer dynamics, despite contributing to the enhancement of long-lived quantum beating in 2D electronic spectra, contrary to speculations in recent publications.

  13. The cavity ringdown spectrum of the visible electronic system of thiophosgene: An estimation of the lifetime of the T{sub 1}({tilde a};{sup 3}A{sub 2}) triplet state

    SciTech Connect

    Moule, D.C.; Burling, I.R.; Liu, H.; Lim, E.C.

    1999-09-01

    To obtain insights into the photophysical properties of collision-free T{sub 1}({tilde a}&hthinsp;{sup 3}A{sub 2}) thiophosgene, Cl{sub 2}CS, the cavity ringdown (CRD) spectrum of the T{sub 1}{l_arrow}S{sub 0} absorption system was recorded under supersonic jet conditions and compared with the corresponding excitation spectrum of the total emission. It was found that none of the T{sub 1}{l_arrow}S{sub 0} bands in the CRD spectrum appears in the excitation spectrum, indicating that the T{sub 1} thiophosgene decays almost exclusively by the nonradiative T{sub 1}{r_arrow}S{sub 0} intersystem crossing (ISC). An estimation of the T{sub 1} nonradiative lifetime was made using the T{sub 1}{endash}S{sub 0} spin-orbit coupling and the Franck{endash}Condon factors for the T{sub 1}{r_arrow}S{sub 0} ISC based on the {ital ab initio} equilibrium structures and vibrational frequencies for the T{sub 1} and S{sub 0} states, computed at the MP2/6-31G(d,p) and MP4/6-31G(d,p) level of theory. The nonradiative life, calculated as the 1/e of the survival probability, is approximately 20 ps for barrier heights of 770{endash}845 cm{sup {minus}1} and out-of-plane angles of 32.07{degree}{endash}32.69{degree}. (The thiophosgene adopts a pyramidal conformation with the C{double_bond}S bond bent from the ClCCl plane by about 32{degree}.) The computed lifetime is comparable to the lower-limit lifetime of {approximately}50 ps obtained from the quantum yields {Phi}{sub P}{le}10{sup {minus}3}{Phi}{sub F} with {Phi}{sub F}{approx}1.0 and the measured S{sub 1} fluorescence lifetime of 4 {mu}s. The short T{sub 1} nonradiative lifetime of thiophosgene can be attributed to the large matrix elements of the T{sub 1}{endash}S{sub 0} spin-orbit coupling (V=150&hthinsp;cm{sup {minus}1}) and the strong out-of-plane deformation of the T{sub 1} state relative to the planar S{sub 0} state, that provides the large Franck{endash}Condon factors for the T{sub 1}{r_arrow}S{sub 0} ISC. It is proposed that a similar

  14. The cavity ringdown spectrum of the visible electronic system of thiophosgene: An estimation of the lifetime of the T[sub 1]([tilde a]; [sup 3]A[sub 2]) triplet state

    SciTech Connect

    Moule, D.C.; Burling, I.R. ); Liu, H.; Lim, E.C. )

    1999-09-01

    To obtain insights into the photophysical properties of collision-free T[sub 1]([tilde a] hthinsp;[sup 3]A[sub 2]) thiophosgene, Cl[sub 2]CS, the cavity ringdown (CRD) spectrum of the T[sub 1][l arrow]S[sub 0] absorption system was recorded under supersonic jet conditions and compared with the corresponding excitation spectrum of the total emission. It was found that none of the T[sub 1][l arrow]S[sub 0] bands in the CRD spectrum appears in the excitation spectrum, indicating that the T[sub 1] thiophosgene decays almost exclusively by the nonradiative T[sub 1][r arrow]S[sub 0] intersystem crossing (ISC). An estimation of the T[sub 1] nonradiative lifetime was made using the T[sub 1][endash]S[sub 0] spin-orbit coupling and the Franck[endash]Condon factors for the T[sub 1][r arrow]S[sub 0] ISC based on the [ital ab initio] equilibrium structures and vibrational frequencies for the T[sub 1] and S[sub 0] states, computed at the MP2/6-31G(d,p) and MP4/6-31G(d,p) level of theory. The nonradiative life, calculated as the 1/e of the survival probability, is approximately 20 ps for barrier heights of 770[endash]845 cm[sup [minus]1] and out-of-plane angles of 32.07[degree][endash]32.69[degree]. (The thiophosgene adopts a pyramidal conformation with the C[double bond]S bond bent from the ClCCl plane by about 32[degree].) The computed lifetime is comparable to the lower-limit lifetime of [approximately]50 ps obtained from the quantum yields [Phi][sub P][le]10[sup [minus]3][Phi][sub F] with [Phi][sub F][approx]1.0 and the measured S[sub 1] fluorescence lifetime of 4 [mu]s. The short T[sub 1] nonradiative lifetime of thiophosgene can be attributed to the large matrix elements of the T[sub 1][endash]S[sub 0] spin-orbit coupling (V=150 hthinsp;cm[sup [minus]1]) and the strong out-of-plane deformation of the T[sub 1] state relative to the planar S[sub 0] state, that provides the large Franck[endash]Condon factors for the T[sub 1][r arrow]S[sub 0] ISC. It is proposed that a similar

  15. Transport of triplet excitons along continuous 100 nm polyfluorene chains

    SciTech Connect

    Xi, Liang; Bird, Matthew; Mauro, Gina; Asaoka, Sadayuki; Cook, Andrew R.; Chen, Hung -Cheng; Miller, John R.

    2014-12-03

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

  16. Transport of triplet excitons along continuous 100 nm polyfluorene chains

    DOE PAGES

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

    2014-12-03

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

  17. Calculating vibrational spectra without determining excited eigenstates: Solving the complex linear equations of damped response theory for vibrational configuration interaction and vibrational coupled cluster states.

    PubMed

    Godtliebsen, Ian H; Christiansen, Ove

    2015-10-07

    It is demonstrated how vibrational IR and Raman spectra can be calculated from damped response functions using anharmonic vibrational wave function calculations, without determining the potentially very many eigenstates of the system. We present an implementation for vibrational configuration interaction and vibrational coupled cluster, and describe how the complex equations can be solved using iterative techniques employing only real trial vectors and real matrix-vector transformations. Using this algorithm, arbitrary frequency intervals can be scanned independent of the number of excited states. Sample calculations are presented for the IR-spectrum of water, Raman spectra of pyridine and a pyridine-silver complex, as well as for the infra-red spectrum of oxazole, and vibrational corrections to the polarizability of formaldehyde.

  18. Calculating vibrational spectra without determining excited eigenstates: Solving the complex linear equations of damped response theory for vibrational configuration interaction and vibrational coupled cluster states

    NASA Astrophysics Data System (ADS)

    Godtliebsen, Ian H.; Christiansen, Ove

    2015-10-01

    It is demonstrated how vibrational IR and Raman spectra can be calculated from damped response functions using anharmonic vibrational wave function calculations, without determining the potentially very many eigenstates of the system. We present an implementation for vibrational configuration interaction and vibrational coupled cluster, and describe how the complex equations can be solved using iterative techniques employing only real trial vectors and real matrix-vector transformations. Using this algorithm, arbitrary frequency intervals can be scanned independent of the number of excited states. Sample calculations are presented for the IR-spectrum of water, Raman spectra of pyridine and a pyridine-silver complex, as well as for the infra-red spectrum of oxazole, and vibrational corrections to the polarizability of formaldehyde.

  19. Aberrant EEG functional connectivity and EEG power spectra in resting state post-traumatic stress disorder: a sLORETA study.

    PubMed

    Imperatori, Claudio; Farina, Benedetto; Quintiliani, Maria Isabella; Onofri, Antonio; Castelli Gattinara, Paola; Lepore, Marta; Gnoni, Valentina; Mazzucchi, Edoardo; Contardi, Anna; Della Marca, Giacomo

    2014-10-01

    The aim of the present study was to explore the modifications of EEG power spectra and EEG connectivity of resting state (RS) condition in patients with post-traumatic stress disorder (PTSD). Seventeen patients and seventeen healthy subjects matched for age and gender were enrolled. EEG was recorded during 5min of RS. EEG analysis was conducted by means of the standardized Low Resolution Electric Tomography software (sLORETA). In power spectra analysis PTSD patients showed a widespread increase of theta activity (4.5-7.5Hz) in parietal lobes (Brodmann Area, BA 7, 4, 5, 40) and in frontal lobes (BA 6). In the connectivity analysis PTSD patients also showed increase of alpha connectivity (8-12.5Hz) between the cortical areas explored by Pz-P4 electrode. Our results could reflect the alteration of memory systems and emotional processing consistently altered in PTSD patients.

  20. Helical Self-Assembly-Induced Singlet-Triplet Emissive Switching in a Mechanically Sensitive System.

    PubMed

    Wu, Hongwei; Zhou, Yunyun; Yin, Liyuan; Hang, Cheng; Li, Xin; Ågren, Hans; Yi, Tao; Zhang, Qing; Zhu, Liangliang

    2017-01-18

    In nanoscience, chirality has shown a significant ability to tune materials' electronic properties, whereas imposing macrochirality into the regulation of singlet-triplet features of organic optoelectronics remains a challenging research topic. Since the tuning for singlet and triplet excited-state properties in a single π-functional molecule connects to its multicolor luminescent application and potential improvement of internal quantum efficiency, we here report that supramolecular chirality can be employed to toggle the singlet and triplet emissions in a well-designed asterisk-shaped molecule. Employing a hexathiobenzene-based single luminophore as a prototype and functionalizing it with chiral α-lipoiate side groups, we find that helical nanoarchitectures can accordingly form in mixed DMF/H2O solution. On this basis, switching between fluorescence and phosphorescence of the material can be realized upon helical self-assembly and dissociation. Such a behavior can be attributed to a helical-conformation-dependent manipulation of the intersystem crossing. Furthermore, reversible mechanoluminescence of the corresponding solid sample was also observed to rely on an analogous molecular self-assembly alternation. These results can probably provide new visions for the development of next-generation supramolecular chiral functional materials.

  1. Identification of redundant and synergetic circuits in triplets of electrophysiological data

    NASA Astrophysics Data System (ADS)

    Erramuzpe, Asier; Ortega, Guillermo J.; Pastor, Jesus; de Sola, Rafael G.; Marinazzo, Daniele; Stramaglia, Sebastiano; Cortes, Jesus M.

    2015-12-01

    Objective. Neural systems are comprised of interacting units, and relevant information regarding their function or malfunction can be inferred by analyzing the statistical dependencies between the activity of each unit. While correlations and mutual information are commonly used to characterize these dependencies, our objective here is to extend interactions to triplets of variables to better detect and characterize dynamic information transfer. Approach. Our approach relies on the measure of interaction information (II). The sign of II provides information as to the extent to which the interaction of variables in triplets is redundant (R) or synergetic (S). Three variables are said to be redundant when a third variable, say Z, added to a pair of variables (X, Y), diminishes the information shared between X and Y. Similarly, the interaction in the triplet is said to be synergetic when conditioning on Z enhances the information shared between X and Y with respect to the unconditioned state. Here, based on this approach, we calculated the R and S status for triplets of electrophysiological data recorded from drug-resistant patients with mesial temporal lobe epilepsy in order to study the spatial organization and dynamics of R and S close to the epileptogenic zone (the area responsible for seizure propagation). Main results. In terms of spatial organization, our results show that R matched the epileptogenic zone while S was distributed more in the surrounding area. In relation to dynamics, R made the largest contribution to high frequency bands (14-100 Hz), while S was expressed more strongly at lower frequencies (1-7 Hz). Thus, applying II to such clinical data reveals new aspects of epileptogenic structure in terms of the nature (redundancy versus synergy) and dynamics (fast versus slow rhythms) of the interactions. Significance. We expect this methodology, robust and simple, can reveal new aspects beyond pair-interactions in networks of interacting units in other

  2. Solvent effect on the absorption and fluorescence spectra of 7-acetoxy-6-(2,3-dibromopropyl)-4,8-dimethylcoumarin: determination of ground and excited state dipole moments.

    PubMed

    Gülseven Sıdır, Yadigar; Sıdır, Isa

    2013-02-01

    The ground state (μ(g)) and excited state (μ(e)) dipole moments of 7-acetoxy-6-(2,3-dibromopropyl)-4,8-dimethylcoumarin (abbreviated as 7ADDC) are estimated from solvatochromic shifts of absorption and fluorescence spectra as a function of the dielectric constant (ε) and refractive index (n). While the ground state dipole moment is determined by using Bilot-Kawski method, the excited state dipole moment is calculated by using Bilot-Kawski, Lippert-Mataga, Bakhshiev, Kawski-Chamma-Viallet and Reichardt correlation methods. Excited state dipole moment is observed as larger than the ground state dipole moment due to substantial π-electron density redistribution. The ground state and excited state dipole moments are observed as parallel to each other with angle of 0°. Solute-solvent interactions are analyzed by means of linear solvation free energy relationships (LSER) using dielectric constant function (f(ε)), refractive index function (f(n)) and Kamlet-Taft parameters (α and β). Atomic charges, electron densities and molecular orbitals are calculated in vacuum and with solvent effect by using both DFT and TDDFT methods. Solvent accessible surface, molecular electrostatic potential (MEP) and electrostatic potential (ESP) are visualized as a result of DFT calculations.

  3. Solvent effect on the absorption and fluorescence spectra of 7-acetoxy-6-(2,3-dibromopropyl)-4,8-dimethylcoumarin: Determination of ground and excited state dipole moments

    NASA Astrophysics Data System (ADS)

    Gülseven Sıdır, Yadigar; Sıdır, İsa

    2013-02-01

    The ground state (μg) and excited state (μe) dipole moments of 7-acetoxy-6-(2,3-dibromopropyl)-4,8-dimethylcoumarin (abbreviated as 7ADDC) are estimated from solvatochromic shifts of absorption and fluorescence spectra as a function of the dielectric constant (ɛ) and refractive index (n). While the ground state dipole moment is determined by using Bilot-Kawski method, the excited state dipole moment is calculated by using Bilot-Kawski, Lippert-Mataga, Bakhshiev, Kawski-Chamma-Viallet and Reichardt correlation methods. Excited state dipole moment is observed as larger than the ground state dipole moment due to substantial π-electron density redistribution. The ground state and excited state dipole moments are observed as parallel to each other with angle of 0°. Solute-solvent interactions are analyzed by means of linear solvation free energy relationships (LSER) using dielectric constant function (f(ɛ)), refractive index function (f(n)) and Kamlet-Taft parameters (α and β). Atomic charges, electron densities and molecular orbitals are calculated in vacuum and with solvent effect by using both DFT and TDDFT methods. Solvent accessible surface, molecular electrostatic potential (MEP) and electrostatic potential (ESP) are visualized as a result of DFT calculations.

  4. Correcting human heart 31P NMR spectra for partial saturation. Evidence that saturation factors for PCr/ATP are homogeneous in normal and disease states

    NASA Astrophysics Data System (ADS)

    Bottomley, Paul A.; Hardy, Christopher J.; Weiss, Robert G.

    Heart PCr/ATP ratios measured from spatially localized 31P NMR spectra can be corrected for partial saturation effects using saturation factors derived from unlocalized chest surface-coil spectra acquired at the heart rate and approximate Ernst angle for phosphor creatine (PCr) and again under fully relaxed conditions during each 31P exam. To validate this approach in studies of normal and disease states where the possibility of heterogeneity in metabolite T1 values between both chest muscle and heart and normal and disease states exists, the properties of saturation factors for metabolite ratios were investigated theoretically under conditions applicable in typical cardiac spectroscopy exams and empirically using data from 82 cardiac 31P exams in six study groups comprising normal controls ( n = 19) and patients with dilated ( n = 20) and hypertrophic ( n = 5) cardiomyopathy, coronary artery disease ( n = 16), heart transplants ( n = 19), and valvular heart disease ( n = 3). When TR ≪ T1,(PCr), with T1(PCr) ⩾ T1(ATP), the saturation factor for PCr/ATP lies in the range 1.5 ± 0.5, regardless of the T1 values. The precise value depends on the ratio of metabolite T1 values rather than their absolute values and is insensitive to modest changes in TR. Published data suggest that the metabolite T1 ratio is the same in heart and muscle. Our empirical data reveal that the saturation factors do not vary significantly with disease state, nor with the relative fractions of muscle and heart contributing to the chest surface-coil spectra. Also, the corrected myocardial PCr/ATP ratios in each normal or disease state bear no correlation with the corresponding saturation factors nor the fraction of muscle in the unlocalized chest spectra. However, application of the saturation correction (mean value, 1.36 ± 0.03 SE) significantly reduced scatter in myocardial PCr/ATP data by 14 ± 11% (SD) ( p ⩽ 0.05). The findings suggest that the relative T1 values of PCr and ATP are

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

    PubMed

    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.

  6. Free-exciton states in crystalline GaTe

    NASA Astrophysics Data System (ADS)

    Wan, J. Z.; Brebner, J. L.; Leonelli, R.

    1995-12-01

    Polarized properties of both the singlet and triplet ground exciton states in the photoluminescence and transmission spectra of crystalline GaTe are explained based on the possible symmetry properties of the energy band edge of GaTe. Some experimental results about excited exciton states in GaTe are presented and discussed. The energy positions of exciton series in GaTe follow the three-dimensional direct allowed Wannier exciton formula just as in the the other III-VI layered compounds of GaSe and InSe. The nonthermalized, ``hot'' nature of excitons inside GaTe under higher optical excitation intensities is also discussed.

  7. Orphan spin operators enable the acquisition of multiple 2D and 3D magic angle spinning solid-state NMR spectra

    NASA Astrophysics Data System (ADS)

    Gopinath, T.; Veglia, Gianluigi

    2013-05-01

    We propose a general method that enables the acquisition of multiple 2D and 3D solid-state NMR spectra for U-13C, 15N-labeled proteins. This method, called MEIOSIS (Multiple ExperIments via Orphan SpIn operatorS), makes it possible to detect four coherence transfer pathways simultaneously, utilizing orphan (i.e., neglected) spin operators of nuclear spin polarization generated during 15N-13C cross polarization (CP). In the MEIOSIS experiments, two phase-encoded free-induction decays are decoded into independent nuclear polarization pathways using Hadamard transformations. As a proof of principle, we show the acquisition of multiple 2D and 3D spectra of U-13C, 15N-labeled microcrystalline ubiquitin. Hadamard decoding of CP coherences into multiple independent spin operators is a new concept in solid-state NMR and is extendable to many other multidimensional experiments. The MEIOSIS method will increase the throughput of solid-state NMR techniques for microcrystalline proteins, membrane proteins, and protein fibrils.

  8. [Neonatal morbidity and hospital mortality of preterm triplets.

    PubMed

    Lamshing-Salinas, Priscilla; Rend Ón-Macías, Mario Enrique; Iglesias-Leboreiro, José; Bernárdez-Zapata, Isabel; Braverman-Bronstein, Ariela

    2013-01-01

    Background: multiple gestations have caused an increase in vulnerable preterm births. Our objective was to analyze neonatal morbidity and mortality in preterm triplets. Methods: we analyzed a cohort of 30 triplets in an obstetrics and gynecology hospital. Data were obtained during pregnancy, childbirth and neonatal period: birth order, sex, weight, height, malformations, advanced resuscitation, assisted ventilation, intraventricular hemorrhage, necrotizing enterocolitis, sepsis, pulmonary hypertension, bronchopulmonary dysplasia, days of hospitalization, and death. Results: 90 infants were analyzed. There was an omphalopagus con-joined twins case; 42 (70 %) had between 30-33 weeks and six between 24-29; 19 (21 %) had low weight for gestational age, and 18 (30 %) had a major malformation; 27 % required ventilatory support, 33 % sepsis, 32 % necrotizing enterocolitis, 21 % pulmonary hypertension, 14 % bronchopulmonary dysplasia and 2 % intraventricular hemorrhage, without statistically significant differences related to the order, presentation at birth, sex and number of placentas and amniotic sacs. Eight 24-week triplets died, four over 28 weeks, and a siamese (p = 38). There was no difference in hospital days between triplets. Conclusions: the triplets mortality is low and mainly associated with extreme prematurity, intrauterine growth restriction and sepsis.

  9. The covariance of the differences between experimental and theoretical chemical shifts as an aid for assigning two-dimensional heteronuclear correlation solid-state NMR spectra

    NASA Astrophysics Data System (ADS)

    Czernek, Jiří; Brus, Jiří

    2014-07-01

    A robust method for the assignment of two-dimensional heteronuclear correlations in the solid-state NMR spectra is described. It statistically evaluates the differences between measured and theoretical (obtained from first-principles calculations of the NMR chemical shielding property of periodic materials) chemical shifts. The values of the covariance of these differences, and of the standard deviations of the respective linear correlations, are elucidative for the spectral assignment process. The efficacy of the method is demonstrated for three crystalline systems: L-tyrosine hydrochloride, L-tyrosine ansolvate, and the polymorphic form I of o-acetylsalicylic acid.

  10. Estimation of ground- and excited-state dipole moments of Nile Red dye from solvatochromic effect on absorption and fluorescence spectra

    NASA Astrophysics Data System (ADS)

    Kawski, A.; Bojarski, P.; Kukliński, B.

    2008-10-01

    The effect of various nonpolar and polar solvents on the location of absorption and fluorescence of Nile Red at room temperature was investigated. Based on the batochromic shift of electronic spectra of Nile Red and Bilot-Kawski theory the following values of ground- and excited-state dipole moments μg = 8.2 ± 1.0 D and μe = 10.0 ± 1.0 D were found. The reasons of high discrepancy between the literature results were discussed.

  11. Excited state solvatochromic and prototropic behaviour of 4-aminodiphenylamine and 4,4'-diaminodiphenylamine—A comparative study by electronic spectra

    NASA Astrophysics Data System (ADS)

    Nayaki, S. Kothai; Swaminathan, M.

    2006-06-01

    Solvatochromic and prototropic behaviour of 4-aminodiphenylamine (4ADA) and 4,4'-diaminodiphenylamine (DADA) have been investigated in the solvents of different polarity and at various acid-base concentrations in the ground and excited states using absorption and fluorescence spectra. Solvatochromic shifts have been analysed and observed shifts are explained by the hydrogen bonding interactions. The prototropic study reveals that (i) absorption maximum of monocation of DADA is red shifted to its neutral form, and (ii) the fluorescence of 4ADA is red shifted on protonation. The abnormal fluorescence of 4ADA + is found to be due to large solvent relaxation in polar medium.

  12. Electronic Raman scattering with excitation between localized states observed in the zinc M{sub 2,3} soft x-ray spectra of ZnS

    SciTech Connect

    Zhou, L.; Callcott, T.A.; Jia, J.J.

    1997-04-01

    Zn M{sub 2,3} soft x-ray fluorescence (SXF) spectra of ZnS and ZnS{sub .5}Se{sub .5} excited near threshold show strong inelastic scattering effects that can be explained using a simple model and an inelastic scattering theory based on second order perturbation theory. This scattering is often called electronic resonance Raman scattering. Tulkki and Aberg have developed this theory in detail for atomic systems, but their treatment can be applied to solid systems by utilizing electronic states characteristic of solids rather than of atomic systems.

  13. Inequality spectra

    NASA Astrophysics Data System (ADS)

    Eliazar, Iddo

    2017-03-01

    Inequality indices are widely applied in economics and in the social sciences as quantitative measures of the socioeconomic inequality of human societies. The application of inequality indices extends to size-distributions at large, where these indices can be used as general gauges of statistical heterogeneity. Moreover, as inequality indices are plentiful, arrays of such indices facilitate high-detail quantification of statistical heterogeneity. In this paper we elevate from arrays of inequality indices to inequality spectra: continuums of inequality indices that are parameterized by a single control parameter. We present a general methodology of constructing Lorenz-based inequality spectra, apply the general methodology to establish four sets of inequality spectra, investigate the properties of these sets, and show how these sets generalize known inequality gauges such as: the Gini index, the extended Gini index, the Rényi index, and hill curves.

  14. Mass spectra and decays of ground and orbitally excited cb¯ states in nonrelativistic quark model

    NASA Astrophysics Data System (ADS)

    Monteiro, Antony Prakash; Bhat, Manjunath; Vijaya Kumar, K. B.

    2017-02-01

    The complete spectrum of cb¯ states is obtained in a phenomenological nonrelativistic quark model (NRQM), which consists of a confinement potential and one gluon exchange potential (OGEP) as effective quark-antiquark potential. We make predictions for the radiative decay (E1 and M1) widths and weak decay widths of cb¯ states in the framework of NRQM formalism.

  15. Evidence for water-mediated triplet-triplet energy transfer in the photoprotective site of the peridinin-chlorophyll a-protein.

    PubMed

    Di Valentin, Marilena; Tait, Claudia E; Salvadori, Enrico; Orian, Laura; Polimeno, Antonino; Carbonera, Donatella

    2014-01-01

    Experimental and theoretical studies indicate that water molecules between redox partners can significantly affect their electron-transfer and possibly also the triplet-triplet energy transfer (TTET) properties when in the vicinity of chromophores. In the present work, the interaction of an intervening water molecule with the peridinin triplet state in the peridinin-chlorophyll a-protein (PCP) from Amphidinium carterae is studied by using orientation selective (2)H electron spin echo envelope modulation (ESEEM) spectroscopy, in conjunction with quantum mechanical calculations. This water molecule is located at the interface between the chlorophyll and peridinin pigments involved in the photoprotection mechanism (Chl601(602)-Per614(624), for nomenclature see reference [1]), based on TTET. The characteristic deuterium modulation pattern is observed in the electron spin-echo envelopes for the PCP complex exchanged against (2)H2O. Simulations of the time- and frequency-domain two-pulse and three-pulse ESEEM require two types of coupled (2)H. The more strongly coupled (2)H has an isotropic coupling constant (aiso) of -0.4MHz. This Fermi contact contribution for one of the two water protons and the precise geometry of the water molecule at the interface between the chlorophyll and peridinin pigments, resulting from the analysis, provide experimental evidence for direct involvement of this structured water molecule in the mechanism of TTET. The PCP antenna, characterised by a unity efficiency of the process, represents a model for future investigations on protein- and solvent-mediated TTET in the field of natural/artificial photosynthesis.

  16. Red Light Activation of Ru(II) Polypyridyl Prodrugs via Triplet-Triplet Annihilation Upconversion: Feasibility in Air and through Meat.

    PubMed

    Askes, Sven H C; Meijer, Michael S; Bouwens, Tessel; Landman, Iris; Bonnet, Sylvestre

    2016-11-01

    Triplet-triplet annihilation upconversion (TTA-UC) is a promising photophysical tool to shift the activation wavelength of photopharmacological compounds to the red or near-infrared wavelength domain, in which light penetrates human tissue optimally. However, TTA-UC is sensitive to dioxygen, which quenches the triplet states needed for upconversion. Here, we demonstrate not only that the sensitivity of TTA-UC liposomes to dioxygen can be circumvented by adding antioxidants, but also that this strategy is compatible with the activation of ruthenium-based chemotherapeutic compounds. First, red-to-blue upconverting liposomes were functionalized with a blue-light sensitive, membrane-anchored ruthenium polypyridyl complex, and put in solution in presence of a cocktail of antioxidants composed of ascorbic acid and glutathione. Upon red light irradiation with a medical grade 630 nm PDT laser, enough blue light was produced by TTA-UC liposomes under air to efficiently trigger full activation of the Ru-based prodrug. Then, the blue light generated by TTA-UC liposomes under red light irradiation (630 nm, 0.57 W/cm²) through different thicknesses of pork or chicken meat was measured, showing that TTA-UC still occurred even beyond 10 mm of biological tissue. Overall, the rate of activation of the ruthenium compound in TTA-UC liposomes using either blue or red light (1.6 W/cm²) through 7 mm of pork fillet were found comparable, but the blue light caused significant tissue damage, whereas red light did not. Finally, full activation of the ruthenium prodrug in TTA-UC liposomes was obtained under red light irradiation through 7 mm of pork fillet, thereby underlining the in vivo applicability of the activation-by-upconversion strategy.

  17. Charge-exchange x-ray spectra: Evidence for significant contributions from radiative decays of doubly excited states

    NASA Astrophysics Data System (ADS)

    Ali, R.; Beiersdorfer, P.; Harris, C. L.; Neill, P. A.

    2016-01-01

    Charge-exchange collisions of slow Ne+10 ions with He, Ne, and Ar targets were studied with simultaneous x-ray and cold-target recoil-ion-momentum spectroscopy proving the contribution of several mechanisms to the radiative stabilization of apparent (4,4) doubly excited states for He and Ne targets and of (5,6) states for Ar. In particular, the stabilization efficiency of the mechanism of dynamic auto-transfer to Rydberg states is confirmed. Moreover, we present evidence for direct radiative decays of (4,4) states populated in collisions with He, which is an experimental indication of the population of so-called unnatural-parity states in such collisions. These mechanisms lead to the emission of x-rays that have considerably higher energies than those predicted by current spectral models and may explain recent observations of anomalously large x-ray emission from Rydberg levels.

  18. The Character of the Long-Lived State Formed from S_1 of Phenylacetylene

    NASA Astrophysics Data System (ADS)

    Johnson, Philip M.; Sears, Trevor J.

    2013-06-01

    Compared to other small aromatic molecules, phenylacetylene (PA) and benzonitrile exhibit strikingly anomalous photophysics on excitation to the S_1 state. Firstly, products are formed on S_1 excitation of a beam-cooled sample that seem to live indefinitely (as defined by the flight time through the apparatus), while action spectra of their formation mirror the rotationally-resolved absorption spectrum of the monomer. Secondly, the long lived products appear immediately during the nsec. laser pulse rather than build up during the lifetime of the singlet level, as is seen in benzene, for example. The question has therefore arisen: is the long lived product of the S_1 excitation the triplet state, as is assumed in all previous work on other molecules, or is it an isomer of some sort? New pump-probe ionization mass spectroscopy experiments have been performed to study the distribution of fragments and metastable ions produced by PA cation derived from the neutral S_1 state, and from the long-lived species. These combined with other experimental results showing weak long-lived components in both the S_1 fluorescence and pump-probe photoelectron spectra that we interpret as recurrence behavior, definitively show the long-lived state is a triplet state of PA, not an isomer. PA with a singlet-triplet gap of 10000 cm^{-1} is acting like intermediate case molecules with much smaller singlet-triplet gaps such as pyrazine and pyrimidine. Calculations point to the existence of four triplet states of PA at or below the energy of S_1 providing a very large density of vibronic states in which to distribute the energy from singlet-triplet crossing. PA T_1 is calculated to be non-planar, in contrast to what is found in benzene, possibly helping to explain the different photophysics. Acknowledgments: We gratefully acknowledge G. V. Lopez for his contributions to some of the experimental masurements. Work at Brookhaven National Laboratory was carried out under Contract No. DE-AC02

  19. DNA CTG triplet repeats involved in dynamic mutations of neurologically related gene sequences form stable duplexes

    NASA Technical Reports Server (NTRS)

    Smith, G. K.; Jie, J.; Fox, G. E.; Gao, X.

    1995-01-01

    DNA triplet repeats, 5'-d(CTG)n and 5'-d(CAG)n, are present in genes which have been implicated in several neurodegenerative disorders. To investigate possible stable structures formed by these repeating sequences, we have examined d(CTG)n, d(CAG)n and d(CTG).d(CAG)n (n = 2 and 3) using NMR and UV optical spectroscopy. These studies reveal that single stranded (CTG)n (n > 2) forms stable, antiparallel helical duplexes, while the single stranded (CAG)n requires at least three repeating units to form a duplex. NMR and UV melting experiments show that the Tm increases in the order of [(CAG)3]2 < [(CTG)3]2 << (CAG)3.(CTG)3. The (CTG)3 duplex is stable and exhibits similar NMR spectra in solutions containing 0.1-4 M NaCl and at a pH range from 4.6 to 8.8. The (CTG)3 duplex, which contains multiple-T.T mismatches, displays many NMR spectral characteristics similar to those of B-form DNA. However, unique NOE and 1H-31P coupling patterns associated with the repetitive T.T mismatches in the CTG repeats are discerned. These results, in conjunction with recent in vitro studies suggest that longer CTG repeats may form hairpin structures, which can potentially cause interruption in replication, leading to dynamic expansion or deletion of triplet repeats.

  20. DNA CTG triplet repeats involved in dynamic mutations of neurologically related gene sequences form stable duplexes.

    PubMed Central

    Smith, G K; Jie, J; Fox, G E; Gao, X

    1995-01-01

    DNA triplet repeats, 5'-d(CTG)n and 5'-d(CAG)n, are present in genes which have been implicated in several neurodegenerative disorders. To investigate possible stable structures formed by these repeating sequences, we have examined d(CTG)n, d(CAG)n and d(CTG).d(CAG)n (n = 2 and 3) using NMR and UV optical spectroscopy. These studies reveal that single stranded (CTG)n (n > 2) forms stable, antiparallel helical duplexes, while the single stranded (CAG)n requires at least three repeating units to form a duplex. NMR and UV melting experiments show that the Tm increases in the order of [(CAG)3]2 < [(CTG)3]2 << (CAG)3.(CTG)3. The (CTG)3 duplex is stable and exhibits similar NMR spectra in solutions containing 0.1-4 M NaCl and at a pH range from 4.6 to 8.8. The (CTG)3 duplex, which contains multiple-T.T mismatches, displays many NMR spectral characteristics similar to those of B-form DNA. However, unique NOE and 1H-31P coupling patterns associated with the repetitive T.T mismatches in the CTG repeats are discerned. These results, in conjunction with recent in vitro studies suggest that longer CTG repeats may form hairpin structures, which can potentially cause interruption in replication, leading to dynamic expansion or deletion of triplet repeats. PMID:7501450