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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. 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.

  4. Triplet state photoassociation of LiNa

    NASA Astrophysics Data System (ADS)

    Rvachov, Timur; Jamison, Alan; Jing, Li; Jiang, Yijun; Zwierlein, Martin; Ketterle, Wolfgang

    2015-05-01

    Ultracold molecules have promise to become a useful tool for studies in quantum simulation and ultracold chemistry. We aim to produce ultracold fermionic 6Li23Na molecules in the triplet ground state. Due to the small mass, small spin-orbit coupling, and fermionic character of LiNa, the triplet ground state is expected to be long lived. We report on photoassociation spectra of LiNa to its triplet excited states from an ultracold mixture. This is the first observation of these excited triplet potentials, which have been previously difficult to observe in heat-pipe experiments due to the small spin-orbit coupling in the system. Determining the excited state potentials is a key milestone towards forming triplet ground state LiNa via two-photon STIRAP. Work supported by the NSF, AFOSR-MURI, ARO-MURI, and NSERC.

  5. Transient resonance Raman spectra of benzophenone and its four isotopic analogues in the lowest excited triplet state

    SciTech Connect

    Tahara, T.; Hamaguchi, H.; Tasumi, M.

    1987-11-05

    Transient resonance Raman spectra of T/sub 1/ benzophenone (T/sub 1/BP) and its four isotopic analogues in carbon tetrachloride solutions were measured. Vibrational assignments of eight T/sub 1/ bands have been made on the basis of the observed isotopic frequency shifts. The assignments clarified the following three points concerning the structure of T/sub 1/ BP in solution. (1) The CO bond order in T/sub 1/ BP is much lower than that in the ground-state benzophenone (S/sub 0/ BP). The CO stretching frequency in T/sub 1/ is found to be 1222 cm/sup -1/, whereas the corresponding value in S/sub 0/ is 1665 cm/sup -1/. The former frequency indicates a single-bond-like character of the CO bonding in the T/sub 1/ state. (2) Vibrational frequencies of several ring modes show marked downshifts in going from S/sub 0/ to T/sub 1/. This suggests the delocalization of the ..pi..* electron into the ring part. (3) The assignment (1302 cm/sup -1/) of the symmetric C-phenyl stretch mode in the T/sub 1/ withdraws S/sub 0/ absorption spectrum is questioned. According to the present assignment, the frequency of this mode (approx. 1100 cm/sup -1/) is slightly lower than that in the ground state (1150 cm/sup -1/). The simple quantum chemical picture of T/sub 1/ BP, which predicted the increase of the C-phenyl bond order with the ..pi..* withdraws n excitation, should therefore be reconsidered.

  6. Time-resolved EPR spectra of the excited triplet states generated from the photoinduced intramolecular proton transfer and from the direct excitation reactions in 2-(N-phenylacetimidoyl)-1-naphthol

    NASA Astrophysics Data System (ADS)

    Tero-Kubota, Shozo; Noguchi, Tetsuji; Katsuki, Akio; Akimaya, Kimio; Ikegami, Yusaku

    1991-12-01

    The excited triplet (T 1) state of the keto tautomer generated from excited state intramolecular proton transfer was observed for 2-(N-phenylacetimidoyl)-1-naphthol using the time-resolved EPR technique in a glassy matrix at 77 K. The direct excitation with the dye laser of the keto tautomer in an EPR matrix was also examined. The principal parameters and the direction of the principal axes for the zero-field splitting tensor were determined from analyses of the magnetophotoselection spectra and semi-empirical SCF-MO calculations.

  7. Resonance Raman Spectroscopy of the T1 Triplet Excited State of Oligothiophenes.

    PubMed

    Wang, Chen; Angelella, Maria; Doyle, Samantha J; Lytwak, Lauren A; Rossky, Peter J; Holliday, Bradley J; Tauber, Michael J

    2015-09-17

    The characterization of triplet excited states is essential for research on organic photovoltaics and singlet fission. We report resonance Raman spectra of two triplet oligothiophenes with n-alkyl substituents, a tetramer and hexamer. The spectra of the triplets are more complex than the ground state, and we find that density functional theory calculations are a useful starting point for characterizing the bands. The spectra of triplet tetrathiophene and hexathiophene differ significantly from one another. This observation is consistent with a T1 excitation that is delocalized over at least five rings in long oligomers. Bands in the 500-800 cm(-1) region are greatly diminished for an aggregated sample of hexathiophene, likely caused by fast electronic dephasing. These experiments highlight the potential of resonance Raman spectroscopy to unequivocally detect and characterize triplets in thiophene materials. The vibrational spectra can also serve as rigorous standards for evaluating computational methods for excited-state molecules. PMID:26291623

  8. Bacteriopheophytin triplet state in Rhodobacter sphaeroides reaction centers.

    PubMed

    Białek, Rafał; Burdziński, Gotard; Jones, Michael R; Gibasiewicz, Krzysztof

    2016-08-01

    It is well established that photoexcitation of Rhodobacter sphaeroides reaction centers (RC) with reduced quinone acceptors results in the formation of a triplet state localized on the primary electron donor P with a significant yield. The energy of this long-lived and therefore potentially damaging excited state is then efficiently quenched by energy transfer to the RC spheroidenone carotenoid, with its subsequent decay to the ground state by intersystem crossing. In this contribution, we present a detailed transient absorption study of triplet states in a set of mutated RCs characterized by different efficiencies of triplet formation that correlate with lifetimes of the initial charge-separated state P(+)H A (-) . On a microsecond time scale, two types of triplet state were detected: in addition to the well-known spheroidenone triplet state with a lifetime of ~4 μs, in some RCs we discovered a bacteriopheophytin triplet state with a lifetime of ~40 μs. As expected, the yield of the carotenoid triplet increased approximately linearly with the lifetime of P(+)H A (-) , reaching the value of 42 % for one of the mutants. However, surprisingly, the yield of the bacteriopheophytin triplet was the highest in RCs with the shortest P(+)H A (-) lifetime and the smallest yield of carotenoid triplet. For these the estimated yield of bacteriopheophytin triplet was comparable with the yield of the carotenoid triplet, reaching a value of ~7 %. Possible mechanisms of formation of the bacteriopheophytin triplet state are discussed. PMID:27368166

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

    PubMed

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

    2015-12-21

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

  10. 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.

  11. Toward Triplet Ground State LiNa Molecules

    NASA Astrophysics Data System (ADS)

    Jamison, Alan; Rvachov, Timur; Jing, Li; Jiang, Yijun; Zwierlein, Martin; Ketterle, Wolfgang

    2015-05-01

    We present progress toward creation of ultracold ground-state triplet LiNa molecules. This 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. Our progress includes the first observation of triplet excited states in this molecule, achieved through photoassociation of ultracold mixtures of 6-Li and Na. We compare experimental results to a variety of near-dissociation expansions as well as ab initio potentials.

  12. Effects of ionic liquid [bmim][PF6] on absorption spectra and reaction kinetics of the duroquinone triplet state in acetonitrile.

    PubMed

    Zhu, Guanglai; Wu, Guozhong; Sha, Maolin; Long, Dewu; Yao, Side

    2008-04-10

    The transient absorption spectra and photoinduced electron-transfer process of duroquinone (DQ) in mixed binary solutions of ionic liquid (IL) [bmim][PF6] and acetonitrile (MeCN) have been investigated by laser photolysis at an excitation wavelength of 355 nm. A spectral blue shift of 3DQ* was observed in the IL/MeCN mixtures compared to MeCN. At lower VIL(volume fraction of IL), the interaction between DQ and the solvent is dominant, and the decay rate constant (kobs) of 3DQ* increases steadily with the increasing of VIL; to the contrary, at higher VIL, the network structures due to the hydrogen bond and viscosity are dominant, and the decay rate constant decreases obviously with increasing VIL. A critical point (turnover) was observed at VIL = approximately 0.30. The dependence of the observed growth rate (kgr) of the photoinduced electron-transfer (PET) products on VIL is complex and shows a special change; kgr first decreases with increasing VIL, then increases, and finally decreases slowly with further increasing of VIL. It is speculated that the PET process in the mixture can be affected by factors including the local structure and the reorganization energy of the solvent and salt and cage effects. The change of local structure of [bmim][PF6]/MeCN is supported by following the steady-state fluorescence behavior of the mixture, in combination with the molecular dynamics simulation of the thermodynamic property. The results revealed that the degree of self-aggregation of monomeric cations (bmim+) to associated forms increases with increasing VIL. This is in good agreement with the laser photolysis results for the same solutions. PMID:18331005

  13. 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

  14. Quenching of excited triplet states by dissolved natural organic matter.

    PubMed

    Wenk, Jannis; Eustis, Soren N; McNeill, Kristopher; Canonica, Silvio

    2013-11-19

    Excited triplet states of aromatic ketones and quinones are used as proxies to assess the reactivity of excited triplet states of the dissolved organic matter ((3)DOM*) in natural waters. (3)DOM* are crucial transients in environmental photochemistry responsible for contaminant transformation, production of reactive oxygen species, and potentially photobleaching of DOM. In recent photochemical studies aimed at clarifying the role of DOM as an inhibitor of triplet-induced oxidations of organic contaminants, aromatic ketones have been used in the presence of DOM, and the question of a possible interaction between their excited triplet states and DOM has emerged. To clarify this issue, time-resolved laser spectroscopy was applied to measure the excited triplet state quenching of four different model triplet photosensitizers induced by a suite of DOM from various aquatic and terrestrial sources. While no quenching for the anionic triplet sensitizers 4-carboxybenzophenone (CBBP) and 9,10-anthraquinone-2,6-disulfonic acid (2,6-AQDS) was detected, second-order quenching rate constants with DOM for the triplets of 2-acetonaphthone (2AN) and 3-methoxyacetophenone (3MAP) in the range of 1.30-3.85 × 10(7) L mol(C)(-1) s(-1) were determined. On the basis of the average molecular weight of DOM molecules, the quenching for these uncharged excited triplet molecules is nearly diffusion-controlled, but significant quenching (>10%) in aerated water is not expected to occur below DOM concentrations of 22-72 mg(C) L(-1). PMID:24083647

  15. 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.

  16. Photocyclization Reactions of Diarylethenes via the Excited Triplet State.

    PubMed

    Murata, Ryutaro; Yago, Tomoaki; Wakasa, Masanobu

    2015-11-12

    Cyclization reactions of three diarylethene derivatives, 1,2-bis(2-methyl-3-benzothienyl)perfluorocyclopentene (BT), 1,2-bis(2-hexyl-3-benzothienyl)perfluorocyclopentene (BTHex), and 1,2-bis(2-isopropyl-3-benzothienyl)perfluorocyclopentene (BTiPr), via their excited triplet states were studied by means of steady-state and nanosecond transient absorption spectroscopy. The excited triplet states of BT, BTHex, and BTiPr were generated by energy transfer from the photoexcited triplet states of sensitizers such as xanthone, phenanthrene, and pyrene. The single-step quantum yields of the cyclization reactions from the excited triplet states of BT, BTHex, and BTiPr were determined to be 0.34, 0.53, and 0.65, respectively. The triplet energies of these three BTs were estimated to be 190-200 kJ mol(-1). PMID:26490486

  17. Flash photolysis and triplet states and free radicals in solution.

    PubMed

    Windsor, Maurice W

    2003-05-01

    A personal account is given of the development of microsecond flash photolysis in George Porter's laboratory at Cambridge in the early 1950s. This made possible, for the first time, the observation of the absorption spectra of the lowest triplet states of many polycyclic aromatic hydrocarbons in fluid solutions. The T-T transitions were found to be very intense with oscillator strengths approaching unity in many cases. Detailed kinetic studies showed that triplet state decay was first order and viscosity dependent and strongly quenched by dissolved oxygen. Several aromatic free radicals such as benzyl were also observed in liquid solution for the first time. The advent of the laser in the early 1960s made it possible to extend flash photolysis studies to the ns and ps and eventually the fs time range. Such studies have revolutionized the study of excited states and free radicals and have made possible advances in the understanding of the dynamics of chemical and biological systems that would have been unimaginable 60 years ago. PMID:12803067

  18. Triplet excitons: Bringing dark states to light

    NASA Astrophysics Data System (ADS)

    Bardeen, Christopher J.

    2014-11-01

    Semiconducting quantum dots have been used to harvest triplet excitons produced through singlet fission in organic semiconductors. These hybrid organic-inorganic materials may boost the efficiency of solar cells.

  19. Positronium quenching via collisions with triplet states of photomagnetic molecules

    SciTech Connect

    Eom, C.I.; Naidu, S.V.; Sharma, S.C.; Kowalski, J.M. )

    1991-04-01

    We have studied positronium quenching resulting from collisions with the triplet states of benzaldehyde, oxygen, benzophenone, and bromonaphthalene. Positronium pick-off decay rates are presented as functions of triplet populations via uv irradiation of benzaldehyde-ethane, benzaldehyde-helium, and oxgyen-ethane gaseous mixtures and of benzophenone and bromonaphthalene adsorbed porous silicas. Our results show that the cross sections for positronium quenching in collisions with excited triplet states are not as high as reported previously. The oxygen data suggest reactions between hot'' (nonthermal) positronium and oxygen molecules.

  20. Ground state of naphthyl cation: Singlet or triplet?

    SciTech Connect

    Dutta, Achintya Kumar; Vaval, Nayana Pal, Sourav; Manohar, Prashant U.

    2014-03-21

    We present a benchmark theoretical investigation on the electronic structure and singlet-triplet(S-T) gap of 1- and 2-naphthyl cations using the CCSD(T) method. Our calculations reveal that the ground states of both the naphthyl cations are singlet, contrary to the results obtained by DFT/B3LYP calculations reported in previous theoretical studies. However, the triplet states obtained in the two structural isomers of naphthyl cation are completely different. The triplet state in 1-naphthyl cation is (π,σ) type, whereas in 2-naphthyl cation it is (σ,σ{sup ′}) type. The S-T gaps in naphthyl cations and the relative stability ordering of the singlet and the triplet states are highly sensitive to the basis-set quality as well as level of correlation, and demand for inclusion of perturbative triples in the coupled-cluster ansatz.

  1. 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.

  2. Calculations of N 2 triplet states vibrational populations and band emissions in venusian dayglow

    NASA Astrophysics Data System (ADS)

    Bhardwaj, Anil; Jain, Sonal Kumar

    2012-02-01

    A model for N 2 triplet states band emissions in the venusian dayglow has been developed for low and high solar activity conditions. Steady state photoelectron fluxes and volume excitation rates for N 2 triplet states have been calculated using the Analytical Yield Spectra (AYS) technique. Model calculated photoelectron flux is in good agreement with Pioneer Venus Orbiter-observed electron flux. Since inter-state cascading is important for the triplet states of N 2, populations of different levels of N 2 triplet states are calculated under statistical equilibrium considering direct electron impact excitation, and cascading and quenching effects. Densities of all vibrational levels of each triplet state are calculated in the model. Height-integrated overhead intensities of N 2 triplet band emissions are calculated, the values for Vegard-Kaplan (A3Σu+-X1Σg+), First Positive (B3Πg-A3Σu+), Second Positive ( C3Π u - B3Π g), and Wu-Benesch ( W3Δ u - B3Π g) bands of N 2, are 1.9 (3.2), 3 (6), 0.4 (0.8), and 0.5 (1.1) kR, respectively, for solar minimum (maximum) conditions. The intensities of the three strong Vegard-Kaplan bands (0, 5), (0, 6), and (0, 7) are 94 (160), 120 (204), and 114 (194) R, respectively, for solar minimum (maximum) conditions. Limb profiles are calculated for VK (0, 4), (0, 5), (0, 6) and (0, 7) bands. The calculated intensities on Venus are about a factor 10 higher than those on Mars. The present study provides a motivation for a search of N 2 triplet band emissions in the dayglow of Venus.

  3. Vibronic interaction and triplet state photophysics of phenylisatin and oxindole

    NASA Astrophysics Data System (ADS)

    Bangal, Prakriti Ranjan; Chakravorti, Sankar

    1999-12-01

    Photophysical study of phenylisatin and oxindole triplet states have been made at room temperature and in different glasses at 77K. Qualitatively, in all respects the compounds have identical spectroscopic characteristics. Phosphorescence emission, excitation along with their polarization and lifetime suggest that a perturbation of the zero-point level of emitting state ( 3ππ*) by a close-lying triplet state ( 3nπ*) leads to a number of new spectral features. The experimental observations have been interpreted satisfactorily in terms of a switch ( 3ππ* state to 3nπ*) in the character of the lowest triplet states (T 1 and T 2) and also a similar switch in the character of the excited singlet states S 1 and S 2 for a change of glass matrix from MCH to ethanol. Invoking of first order and second order spin-orbit coupling explains the phosphorescence emission unambiguously.

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

    PubMed

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

    2016-03-24

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

  5. 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.

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

    PubMed

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

    2016-03-21

    The solvent plays a decisive role in the photochemistry and photophysics of aromatic ketones. Xanthone (XT) is one such aromatic ketone and its triplet-triplet (T-T) absorption spectra show intriguing solvatochromic behavior. Also, the reactivity of XT towards H-atom abstraction shows an unprecedented decrease in protic solvents relative to aprotic solvents. Therefore, a comprehensive solvatochromic analysis of the triplet-triplet absorption spectra of XT was carried out in conjunction with time dependent density functional theory using the ad hoc explicit solvent model approach. A detailed solvatochromic analysis of the T-T absorption bands of XT suggests that the hydrogen bonding interactions are different in the corresponding triplet excited states. Furthermore, the contributions of non-specific and hydrogen bonding interactions towards differential solvation of the triplet states in protic solvents were found to be of equal magnitude. The frontier molecular orbital and electron density difference analysis of the T1 and T2 states of XT indicates that the charge redistribution in these states leads to intermolecular hydrogen bond strengthening and weakening, respectively, relative to the S0 state. This is further supported by the vertical excitation energy calculations of the XT-methanol supra-molecular complex. The intermolecular hydrogen bonding potential energy curves obtained for this complex in the S0, T1, and T2 states support the model. In summary, we propose that the different hydrogen bonding mechanisms exhibited by the two lowest triplet excited states of XT result in a decreasing role of the nπ(∗) triplet state, and are thus responsible for its reduced reactivity towards H-atom abstraction in protic solvents. PMID:27004870

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

    The solvent plays a decisive role in the photochemistry and photophysics of aromatic ketones. Xanthone (XT) is one such aromatic ketone and its triplet-triplet (T-T) absorption spectra show intriguing solvatochromic behavior. Also, the reactivity of XT towards H-atom abstraction shows an unprecedented decrease in protic solvents relative to aprotic solvents. Therefore, a comprehensive solvatochromic analysis of the triplet-triplet absorption spectra of XT was carried out in conjunction with time dependent density functional theory using the ad hoc explicit solvent model approach. A detailed solvatochromic analysis of the T-T absorption bands of XT suggests that the hydrogen bonding interactions are different in the corresponding triplet excited states. Furthermore, the contributions of non-specific and hydrogen bonding interactions towards differential solvation of the triplet states in protic solvents were found to be of equal magnitude. The frontier molecular orbital and electron density difference analysis of the T1 and T2 states of XT indicates that the charge redistribution in these states leads to intermolecular hydrogen bond strengthening and weakening, respectively, relative to the S0 state. This is further supported by the vertical excitation energy calculations of the XT-methanol supra-molecular complex. The intermolecular hydrogen bonding potential energy curves obtained for this complex in the S0, T1, and T2 states support the model. In summary, we propose that the different hydrogen bonding mechanisms exhibited by the two lowest triplet excited states of XT result in a decreasing role of the nπ∗ triplet state, and are thus responsible for its reduced reactivity towards H-atom abstraction in protic solvents.

  8. Photoswitching of the triplet excited state of diiodobodipy-dithienylethene triads and application in photo-controllable triplet-triplet annihilation upconversion.

    PubMed

    Ma, Jie; Cui, Xiaoneng; Wang, Fen; Wu, Xueyan; Zhao, Jianzhang; Li, Xingwei

    2014-11-21

    Dithienylethene (DTE)-2,6-diiodoBodipy triads were prepared with the aim to photoswitch the triplet excited state of the 2,6-diiodoBodipy moiety. Bodipy was selected due to its low T1 state energy level to avoid sensitized photocyclization of DTE, which is very often encountered in DTE photoswitches, so that the photochemistry of DTE and the organic chromophore can be addressed independently. This is the first time that DTE was covalently connected with an organic triplet photosensitizer. For the triad with DTE-o structure, selective photoexcitation into the diiodoBodipy part did not initiate photocyclization of DTE-o. Upon photoirradiation at 254 nm, thus the DTE-o → DTE-c transformation, the intersystem crossing (ISC) of 2,6-diiodoBodipy moiety was competed by the photoactivated resonance energy transfer (RET), with Bodipy as the intramolecular energy donor and DTE-c as energy acceptor. The fluorescence of Bodipy was quenched and the triplet state lifetime of Bodipy was reduced from 105.1 to 40.9 μs. The photoreversion is O2-independent, but can be greatly accelerated upon selective photoexcitation into the diiodoBodipy absorption band (at 535 nm). We concluded that ISC is not outcompeted by RET. The photoswitching of the triplet state was transduced to the singlet oxygen photosensitizing, as well as triplet-triplet annihilation upconversion. PMID:25341016

  9. On-chip generation of photon-triplet states.

    PubMed

    Krapick, Stephan; Brecht, Benjamin; Herrmann, Harald; Quiring, Viktor; Silberhorn, Christine

    2016-02-01

    Efficient sources of many-partite non-classical states are key for the advancement of quantum technologies and for the fundamental testing of quantum mechanics. We demonstrate the generation of time-correlated photon triplets at telecom wavelengths via pulsed cascaded parametric down-conversion in a monolithically integrated source. By detecting the generated states with success probabilities of (6.25 ± 1.09) × 10(-11) per pump pulse at injected powers as low as 10 μW, we benchmark the efficiency of the complete system and deduce its high potential for scalability. Our source is unprecedentedly long-term stable, it overcomes interface losses intrinsically due to its monolithic architecture, and the photon-triplet states dominate uncorrelated noise significantly. These results mark crucial progress towards the proliferation of robust, scalable, synchronized and miniaturized quantum technology. PMID:26906852

  10. Determining Oxygen Abundances in Metal Poor Subdwarfs from Medium Resolution Spectra of the OI Triplet

    NASA Astrophysics Data System (ADS)

    James, C. R.; Pilachowski, C. A.; Beers, T.; Sneden, C.; Cavallo, R. M.

    2002-12-01

    In the determination of oxygen abundances in unevolved metal-poor stars, the OI triplet remains the most accessible feature, but is still quite weak in the most metal-poor (oldest) stars. Pilachowski & Armandroff (1996) have explored a technique to determine oxygen and iron abundances in faint evolved stars using low-dispersion spectroscopy of the oxygen triplet. At moderate resolution, the triplet lines are blended into a single feature that can be measured and analyzed as a spectroscopic blend. Because the lines are separated by only 3.4 Å, the blended feature is more easily detected than the individual features; thus reliable oxygen measurements can be made in much fainter stars. Also, the immediate vicinity of the oxygen triplet is free of atmospheric absorption line contamination, and the feature is unblended with other stellar lines from additional elements. In this work, we have attempted to apply the Pilachowski and Armandroff (1996) methods to a sample of unevolved stars. Approximately half of the sample has been previously studied, allowing for a thorough assessment of the feasibility of applying the Pilachowski-Armandroff method to this population of stars. We find that the employing spectrum synthesis analysis to these low-dispersion spectra does sometimes yield meaningful results, and those results are consistent with high-resolution studies. However, in many cases, the weakness of the triplet allows for only determinations of upper limits, most of which are unenlightening. We explore the advantages and disadvantages of this method. Support from NOAO and SHSU is gratefully acknowledged.

  11. Triplet State Delocalization in a Conjugated Porphyrin Dimer Probed by Transient Electron Paramagnetic Resonance Techniques

    PubMed Central

    2015-01-01

    The delocalization of the photoexcited triplet state in a linear butadiyne-linked porphyrin dimer is investigated by time-resolved and pulse electron paramagnetic resonance (EPR) with laser excitation. The transient EPR spectra of the photoexcited triplet states of the porphyrin monomer and dimer are characterized by significantly different spin polarizations and an increase of the zero-field splitting parameter D from monomer to dimer. The proton and nitrogen hyperfine couplings, determined using electron nuclear double resonance (ENDOR) and X- and Q-band HYSCORE, are reduced to about half in the porphyrin dimer. These data unequivocally prove the delocalization of the triplet state over both porphyrin units, in contrast to the conclusions from previous studies on the triplet states of closely related porphyrin dimers. The results presented here demonstrate that the most accurate estimate of the extent of triplet state delocalization can be obtained from the hyperfine couplings, while interpretation of the zero-field splitting parameter D can lead to underestimation of the delocalization length, unless combined with quantum chemical calculations. Furthermore, orientation-selective ENDOR and HYSCORE results, in combination with the results of density functional theory (DFT) calculations, allowed determination of the orientations of the zero-field splitting tensors with respect to the molecular frame in both porphyrin monomer and dimer. The results provide evidence for a reorientation of the zero-field splitting tensor and a change in the sign of the zero-field splitting D value. The direction of maximum dipolar coupling shifts from the out-of-plane direction in the porphyrin monomer to the vector connecting the two porphyrin units in the dimer. This reorientation, leading to an alignment of the principal optical transition moment and the axis of maximum dipolar coupling, is also confirmed by magnetophotoselection experiments. PMID:25914154

  12. 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.

  13. Step-Scan FTIR spectroscopy and quantum chemical calculations of xanthone in the triplet state

    NASA Astrophysics Data System (ADS)

    Buschhaus, L.; Kleinermanns, K.

    2014-10-01

    Step-Scan-FTIR spectroscopy has been used to measure the infrared spectrum of xanthone in the triplet state using chloroform as solvent. Xanthone is an important triplet sensitizer and therefore suitable as model system. Xanthone was excited at 266 nm and its IR triplet spectrum measured in the range 1000-1750 cm-1. The spectrum was analyzed by comparison with DFT/B3LYP/TZVP/COSMO calculations. Further on the results were compared to gas phase IR measurements of triplet xanthone and calculations of isolated xanthone. Mainly based on the calculations we tried to identify the geometry changes from the electronic ground state to the first triplet state.

  14. Room temperature triplet state spectroscopy of organic semiconductors

    NASA Astrophysics Data System (ADS)

    Reineke, Sebastian; Baldo, Marc A.

    2014-01-01

    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.

  15. Room temperature triplet state spectroscopy of organic semiconductors

    PubMed Central

    Reineke, Sebastian; Baldo, Marc A.

    2014-01-01

    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. PMID:24445870

  16. Electron-Phonon Coupling and CT-Character in the lowest Triplet Excited State of Anthracene EDA-Complex Crystals

    NASA Astrophysics Data System (ADS)

    Maier, S.; Port, H.

    1987-11-01

    Photoexcitation spectra of triplet (T1← S0) zero-phonon lines and phonon sidebands in different anthracene electron donor-acceptor (EDA) complex crystals (A-PMDA, A-TCNB, A-TCPA) have been analyzed between 1.3 K and 50 K at high spectral resolution. From the electron-phonon coupling strength at T = 0 K values of the charge-transfer (CT) character in the range between 6% and 10% are calculated. The differences in these values are found to be correlated with the energetic positions of the triplet state, which are explained within the framework of the Mulliken theory.

  17. 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

  18. Aromaticity Reversal in the Lowest Excited Triplet State of Archetypical Möbius Heteroannulenic Systems.

    PubMed

    Oh, Juwon; Sung, Young Mo; Kim, Woojae; Mori, Shigeki; Osuka, Atsuhiro; Kim, Dongho

    2016-05-23

    The aromaticity reversal in the lowest triplet state (T1 ) of a comparable set of Hückel/Möbius aromatic metalated expanded porphyrins was explored by optical spectroscopy and quantum calculations. In the absorption spectra, the T1 states of the Möbius aromatic species showed broad, weak, and ill-defined spectral features with small extinction coefficients, which is in line with typical antiaromatic expanded porphyrins. In combination with quantum calculations, these results indicate that the Möbius aromatic nature of the S0 state is reversed to Möbius antiaromaticity in the T1 state. This is the first experimental observation of aromaticity reversal in the T1 state of Möbius aromatic molecules. PMID:27079620

  19. 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.

  20. 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.

  1. Excited-state properties and physiological functions of biological polyenes: the triplet-excited region of retinoids and carotenoids

    NASA Astrophysics Data System (ADS)

    Koyama, Y.; Mukai, Yumiko; Kuki, Michitaka

    1993-06-01

    Both experimental and theoretical results which indicate the presence of the triplet-excited region in retinoids and carotenoids are reviewed. The triplet- excited region is defined as a region where changes in the bond order take place, upon triplet excitation, toward its inversion, i.e., a double bond becomes more signal bond-like and a single bond becomes more double bond-like. (1) It has a span of approximately six conjugated double bonds, (2) it is localized in the central part of a conjugated chain, and (3) it triggers `cis' to `trans' isomerization in the T1 state. The experimental and theoretical results include: (1) the T1 Raman spectra of all-trans-retinal and its homologues; (2) the T1-state isomerization of isomeric retinal; (3) the T1-state isomerization of isomeric (beta) -carotene; (4) the PPP-SD-CI calculations of the bond orders of the carbon-carbon bonds in a set of model polyenes; and (5) the normal-coordinate analysis of the T1 Raman lines of undeuterated and deuterated all-trans-retinal. Finally, (6) the biological implication of 'the triplet-excited region' is discussed in relation to the photo-protective function of a 15-cis carotenoid bound to the bacterial photoreaction center.

  2. Automatic stellar spectra parameterisation in the IR Ca ii triplet region

    NASA Astrophysics Data System (ADS)

    Kordopatis, G.; Recio-Blanco, A.; de Laverny, P.; Bijaoui, A.; Hill, V.; Gilmore, G.; Wyse, R. F. G.; Ordenovic, C.

    2011-11-01

    Context. Galactic archaeology aims to determine the evolution of the Galaxy from the chemical and kinematical properties of its individual stars. This requires the analysis of data from large spectroscopic surveys, with sample sizes in tens of thousands at present, with millions of stars being reached in the near future. Such large samples require automated analysis techniques and classification algorithms to obtain robust estimates of the stellar parameter values. Several on-going and planned spectroscopic surveys have selected their wavelength region to contain the IR Ca ii triplet (~λλ 8500 Å) and the work presented in this paper focuses on the automatic analysis of such spectra. Aims: We aim to develop and test an automatic method by which one can obtain estimates of values of the stellar atmospheric parameters (effective temperature, surface gravity, overall metallicity) from a stellar spectrum. We also explore the degeneracies in parameter space, estimate the uncertainties in the derived parameter values and investigate the consequences of these limitations for achieving the goals of galactic archaeology. Methods: We investigated two algorithms, both of which compare the observed spectrum to a grid of synthetic spectra, but each uses a different mathematical approach for finding the optimum match and hence the best values of the stellar parameters. Our investigation of these algorithms' robustness can be widely applied because it amplifies the main problems that the other methods can encounter. The first algorithm, MATISSE, derives the values of each stellar parameter through a local fit to the spectrum such that each pixel in wavelength space is treated separately. The sensitivity of the flux at each wavelength to the value of a given stellar parameter is determined from the synthetic spectra. The observed spectrum is then projected using these sensitivity vectors to give an estimated value of the stellar parameters. This value depends on finding the true

  3. 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

    2015-10-01

    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. PMID:26381591

  4. 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.

  5. Transient EPR Reveals Triplet State Delocalization in a Series of Cyclic and Linear π-Conjugated Porphyrin Oligomers.

    PubMed

    Tait, Claudia E; Neuhaus, Patrik; Peeks, Martin D; Anderson, Harry L; Timmel, Christiane R

    2015-07-01

    The photoexcited triplet states of a series of linear and cyclic butadiyne-linked porphyrin oligomers were investigated by transient Electron Paramagnetic Resonance (EPR) and Electron Nuclear DOuble Resonance (ENDOR). The spatial delocalization of the triplet state wave function in systems with different numbers of porphyrin units and different geometries was analyzed in terms of zero-field splitting parameters and proton hyperfine couplings. Even though no significant change in the zero-field splitting parameters (D and E) is observed for linear oligomers with two to six porphyrin units, the spin polarization of the transient EPR spectra is particularly sensitive to the number of porphyrin units, implying a change of the mechanism of intersystem crossing. Analysis of the proton hyperfine couplings in linear oligomers with more than two porphyrin units, in combination with density functional theory calculations, indicates that the spin density is localized mainly on two to three porphyrin units rather than being distributed evenly over the whole π-system. The sensitivity of the zero-field splitting parameters to changes in geometry was investigated by comparing free linear oligomers with oligomers bound to a hexapyridyl template. Significant changes in the zero-field splitting parameter D were observed, while the proton hyperfine couplings show no change in the extent of triplet state delocalization. The triplet state of the cyclic porphyrin hexamer has a much decreased zero-field splitting parameter D and much smaller proton hyperfine couplings with respect to the monomeric unit, indicating complete delocalization over six porphyrin units in this symmetric system. This surprising result provides the first evidence for extensive triplet state delocalization in an artificial supramolecular assembly of porphyrins. PMID:26035477

  6. Transient EPR Reveals Triplet State Delocalization in a Series of Cyclic and Linear π-Conjugated Porphyrin Oligomers

    PubMed Central

    2015-01-01

    The photoexcited triplet states of a series of linear and cyclic butadiyne-linked porphyrin oligomers were investigated by transient Electron Paramagnetic Resonance (EPR) and Electron Nuclear DOuble Resonance (ENDOR). The spatial delocalization of the triplet state wave function in systems with different numbers of porphyrin units and different geometries was analyzed in terms of zero-field splitting parameters and proton hyperfine couplings. Even though no significant change in the zero-field splitting parameters (D and E) is observed for linear oligomers with two to six porphyrin units, the spin polarization of the transient EPR spectra is particularly sensitive to the number of porphyrin units, implying a change of the mechanism of intersystem crossing. Analysis of the proton hyperfine couplings in linear oligomers with more than two porphyrin units, in combination with density functional theory calculations, indicates that the spin density is localized mainly on two to three porphyrin units rather than being distributed evenly over the whole π-system. The sensitivity of the zero-field splitting parameters to changes in geometry was investigated by comparing free linear oligomers with oligomers bound to a hexapyridyl template. Significant changes in the zero-field splitting parameter D were observed, while the proton hyperfine couplings show no change in the extent of triplet state delocalization. The triplet state of the cyclic porphyrin hexamer has a much decreased zero-field splitting parameter D and much smaller proton hyperfine couplings with respect to the monomeric unit, indicating complete delocalization over six porphyrin units in this symmetric system. This surprising result provides the first evidence for extensive triplet state delocalization in an artificial supramolecular assembly of porphyrins. PMID:26035477

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

    PubMed

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

    2016-09-14

    We report on spectroscopic studies of resonances related to ladder of states of a charged exciton in single GaAlAs/AlAs quantum dot structures. Polarization-resolved photoluminescence, photoluminescence excitation and photon-correlation measurements were performed at low (T  =  4.2 K) temperature also in magnetic field applied in Faraday configuration. The investigated resonances are assigned to three different configurations of a positively charged exciton. Together with a singlet ground state and a conventional triplet state (involving an electron from the ground state electronic s-shell), an excited triplet state, which involved an electron from the excited electronic p-shell was identified in single dots. The appearance of an emission line related to the latter complex is due to a partially suppressed electron relaxation in the investigated dots. An analysis of this emission line allows us to scrupulously determine properties of the excited triplet state and compare them with those of the conventional triplet state. Both triplets exhibit similar patterns of anisotropic fine structure and Zeeman splitting, however their amplitudes significantly differ for those two states. Presented results emphasize the role of the symmetry of the electronic state on the properties of the triplet states of two holes  +  electron excitonic complex. PMID:27391126

  8. 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.

  9. Singlet and triplet excited state properties of natural chlorophylls and bacteriochlorophylls

    SciTech Connect

    Niedzwiedzki, Dariusz; Blankenship, R. E.

    2010-11-18

    Ten naturally occurring chlorophylls (a, b, c{sub 2}, d) and bacteriochlorophylls (a, b, c, d, e, g) were purified and studied using the optical spectroscopic techniques of both steady state and time-resolved absorption and fluorescence. The studies were carried out at room temperature in nucleophilic solvents in which the central Mg is hexacoordinated. The comprehensive studies of singlet excited state lifetimes show a clear dependency on the structural features of the macrocycle and terminal substituents. The wide-ranging studies of triplet state lifetime demonstrate the existence of an energy gap law for these molecules. The knowledge of the dynamics and the energies of the triplet state that were obtained in other studies allowed us to construct an energy gap law expression that can be used to estimate the triplet state energies of any (B)chlorophyll molecule from its triplet lifetime obtained in a liquid environment.

  10. 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.

  11. Spectroscopy of triplet states of Rb{sub 2} by femtosecond pump-probe photoionization of doped helium nanodroplets

    SciTech Connect

    Mudrich, M.; Heister, Ph.; Hippler, T.; Giese, Ch.; Stienkemeier, F.; Dulieu, O.

    2009-10-15

    The dynamics of vibrational wave packets in triplet states of rubidium dimers (Rb{sub 2}) formed on helium nanodroplets are studied using femtosecond pump-probe photoionization spectroscopy. Due to fast desorption of the excited Rb{sub 2} molecules off the droplets and due to their low internal temperature, wave-packet oscillations can be followed up to very long pump-probe delay times > or approx. 1.5 ns. In the first-excited triplet state (1){sup 3}{sigma}{sub g}{sup +}, full and fractional revivals are observed with high contrast. Fourier analysis provides high-resolution vibrational spectra which are in excellent agreement with ab initio calculations.

  12. Identifying the efficient inter-conversion between singlet and triplet charge-transfer states by magneto-electroluminescence study

    NASA Astrophysics Data System (ADS)

    Chen, Ping; Peng, Qiming; Yao, Liang; Gao, Na; Li, Feng

    2013-02-01

    Using the magneto-electroluminescence (MEL) as a tool, we demonstrated the efficient inter-conversion between singlet and triplet charge-transfer (CT) states in exciplex-based organic light-emitting diodes (OLEDs). Results show that the MEL of exciplex-based device is larger than that of exciton-based device by a factor of 3.2. The emission of exciplex-based devices comes from the direct intermolecular electron-hole pair recombination and their spin exchange energy is much smaller, which causes the efficient inter-conversion between singlet and triplet states. This argument was supported by the consistent evolutions of the MEL and EL spectra versus applied bias and donor concentrations. Finally, the bandgap effects on the MEL as well as the external quantum efficiency of exciplex-based devices were discussed. Our findings of MEL may offer a feasible way to unravel underlying mechanisms that limit the EL efficiency in the OLEDs.

  13. 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). PMID:23136952

  14. Quantum chemistry-based interpretations on the lowest triplet state of luminescent lanthanides complexes. Part 1. Relation between the triplet state energy of hydroxamate complexes and their luminescence properties.

    PubMed

    Gutierrez, Fabien; Tedeschi, Christine; Maron, Laurent; Daudey, Jean-Pierre; Poteau, Romuald; Azema, Joëlle; Tisnès, Pierre; Picard, Claude

    2004-05-01

    In this paper, we evaluate the potential use of theoretical calculations to obtain an energy scale of the lowest ligand-centred triplet excited state in luminescent terbium(III) complexes. In these complexes, non-radiative deactivation of the terbium emitting state via a back-energy transfer process (T1<--Tb(5D4)) is a common quenching process. Consequently the prediction of the energy gap between these two excited states should be useful for programming highly luminescent Tb(III) systems. We report on a strategy based upon experimental and theoretical investigations of the excited state properties of a series of four simple aromatic hydroxamate ligands coordinated to Tb(III) and Gd(III) ions. By using previously reported crystallographic data, the structural and energies properties of these systems were investigated in the ground and first excited triplet states at the density functional theory (DFT) level of calculations. Our theoretical results are consistent with a triplet excited state T1 which is localised on one ligand only and whose the energy level is independent of the lanthanide ion nature (Tb(III), Gd(III)). A good agreement between the calculated adiabatic transition energies and experimental data derived from emission spectra is obtained when a corrective term is considered. These satisfactory results are an indication that this type of modelling can lead to discriminate in terms of the position of the lowest ligand triplet energy level the best antenna among a family of chromophoric compounds. In addition this theoretical approach has provided indications that the difference between the adiabatic transition energies of all the investigated complexes can be mainly explained by metal-ligand electrostatic interactions. The influence of the number of antennae on the quantum yield and the luminescence lifetime is discussed. PMID:15252626

  15. Quenching of triplet states of phenazine and its mono-, di-,and tetrabenzo derivatives and of their triplet exciplexes with dimethylaniline by oxygen

    SciTech Connect

    Osipov, V.V.; Dilung, I.I.; Usacheva, M.N.

    1986-05-01

    This paper studies the quenching of triplet states of phenazine and its benzo derivatives, as well as of their triplet exciplexes with dimethylaniline, by oxygen. A method which permits the quantitative evaluation of the concentration of the dissolved oxygen has been described. The calculated values of the rate constants of the quenching of the T states of the azines studied and their exiplexes have been presented. The role of donor-acceptor interactions in the quenching mechanism has been discussed.

  16. 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. PMID:25919420

  17. Orbital rotation in the lowest triplet state of benzophenone

    SciTech Connect

    Dinse, K.P.; Pratt, D.W.

    1982-04-07

    Optically detected magnetic resonance (ODMR) and electron-nuclear double resonance (ODENDOR) spectroscopy at both zero and high magnetic fields were used to examine single crystals of 4,4'-dibromodiphenyl ether (DOE) containing 0.1 mol % of an enriched perdeuterio (/sup 17/O) benzophenone (/sup 17/O-BP-d/sub 10/) guest. Representative spectra are presented and explanations are offered for the electron spin transitions. The summarized results indicate the currently used atomic orbital functions do not provide an accurate description of the lowest excited states of many aromatic carbonyls. (BLM)

  18. 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.

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

    PubMed

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

    2013-10-01

    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. PMID:23437906

  20. The photochemistry of lipoic acid: photoionization and observation of a triplet excited state of a disulfide.

    PubMed

    Bucher, Götz; Lu, Changyuan; Sander, Wolfram

    2005-12-01

    Under short-wavelength UV irradiation, lipoic acid (LipSS) and its reduced form, dihydrolipoic acid (DHLA), undergo photoionization processes through a bi- or monophotonic pathway. After ionization, the LipSS radical cation (LipSS*+) and radical anion (LipSS*-) are generated. LipSS*- can be converted to equimolar amounts of LipSS and DHLA through second-order decay. Triplet acetone can be quenched by LipSS and DHLA with a rate close to the diffusion-controlled limit. The mechanism was further confirmed by continuous irradiation experiments. When LipSS is directly irradiated with UVA light, the first excited triplet state of LipSS is observed, with a lifetime tau=75 ns. Characteristic reactions include triplet energy transfer to oxygen and beta-carotene and addition to isoprene. The lifetime of triplet LipSS is also shortened by addition of water and methanol. PMID:16331730

  1. Effects of spin transitions degeneracy in pulsed EPR of the fullerene C70 triplet state produced by continuous light illumination.

    PubMed

    Uvarov, Mikhail N; Kulik, Leonid V; Pichugina, Tatiana I; Dzuba, Sergei A

    2011-05-01

    X-band echo-detected electron paramagnetic resonance (ED EPR) spectra of triplet state of fullerene C(70) generated by continuous light illumination were found to correspond below 30K to a non-equilibrium electron spin polarization. Above 30K spectra are characteristic of Boltzmann equilibrium. Spectra were simulated fairly well with zero-field splitting parameters D=153 MHz and E and distributed within the range of 6-42 MHz. The origin of E distribution is attributed to the Jahn-Teller effect, which in glassy matrix is expected to depend on the local surrounding of a fullerene molecule (a so-called E-strain). In the center of ED EPR spectra a narrow hole was observed. With increase of the microwave pulse turning angle this hole transforms into a single narrow absorptive line. Numerical simulations by density matrix formalism confirm that central hole originates from a simultaneous excitation of both allowed electron spin transitions of the triplet (T(0)↔T(+) and T(0)↔T(-)), because of their degeneracy at this spectral position. Also explanations are given why this hole has not been observed in the previously reported experiments on continuous wave EPR and on ED EPR under laser pulse excitation. PMID:21339084

  2. 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

    2011-11-01

    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. PMID:21936539

  3. The lowest triplet state of azulene- h8 and azulene- d8 in liquid solution. I. Survey, kinetic considerations, experimental technique, and temperature dependence of triplet decay

    NASA Astrophysics Data System (ADS)

    Nickel, Bernhard; Klemp, Dieter

    1993-08-01

    The decay rate constant k for the lowest triplet state of azulene (T 1) can be determined from the time dependence of three kinetically different delayed luminescences: (1) delayed S 2 → S 0 fluorescence due to hetero triplet-triplet annihilation T 1+T' 1 ⇝ S 2+S' 0, where T' 1 is the lowest triplet state of a sensitizer; (2) delayed S 2→S 0 fluorescence due to thermally activated homo triplet-triplet annihilation T 1+T 1⇝S 2+S 0; (3) phosphorescence and E-type delayed S 1→S 0 fluorescence. The kinetic and experimental conditions for the reliable determination of k are treated in detail. k has been determined between 130 and 270 K for azulene- h8 and azulene- d8 in isopentane. The temperature dependence of k can be represented by k= k0+ k1 exp(- Ea/ kBT). The values of k0, k1 and Ea are significantly different for azulene- h8 and azulene- d8.

  4. Detecting luminescence from triplet states of organic semiconductors at room temperatures using delayed electroluminescence spectroscopy

    NASA Astrophysics Data System (ADS)

    Wang, Qi; Aziz, Hany

    2014-08-01

    We demonstrate a unique approach for detecting luminescence from triplet states of organic materials in the solid state at room temperatures. The technique is based on measuring delayed electroluminescence from the material. The approach overcomes limitations of conventional spectroscopic techniques, such as the need for cooling to cryogenic temperatures, and works for a wide range of organic materials. The underlying mechanisms behind observing materials phosphorescence using this technique are studied. The results show that using a low concentration of the target material doped in a host material and a large energy differences between triplet states of target and host materials are necessary for obtaining efficient phosphorescence at room temperatures.

  5. Vibrational states of the triplet electronic state of H3+. The role of non-adiabatic Jahn-Teller coupling

    NASA Astrophysics Data System (ADS)

    Alijah, Alexander; Kokoouline, Viatcheslav

    2015-10-01

    Vibrational energies and wave functions of the triplet state of the H3+ ion have been determined. In the calculations, the ground and first excited triplet electronic states are included as well as the most important part of the non-Born-Oppenheimer coupling between them. The diabatization procedure proposed by Longuet-Higgins is then applied to transform the two adiabatic ab initio potential energy surfaces of the triplet-H3+ state into a 2 × 2 diabatic matrix. The diabatization takes into account the effect of the geometrical phase due to the conical intersection between the two adiabatic potential surfaces. The results are compared to the calculation involving only the lowest adiabatic potential energy surface of the triplet-H3+ ion and neglecting the geometrical phase. The energy difference between results with and without the non-adiabatic coupling and the geometrical phase is about one wave number for the lowest vibrational levels.

  6. 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. PMID:25515745

  7. Photophysics of protoporphyrin ions in vacuo: Triplet-state lifetimes and quantum yields

    NASA Astrophysics Data System (ADS)

    Calvo, M. Reyes; Andersen, Jens Ulrik; Hvelplund, Preben; Nielsen, Steen Brøndsted; Pedersen, Ulrik V.; Rangama, Jimmy; Tomita, Shigeo; Forster, James S.

    2004-03-01

    Lifetimes of triplet-state molecules and triplet quantum yields are important parameters in photobiology as they determine the generation of singlet-oxygen upon irradiation with visible light. Here we report lifetimes of protoporphyrin IX (pp) in vacuo measured in an ion storage ring. We find that after 532 nm photon absorption, pp- (free base and negatively charged carboxylate) and pp+ (single protonation of ring nitrogen) have triplet-state lifetimes of 12 and 6 ms, respectively. After 415 or 390 nm absorption the lifetime of the anion is shorter (1.5 and 0.6 ms) as expected from the increase in temperature. Triplet quantum yields of pp- and pp+ are similar, 0.6-0.7, close to values reported for the free base and monocation in solution. The other channel, direct decay to the electronic ground state and subsequent dissociation of vibrationally excited ions, is much faster than triplet-singlet intersystem crossing. We measured lifetimes of 63 μs, 96 μs, and 0.3 ms after 390, 415, and 532 nm excitation, respectively. A fit of a statistical model to the pp- decay results in an Arrhenius activation energy of 0.5±0.2 eV for CO2 loss and a low preexponential factor (106-1010 s-1), indicative of an entropic barrier.

  8. 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.

  9. Investigation of the triplet state of chlorophylls. Technical progress report, May 1, 1979-April 30, 1980

    SciTech Connect

    Clarke, R.H.

    1980-01-01

    The triplet state of chlorophyll has been utilized as a nondestructive probe into the structural and dynamical nature of the photosynthetic apparatus, both in vitro and in isolated in vivo subunits. During the past year, using zero-field triplet state optically detected magnetic resonance spectroscopy, the research program has examined triplet energy transfer between photosynthetic pigments in solution; has isolated and studied subchloroplast particles enriched with photo-system I and the light harvesting chlorophyll protein (antenna) system; and has examined model chlorophyll-protein systems, specifically chlorophyll protein 668 and the reconstituted myoglobins. The overall aim of the research program has been to detail the physical features and interactions of the photosynthetic pigment systems through examination of structural subunits of the photosynthetic apparatus and model systems which represent them.

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

    NASA Astrophysics Data System (ADS)

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

    2015-07-01

    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.

  11. 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

  12. Conditions for Describing Triplet States in Reduced Density Matrix Functional Theory.

    PubMed

    Theophilou, Iris; Lathiotakis, Nektarios N; Helbig, Nicole

    2016-06-14

    We consider necessary conditions for the one-body reduced density matrix (1RDM) to correspond to a triplet wave function of a two-electron system. The conditions concern the occupation numbers and are different for the high spin projections, Sz = ±1, and the Sz = 0 projection. Hence, they can be used to test if an approximate 1RDM functional yields the same energies for both projections. We employ these conditions in reduced density matrix functional theory calculations for the triplet excitations of two-electron systems. In addition, we propose that these conditions can be used in the calculation of triplet states of systems with more than two electrons by restricting the active space. We assess this procedure in calculations for a few atomic and molecular systems. We show that the quality of the optimal 1RDMs improves by applying the conditions in all the cases we studied. PMID:27171683

  13. 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.

  14. 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.

  15. 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.

  16. Aqueous secondary organic aerosol (SOA) production from the oxidation of phenols by triplet excited state organics

    NASA Astrophysics Data System (ADS)

    Smith, J.; Yu, L.; Zhang, Q.; Anastasio, C.

    2011-12-01

    Recent literature has shown that atmospheric condensed-phase chemistry can play a significant role in the evolution of organic aerosols, including the formation of secondary organic aerosol (SOA). SOA formation from the oxidation of volatile organic compounds (VOCs) in the aqueous phase has largely focused on oxidations involving the hydroxyl radical and other oxidants, such as photochemically created triplet excited states, have not been fully investigated. Phenolic compounds are one of the primary carbon emission classes from biomass and wood combustion and have significant water solubility. Once in the aqueous phase, phenolic compounds can react with the triplet excited states of non-phenolic aromatic carbonyls (NPCs), particle-bound organics that are also emitted in large quantities from wood combustion. The oxidation of phenolic species in the condensed phase by triplet excited states can result in the production of SOA. A main goal of this study was to investigate bulk solution reaction kinetics under atmospherically relevant conditions in order to ascertain how these reactions can impact aqueous-phase SOA production. In our experiments, we studied the reactions of five phenols (phenol, guaiacol, syringol, catechol, and resorcinol) with the triplet state of 3,4-dimethoxybenzaldehyde (34-DMB) during simulated solar radiation. We have characterized the impacts of pH, ionic strength and reactant concentrations on the reaction behavior of this system. In addition, we analyzed the SOA formed using high-resolution aerosol mass spectrometry, ion chromatography, and liquid chromatography-mass spectrometry to infer the reaction mechanisms. Our evidence suggests that under atmospherically relevant conditions, triplet excited states can be the dominant oxidant of phenolics and contribute significantly to the total SOA budget.

  17. Optically detected magnetic resonance studies of photoexcited /sup 17/O-benzophenone. Orbital rotation in the lowest triplet state

    SciTech Connect

    Waeckerle, G.; Baer, M.; Zimmermann, H.; Dinse, K.H.; Yamauchi, S.; Kashmar, R.J.; Pratt, D.W.

    1982-03-01

    The magnetically active isotope of oxygen /sup 17/O has been used to probe the changes in the electron charge and spin density distributions in oxygen valence orbitals which occur when benzophenone is excited to its lowest triplet state. The data obtained include the optically detected magnetic resonance (ODMR) and electron-nuclear double resonance spectra at both zero and high magnetic fields. New methods of analysis of zero-field ODMR spectra, appropriate when the second-order hyperfine splitting exceeds the quadrupole coupling, are described. This analysis yields the principal values of the electron fine-structure (D), oxygen hyperfine (A), and oxygen quadrupole (Q) tensors, and the orientation of their principal axes with respect to the molecular frame. It is found, consistent with expectations for an n..pi..( state, that the direction of the largest component of Q is different from that of the ground state. It is also found, by two independent methods, that the principal transverse axes of A and Q do not conform to the local C/sub 2v/ symmetry axes of the carbonyl group. This result is interpreted to mean that the axis of the n-type oxygen 2p orbital is rotated out of the carbonyl plane, a rotation which appears to be direct consequence of n..pi..(/..pi pi..( configurational mixing. In agreement with this, the principal values of D, A, and Q are different from those expected for a ''pure'' n..pi..( state. Other consequences of n..pi..(/..pi pi..( mixing, not only in benzophenone but also in the lowest triplet states of other aromatic carbonyls, are discussed briefly.

  18. Kinetic Parameters of Photo-Excited Triplet State of Pentacene Determined by Dynamic Nuclear Polarization

    NASA Astrophysics Data System (ADS)

    Kawahara, Tomomi; Sakaguchi, Satoshi; Tateishi, Kenichiro; Tang, Tsz Leung; Uesaka, Tomohiro

    2015-04-01

    The lifetimes and spin-lattice relaxation time of photo-excited triplet electron of pentacene doped in p-terphenyl at room temperature have been investigated. Values of spin-lattice relaxation time previously reported in ESR studies are inconsistent with each other. In this paper, we determined these time constants based on proton signals enhanced by dynamic nuclear polarization using the electrons (Triplet-DNP). The combined analysis of dependences of proton signal intensities on the delay time of polarization transfer and laser pulse structure allows us to disentangle contributions of the lifetimes and spin-lattice relaxation time. The lifetimes of triplet sublevels with ms = 0 and ±1 were determined to be 22.3 and 88 µs, respectively. The spin-lattice relaxation time was found to be longer than 300 µs, hence the time evolution of the electron population in the triplet state is governed by the lifetimes. It was also found that the proton signal enhancement is limited at a high repetition rate by the partial cancellation of the electron spin polarization by the remaining population produced by the preceding laser pulses.

  19. 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.

  20. 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.

  1. Investigation of the triplet state of chlorophylls. Progress report, May 1, 1980-April 30, 1981

    SciTech Connect

    Clarke, R.H.

    1980-12-22

    The triplet state of chlorophyll has been utilized as a nondestructive probe into the structural and dynamical nature of the photosynthetic apparatus. During the past year, using zero-field triplet state optically detected magnetic resonance spectroscopy, chlorophyll aggregates were examined in both their natural environment in vivo and in model complexes in vitro. Research efforts have focused on subchloroplast particles extracted from green plants, on chlorophyll monolayers, and on isolated chlorophyll molecules bound to both simple ligands and to complete proteins. The overall aim of the research program is to detail the physical features and interactions of the photosynthetic pigment systems through examination of structural subunits of the photosynthetic apparatus and model systems which represent them.

  2. Quenching of triplet states of aromatic ketones by sulfur-containing amino acids in solution. Evidence for electron transfer

    SciTech Connect

    Marciniak, B.; Bobrowski, K.; Hug, G.L. )

    1993-11-18

    The mechanism for quenching triplet states of benzophenones by sulfur-containing amino acids in water/acetonitrile solution was investigated by laser flash photolysis. The amino acids in the study were methionine, S-methylcysteine, and S-carboxymethylcysteine, and the eight aromatic triplets were those of benzophenone and its derivatives possessing electron-withdrawing or electron-donating groups. The presence of radical ions in the transient spectra and correlations of the quenching rate constants with the free energy change for electron transfer are strong indications that the process involves an electron transfer. These correlations were displayed as Rehm-Weller plots (logarithm of quenching rate vs free energy). Classical theoretical formulations of the Rehm-Weller correlations were used to estimate the intrinsic barriers and the transmission coefficients for the electron-transfer processes. Applying both [open quotes]quadratic[close quotes] Marcus and [open quotes]asymptotic[close quotes] Agmon-Levine free energy relationships led to the values of intrinsic barriers lower than the solvent reorganization energy calculated within the framework of the dielectric continuum model. These relationships also led to low electronic transmission coefficients. The low values of the intrinsic barriers for electron transfer were also obtained using the recently developed Tachiya approach. 58 refs., 5 figs., 2 tabs.

  3. Pigment-pigment interactions in thylakoids and LHCII of chlorophyll a/ c containing alga Pleurochloris meiringensis: analysis of fluorescence-excitation and triplet-minus-singlet spectra

    NASA Astrophysics Data System (ADS)

    Büchel, C.; Razi Naqvi, K.; Melø, T. B.

    1998-05-01

    Time-resolved triplet-minus-singlet (TmS) difference spectra, Δ A( λ; t), fluorescence excitation spectra, X( λ), and absorption spectra, A( λ), are used for probing pigment-pigment interactions in the thylakoids (Chl a/ c-Thyl) and isolated light-harvesting complexes associated with photosystem II (Chl a/ c-LHCII) of the alga Pleurochloris meiringensis, whose chromophores comprise chlorophyll a (Chl a), chlorophyll c (Chl c), and several carotenoids. The data provide information about interactions between Car*-and-Chl a0, Chl a†-and-Car 0, Car †-and-Chl a0 (where the abbreviation Car stands for carotenoid, an asterisk and a dagger denote singlet and triplet excitation, respectively, and the superscript 0 denotes a molecule in the ground state). In Chl a/c-Thyl, the efficiency of Car*→Chl a* transfer ( φLH), determined by comparing A( λ) and X( λ), is slightly less than unity (ca. 0.85), whereas the efficiency of Chl a†→Car † transfer of triplet energy ( φTT) must be much closer to unity, since no long-lived Chl a† could be detected; an interaction between Car † and Chl a0, already familiar from investigations concerning the TmS spectra of the trimers and aggregates of Chl a/ b-LHCII (the light-harvesting complex associated with the photosystem II of higher plants), which manifests itself through a depletion signal (in the Qy region of Chl a) decaying at the same rate as the Car TmS signal, is observed, and explained likewise. In Chl a/ c-LHCII, both efficiencies are found to be much lower; the drastic reduction in the two yields is attributed to the perturbation of the native molecular architecture of the complex by the detergent used in the isolation procedure. The overall TmS signal from Chl a/ c-LHCII can be decomposed into two contributions, Δ A( λ; t)=Δ 1A( λ; t)+Δ 2A( λ; t), where Δ 1A( λ; t) with a lifetime of about 8 μs; Δ 2A( λ; t), which persists for several hundred microseconds, is contributed by those Chl a

  4. Electron transfer in the quenching of protonated triplet thionine and methylene blue by ground state thionine

    SciTech Connect

    Kamat, P.V.; Lichtin, N.N.

    1981-01-01

    Use of thiazine dyes, e.g., thionine and methylene blue, in the conversion of light energy into electrical energy has been studied extensively in recent years. Despite continuing efforts to improve the performance of photogalvanic cells, the highest reported engineering efficiency for photogalvanic conversion of sunlight into electricity is still less than 0.1%. One of the proposed steps to increase efficiency is to employ high concentrations of light-absorbing dye, e.g., 0.1 M. However, use of such high concentrations of dye may lead to wastage of absorbed quantum energy via a variety of processes, one of which is quenching of triplet dye by ground-state dye. A study of such ground-state quenching of protonated triplet methylene blue, /sup 3/MBH/sup 2 +/, with efficiency of net electron transfer in quenching, F/sub 1/, less than 0.5 was reported previously. Quenching without net electron-transfer inevitably reduces the conversion efficiency of photogalvanic cells. The results of a laser flash-photolytic, kinetic spectrometric study of kinetics and mechanism of quenching of protonated triplet thionine, /sup 3/TH/sub 2//sup 2 +/, and /sup 3/MBH/sup 2 +/ by ground-state thionine, TH/sup +/, in water, aqueous CH/sub 3/CN and aqueous ethanol are presented.

  5. Magnetic edge states and mixed-parity pairing in spin-triplet superconductors

    NASA Astrophysics Data System (ADS)

    Cuoco, Mario; Gentile, Paola; Noce, Canio; Vekhter, Ilya; Romano, Alfonso

    2014-03-01

    We show that a spontaneous magnetic moment may appear at the edge of a spin-triplet superconductor if the system allows for pairing in a subdominant channel and non-uniform spatial profile. To unveil the microscopic mechanism behind such effect we combine numerical solution of the Bogoliubov-De Gennes equations for a tight-binding model with nearest-neighbor attraction, and the symmetry based Ginzburg-Landau approach. We find that a modulation of the electronic density near the edge of the system leads to a non-unitary superconducting state where spin-singlet pairing coexists with the dominant triplet superconducting order. We demonstrate that the spin polarization at the edge appears due to the inhomogeneity of the non-unitary state and originates in the lifting of the spin-degeneracy of the Andreev bound-states. For chiral spin-triplet superconductors spin current flows along the interface and surface charge currents exhibit anomalous dependence on the magnetization. - A. Romano, P. Gentile, C. Noce, I. Vekhter, M. Cuoco, Phys. Rev. Lett. 110, 267002 (2013). This research has received funding from the EU -FP7/2007-2013 under grant agreement N. 264098 - MAMA, and was supported in part by US NSF via Grant No. DMR-1105339

  6. The role of triplet states in the emission mechanism of polymer light-emitting diodes

    NASA Astrophysics Data System (ADS)

    Arif, M.; Mukhopadhyay, S.; Ramasesha, S.; Guha, S.

    2009-09-01

    The blue emission of polyfluorene (PF)-based light-emitting diodes (LEDs) is known to degrade due to a low-energy green emission, which hitherto has been attributed to oxidative defects. By studying the electroluminescence (EL) from ethyl-hexyl substituted PF LEDs in the presence of oxygen and in an inert atmosphere, and by using trace quantities of paramagnetic impurities (PM) in the polymer, we show that the triplet states play a major role in the low-energy emission mechanism. Our time-dependent many-body studies show a large cross-section for the triplet formation in the EL process in the presence of PM, primarily due to electron-hole recombination processes.

  7. Improved triplet state parameters for indium octacarboxy phthalocyanines when conjugated to quantum dots and magnetite nanoparticles

    NASA Astrophysics Data System (ADS)

    Tshangana, Charmaine; Nyokong, Tebello

    2015-06-01

    Fe3O4 magnetic nanoparticles (MNPs) and glutathione (GSH) capped CdSe@ZnS quantum dots (QDs) were separately coordinated to indium octacarboxy phthalocyanine (InPc(COOH)8) to form ClInPc(COOH)8-MNPs and ClInPc(COOH)8-GSH-CdSe@ZnS, respectively. The photophysical parameters (triplet state and fluorescence quantum yields and lifetimes) were determined for the conjugates. The triplet quantum yields increased from ΦT = 0.49 for InPc(COOH)8 alone to ΦT = 0.61 and 0.56 for InPc(COOH)8 in the conjugates: ClInPc(COOH)8-MNPs and ClInPc(COOH)8-GSH-CdSe@ZnS, respectively. The lifetimes also became longer for the conjugates compared to Pc alone.

  8. Prediction of Excited-State Energies and Singlet-Triplet Gaps of Charge-Transfer States Using a Restricted Open-Shell Kohn-Sham Approach.

    PubMed

    Hait, Diptarka; Zhu, Tianyu; McMahon, David P; Van Voorhis, Troy

    2016-07-12

    Organic molecules with charge-transfer (CT) excited states are widely used in industry and are especially attractive as candidates for fabrication of energy efficient OLEDs, as they can harvest energy from nonradiative triplets by means of thermally activated delayed fluorescence (TADF). It is therefore useful to have computational protocols for accurate estimation of their electronic spectra in order to screen candidate molecules for OLED applications. However, it is difficult to predict the photophysical properties of TADF molecules with LR-TDDFT, as semilocal LR-TDDFT is incapable of accurately modeling CT states. Herein, we study absorption energies, emission energies, zero-zero transition energies, and singlet-triplet gaps of TADF molecules using a restricted open-shell Kohn-Sham (ROKS) approach instead and discover that ROKS calculations with semilocal hybrid functionals are in good agreement with experiments-unlike TDDFT, which significantly underestimates energy gaps. We also propose a cheap computational protocol for studying excited states with large CT character that is found to give good agreement with experimental results without having to perform any excited-state geometry optimizations. PMID:27267803

  9. Elastic Scattering between Ultracold 23Na and 85Rb Atoms in the Triplet State

    NASA Astrophysics Data System (ADS)

    Hu, Qiu-Bo; Zhang, Yong-Sheng; Sun, Jin-Feng; Yu, Ke

    2011-04-01

    The elastic scattering properties between ultracold 23Na and 85Rb atoms for the triplet state (a3 Σ+u) are researched. The s-wave scattering lengths of 23Na and 85Rb are calculated by the Numerov and semiclassical method with two kinds of interatomic potentials, which are the interpolation potential and Lennard—Jones potential (LJ12,6) by the same phase Φ. Shape resonances appear clearly in the l = 5 partial waves for the a3 Σ+u state. Moreover, the s-wave scattering cross section, total cross section and energy positions of shape resonances are also discussed.

  10. Protection of densely populated excited triplet state ensembles against deactivation by molecular oxygen.

    PubMed

    Filatov, Mikhail A; Baluschev, Stanislav; Landfester, Katharina

    2016-08-22

    This critical review discusses different approaches towards protection of photoactive materials based on triplet excited state ensembles against deactivation by molecular oxygen though quenching and photooxidation mechanisms. Passive protection, based on the application of barrier materials for packaging, sealing, or encapsulation of the active substances, which prevent oxygen molecules from penetration and physical contact with excited states and active protection, based on the application of oxygen scavenging species are compared. Efficiencies of different approaches together with examples and prospects of their applications are outlined. PMID:27277068

  11. 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.

  12. 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.

  13. Energy linkage between the singlet and triplet manifolds in LaH, and observation of new low-energy states

    NASA Astrophysics Data System (ADS)

    Mukund, Sheo; Yarlagadda, Suresh; Bhattacharyya, Soumen; Nakhate, S. G.

    2012-12-01

    Wavelength-resolved fluorescence spectra of jet-cooled LaH were obtained from D1, E1, and 0+(3Σ-) states by exciting isolated rotational levels. The observation of a3Δ1 and a3Δ2 states at 1259.5(5) and 1646(1) cm-1, respectively, established the missing energy link between the singlet and triplet manifolds. The low-energy b3Π0,1 and B1Δ2 states predicted earlier from ab initio studies were also observed for the first time. Vibrational constants ωe = 1418(2) cm-1, ωexe = 15.6(7) cm-1 for the ground and ΔG1/2 = 1326.1(7) and 1312(1) cm-1, respectively, for the a3Δ1 and b3Π1 states were also determined. Vibrational frequencies were found to be in excellent agreement with earlier ab initio values. However, ab initio term energies and spin-orbit separation of 3Δ2-3Δ1 and 3Π1-3Π0 were found to be in poor agreement with the present observations. Also, the 3Π state that was predicted to be inverted is observed to be regular.

  14. 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. PMID:25891838

  15. Modulating the generation of long-lived charge separated states exclusively from the triplet excited states in palladium porphyrin-fullerene conjugates

    NASA Astrophysics Data System (ADS)

    O. Obondi, Christopher; Lim, Gary N.; Churchill, Brittani; Poddutoori, Prashanth K.; van der Est, Art; D'Souza, Francis

    2016-04-01

    . By tuning the rate of intersystem crossing (ISC) and the donor-acceptor distance, electron transfer can be made to occur exclusively from the triplet excited state of the electron donor resulting in long-lived charge separation. To achieve this, three new palladium porphyrin-fullerene donor-acceptor systems were synthesized. The heavy Pd atom enhances the rate of ISC in the porphyrin and the rates of electron and energy transfer are modulated by varying the redox potential of the porphyrin and the porphyrin-fullerene distance. In the case of the meso-tris(tolyl)porphyrinato palladium(ii)-fulleropyrrolidine, the donor-acceptor distance is relatively long (13.1 Å) and the driving force for electron transfer is low. As a result, excitation of the porphyrin leads to rapid ISC followed by triplet-triplet energy transfer to fullerene. When the fullerene is bound directly to the porphyrin shortening the donor-acceptor distance to 2.6 Å electron transfer from the singlet excited palladium porphyrin leading to the generation of a short-lived charge separated state is the main process. Finally, when the palladium porphyrin is substituted with three electron rich triphenylamine entities, the lower oxidation potential of the porphyrin and appropriate donor-acceptor distance (~13 Å), lead to electron transfer exclusively from the triplet excited state of palladium porphyrin with high quantum yield. The results show that when electron transfer occurs from the triplet state, its increased lifetime allows the distance between the donor and acceptor to be increased which results in a longer lifetime for the charge separated state. Electronic supplementary information (ESI) available: Spectroelectrochemical results of oxidized (TTP)Pd and (TPA)4Pd in benzonitrile; femto- and nanosecond transient spectra of (TTP)Pd in benzonitrile and toluene, (TPA)4Pd in benzonitrile and toluene, compounds 1-3 in toluene; complete experimental details including synthesis, instrumentation and

  16. Elastic Scattering of Ultracold 133Cs and 85Rb Atoms in Triplet State

    NASA Astrophysics Data System (ADS)

    Sun, Jin-Feng; Hu, Qiu-Bo; Zhu, Zun-Lue; Wang, Xiao-Fei; Zhang, Ji-Cai

    2007-06-01

    Elastic scattering properties of the ultracold interaction for the triplet state of 133Cs and 85Rb atoms are studied using two kinds of potentials by the same phase Φ. One is the interpolation potential, and another is Lennard-Jones potential (LJ12,6). The radial Schrödinger equation is also solved using two computational methods, the semiclassical method (WKB), and the Numerov method. Our results are found to be in an excellent agreement with the more recent theoretical values. It shows that the two potentials and methods are applicable for studying ultracold collisions between the mixing alkali atoms.

  17. 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.

  18. Photophysical processes of triplet states and radical ions in pure and molecularly doped polymers. Final report

    SciTech Connect

    Burkhart, R.D.

    1998-01-01

    Both the past and current objectives are to learn how to control the rate and direction of triplet exciton migration in both pure and molecularly doped polymer systems. Since triplet excimers are efficient traps for migrating excitons, a secondary objective has been to characterize these excimers with a view toward their use as rate modifiers or excited state quenchers. Further objectives included those stated above as past and current objectives but with an additional goal. The authors learned that fluid solutions of many of the nitrogen containing chromophores with which they work produce both radical cations and anions upon excimer laser excitation. They also learned that a phosphorus analogue behaves similarly. At this time the mechanism of charge generation in these systems is not well established but they do know that the electronically excited states and radical ions can potentially interconvert. They wanted to find out whether or not the pure or molecularly doped polymer systems could be used in a step-wise sequence involving light absorption followed by charge generation. All of their activities are oriented toward the potential end use of polymeric systems in the conversion of light energy to perform various types of useful work.

  19. Photoformation of Triplet Excited States and Other Oxidants in Fog Waters and Their Impact on Fog Processing of Organic Compounds

    NASA Astrophysics Data System (ADS)

    Kaur, R.; Anastasio, C.; Valsaraj, K. T.; Vempati, H. S.; Vaitilingom, M.

    2014-12-01

    Reactions in fog and cloud drops are important for a number of processes, such as formation of secondary organic aerosol (SOA), cycling of organic carbon and nitrogen, and determining the lifetimes of pollutants. The rates of these processes depend upon the steady-state concentrations of the major photooxidants, namely, hydroxyl radical (.OH), singlet molecular oxygen (1O2*) and triplet excited states of organic compounds (3C*). While there are some past measurements of .OH and 1O2* concentrations in fog and cloud drops, there are no data for the concentrations of triplet excited states. However, there is increasing evidence that triplets might be important for the processing of organics in a cloudy or foggy atmosphere. To address this question, we collected fog water samples from Davis, CA and Baton Rouge, LA, illuminated them with simulated sunlight, and measured the steady-state concentrations of .OH , 1O2* and 3C* . To understand the relative importance of these photooxidants, we also measured the photochemical loss of two added model organic compounds in the illuminated fog waters - syringol (a biomass burning phenol) and methyl jasmonate (a green leaf volatile). Our results show that triplet excited states can play a major role in oxidizing the model compounds, typically accounting for 30 - 90% of the loss of both model compounds. Given that atmospheric triplets are relatively less understood, our results highlight the importance of deeper investigation into their nature.

  20. Accessing the Triplet State in Heavy-Atom-Free Perylene Diimides.

    PubMed

    Yu, Zhenyi; Wu, Yishi; Peng, Qian; Sun, Chunlin; Chen, Jianwei; Yao, Jiannian; Fu, Hongbing

    2016-03-24

    Previous studies of perylenediimides (PDIs) mostly utilized the lowest singlet excited state S1 . Generation of a triplet excited state (T1 ) in PDIs is important for applications ranging from photodynamic therapy to photovoltaics; however, it remains a formidable task. Herein, we developed a heavy-atom-free strategy to prompt the T1 ←S1 intersystem crossing (ISC) by introducing electron-donating aryl (Ar) groups at the head positions of an electron-deficient perylenediimide (PDI) core. We found that the ISC efficiency increases from 8 to 54 % and then to 86 % by increasing the electron-donating ability of head-substituted aryl groups from phenyl (p-PDI) to methoxyphenyl (MeO-PDI) and then to methylthioxyphenyl (MeS-PDI). By enhancing the intramolecular charge-transfer (ICT) interaction from p-PDI to MeO-PDI, and then to MeS-PDI, singlet oxygen generation via energy-transfer reactions from T1 of PDIs to (3)O2 was demonstrated with the highest yield of up to 80 %. These results provide guidelines for developing new triplet-generating PDIs and related rylene diimides for optoelectronic applications. PMID:26853213

  1. 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.

  2. 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 .

  3. 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.

  4. 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.

  5. Temperature dependence of the disulfide perturbation to the triplet state of tryptophan

    PubMed Central

    Li, Zhi; Bruce, Allan; Galley, William C.

    1992-01-01

    Variability in the temperature dependence of disulfide quenching of the tryptophan phosphorescence of globular proteins in rigid glasses is illustrated with lysozyme and α-bungarotoxin. A laser-pulsed phosphorescence study of this short-range interaction with a model indole-disulfide system is described. The perturbation of secondary dibutyl disulfide on the triplet state of the indole moiety in 2-(3-indolyl)ethyl phenyl ketone in rigid media is found to display a bimodal temperature dependence. The quenching rate constant at contact between chromophore and perturber is observed to be temperature independent below 30 K, but to increase with temperature between 30 and 100 K with an activation energy of ∼200 cm-1. The results suggest that the underlying quenching interaction involves a photo-induced one-electron transfer from the excited state of indole to the disulfide. PMID:19431831

  6. 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.

  7. Photoinduced electron transfer between sulfur-containing carboxylic acids and the 4-carboxybenzophenone triplet state in aqueous solution

    SciTech Connect

    Marciniak, B. A. Mickiewicz Univ., Poznan ); Bobrowski, K.; Hug, G.L. ); Rozwadowski, J. )

    1994-05-05

    The mechanism of photoinduced electron transfer was investigated using laser flash photolysis and steady-state photolysis techniques. Bimolecular rate constants for quenching of the CB triplet state by six sulfur-containing acids, with varying numbers of COO[sup [minus

  8. Efficient up-conversion of triplet excitons into a singlet state and its application for organic light emitting diodes

    NASA Astrophysics Data System (ADS)

    Endo, Ayataka; Sato, Keigo; Yoshimura, Kazuaki; Kai, Takahiro; Kawada, Atsushi; Miyazaki, Hiroshi; Adachi, Chihaya

    2011-02-01

    A material possessing a very small energy gap between its singlet and triplet excited states, ΔE1-3, which allows efficient up-conversion of triplet excitons into a singlet state and leads to efficient thermally activated delayed fluorescence (TADF), is reported. The compound, 2-biphenyl-4,6-bis(12-phenylindolo[2,3-a] carbazole-11-yl)-1,3,5-triazine, breaks the restriction of a large energy gap, with a ΔE1-3 of just 0.11 eV, while maintaining a high fluorescent radiative decay rate (kr˜107). The intense TADF provides a pathway for highly efficient electroluminescence.

  9. Climatic Spectra of Extreme Sea States

    NASA Astrophysics Data System (ADS)

    Boukhanovsky, A.; Lopatoukhin, L.; Sas'kov, K.

    Climatic variability of sea waves is described in the terms of statistical ensemble of directional spectra, dependent from spatial coordinates (x,y) and time t. The major probabilistic characteristics of the ensemble are the climatic spectra, i.e. spectra ap- propriate to certain wavemaking conditions with certain probability. Traditionally the definition of climatic wave spectra is based on a buoy measurements in a point. How- ever such data are restricted, and are unsuitable for estimation of climatic spectra of extreme waves with return period up to 100 years or longer. Hindcasting of statistical ensemble of spectra by mean of some numerical model allows to expand the informa- tion base significantly. In this report the approach to analysis and synthesis of climatic spectra, corresponding to extreme sea states, is proposed. The Barents sea is consid- ered as an example. A set of 43800 directional spectra of wind sea and swell (1970- 1999, every 6 hours) for any of 565 points of regular grid 0.50x1.50 are calculated. Numerical wave model Wave Watch III for computation on the parallel supercomputer Parsytec CC/20 was used. The NCEP/NCAR reanalysis wind fields were used as input data. Statistical analysis of computed spectra allows to separate a set of genetic types appropriate to various stable sea states. For each of types the system of parameters as discriminant variables are proposed. Probabilistic values of these parameters allows to approximate the probabilistic characteristic of all the spectra ensemble in terms of non-random function of random arguments. It allows to synthesize the results of the analysis in terms of multiscale stochastic model of spectral wave climate, with tak- ing into account the temporal nonstationary and spatial inhomogeneity of wave fields. The Monte-Carlo approach is employed for stochastic simulation. Stochastic simu- lation proves the extrapolation procedure for climatic spectra of rare (extreme) sea states. Specific climatic wave

  10. Role of the triplet state in the green emission peak of polyfluorene films: A time evolution study

    NASA Astrophysics Data System (ADS)

    Mukhopadhyay, S.; Ramasesha, S.; Guha, S.

    2010-01-01

    The blue emission of ethyl-hexyl substituted polyfluorene (PF2/6) films is accompanied by a low energy green emission peak around 500 nm in inert atmosphere. The intensity of this 500 nm peak is large in electroluminescence (EL) compared to photoluminescence (PL) measurements. Furthermore, the green emission intensity reduces dramatically in the presence of molecular oxygen. To understand this, we have modeled various nonradiative processes by time dependent quantum many body methods. These are (i) intersystem crossing to study conversion of excited singlets to triplets leading to a phosphorescence emission, (ii) electron-hole recombination (e-hR) process in the presence of a paramagnetic impurity to follow the yield of triplets in a polyene system doped with paramagnetic metal atom, and (iii) quenching of excited triplet states in the presence of oxygen molecules to understand the low intensity of EL emission in ambient atmosphere, when compared with that in nitrogen atmosphere. We have employed the Pariser-Parr-Pople Hamiltonian to model the molecules and have invoked electron-electron repulsions beyond zero differential approximation while treating interactions between the organic molecule and the rest of the system. Our time evolution methods show that there is a large cross section for triplet formation in the e-hR process in the presence of paramagnetic impurity with degenerate orbitals. The triplet yield through e-hR process far exceeds that in the intersystem crossing pathway, clearly pointing to the large intensity of the 500 nm peak in EL compared to PL measurements. We have also modeled the triplet quenching process by a paramagnetic oxygen molecule which shows a sizable quenching cross section especially for systems with large sizes. These studies show that the most probable origin of the experimentally observed low energy EL emission is the triplets.

  11. Singlet and triplet excited states and intersystem crossing in free-base porphyrin: TDDFT and DFT/MRCI study.

    PubMed

    Perun, Serhiy; Tatchen, Jörg; Marian, Christel M

    2008-02-01

    Extensive time-dependent DFT (TDDFT) and DFT/multireference configuration interaction (MRCI) calculations are performed on the singlet and triplet excited states of free-base porphyrin, with emphasis on intersystem crossing processes. The equilibrium geometries, as well as the vertical and adiabatic excitation energies of the lowest singlet and triplet excited states are determined. Single and double proton-transfer reactions in the first excited singlet state are explored. Harmonic vibrational frequencies are calculated at the equilibrium geometries of the ground state and of the lowest singlet and triplet excited states. Furthermore, spin-orbit coupling matrix elements of the lowest singlet and triplet states and their numerical derivatives with respect to nuclear displacements are computed. It is shown that opening of an unprotonated pyrrole ring as well as excited-state single and double proton transfer inside the porphyrin cavity lead to crossings of the potential energy curves of the lowest singlet and triplet excited states. It is also found that displacements along out-of-plane normal modes of the first excited singlet state cause a significant increase of the , , and spin-orbit coupling matrix elements. These phenomena lead to efficient radiationless deactivation of the lowest excited states of free-base porphyrin via intercombination conversion. In particular, the S1-->T1 population transfer is found to proceed at a rate of approximately 10(7) s(-1) in the isolated molecule. PMID:18189251

  12. A doorway state leads to photostability or triplet photodamage in thymine DNA.

    PubMed

    Kwok, Wai-Ming; Ma, Chensheng; Phillips, David Lee

    2008-04-16

    Ultraviolet irradiation of DNA produces electronic excited states that predominantly eliminate the excitation energy by returning to the ground state (photostability) or following minor pathways into mutagenic photoproducts (photodamage). The cyclobutane pyrimidine dimer (CPD) formed from photodimerization of thymines in DNA is the most common form of photodamage. The underlying molecular processes governing photostability and photodamage of thymine-constituted DNA remain unclear. Here, a combined femtosecond broadband time-resolved fluorescence and transient absorption spectroscopies were employed to study a monomer thymidine and a single-stranded thymine oligonucleotide. We show that the protecting deactivation of a thymine multimer is due to an ultrafast single-base localized stepwise mechanism where the initial excited state decays via a doorway state to the ground state or proceeds via the doorway state to a triplet state identified as a major precursor for CPD photodamage. These results provide new mechanistic characterization of and a dynamic link between the photoexcitation of DNA and DNA photostability and photodamage. PMID:18335986

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

    NASA Astrophysics Data System (ADS)

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

    2012-06-01

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

  14. Spin-Free CC2 Implementation of Induced Transitions between Singlet Ground and Triplet Excited States.

    PubMed

    Helmich-Paris, Benjamin; Hättig, Christof; van Wüllen, Christoph

    2016-04-12

    In most organic molecules, phosphorescence has its origin in transitions from triplet exited states to the singlet ground state, which are spin-forbidden in nonrelativistic quantum mechanics. A sufficiently accurate description of phosphorescence lifetimes for molecules that contain only light elements can be achieved by treating the spin-orbit coupling (SOC) with perturbation theory (PT). We present an efficient implementation of this approach for the approximate coupled cluster singles and doubles model CC2 in combination with the resolution-of-the-identity approximation for the electron repulsion integrals. The induced oscillator strengths and phosphorescence lifetimes from SOC-PT are computed within the response theory framework. In contrast to previous work, we employ an explicitly spin-coupled basis for singlet and triplet operators. Thereby, a spin-orbital treatment can be entirely avoided for closed-shell molecules. For compounds containing only light elements, the phosphorescence lifetimes obtained with SOC-PT-CC2 are in good agreement with those of exact two-component (X2C) CC2, whereas the calculations are roughly 12 times faster than with X2C. Phosphorescence lifetimes computed for two thioketones with the SOC-PT-CC2 approach agree very well with reference results from experiment and are similar to those obtained with multireference spin-orbit configuration interaction and with X2C-CC2. An application to phosphorescent emitters for metal-free organic light-emitting diodes (OLEDs) with almost 60 atoms and more than 1800 basis functions demonstrates how the approach extends the applicability of coupled cluster methods for studying phosphorescence. The results indicate that other decay channels like vibrational relaxation may become important in such systems if lifetimes are large. PMID:26881830

  15. 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. PMID:22575209

  16. Observation of a thermally accessible triplet state resulting from rotation around a main-group π bond.

    PubMed

    Kostenko, Arseni; Tumanskii, Boris; Karni, Miriam; Inoue, Shigeyoshi; Ichinohe, Masaaki; Sekiguchi, Akira; Apeloig, Yitzhak

    2015-10-01

    We report the first direct spectroscopic observation by electron paramagnetic resonance (EPR) spectroscopy of a triplet diradical that is formed in a thermally induced rotation around a main-group π bond, that is, the SiSi double bond of tetrakis(di-tert-butylmethylsilyl)disilene (1). The highly twisted ground-state geometry of singlet 1 allows access to the perpendicular triplet diradical 2 at moderate temperatures of 350-410 K. DFT-calculated zero-field splitting (ZFS) parameters of 2 accurately reproduce the experimentally observed half-field transition. Experiment and theory suggest a thermal equilibrium between 1 and 2 with a very low singlet-triplet energy gap of only 7.3 kcal mol(-1) . PMID:26297814

  17. The Ca II triplet in red giant spectra: [Fe/H] determinations and the role of [Ca/Fe

    NASA Astrophysics Data System (ADS)

    Da Costa, G. S.

    2016-01-01

    Measurements are presented and analysed of the strength of the Ca II triplet lines in red giants in Galactic globular and open clusters, and in a sample of red giants in the LMC disc that have significantly different [Ca/Fe] abundance ratios to the Galactic objects. The Galactic objects are used to generate a calibration between Ca II triplet line strength and [Fe/H], which is then used to estimate [Fe/H]CaT for the LMC stars. The values are then compared with the [Fe/H]spec determinations from high-dispersion spectroscopy. After allowance for a small systematic offset, the two abundance determinations are in excellent agreement. Further, as found in earlier studies, the difference is only a very weak function of the [Ca/Fe] ratio. For example, changing [Ca/Fe] from +0.3 to -0.2 causes the Ca II-based abundance to underestimate [Fe/H]spec by only ˜0.15 dex, assuming a Galactic calibration. Consequently, the Ca II triplet approach to metallicity determinations can be used without significant bias to study stellar systems that have substantially different chemical evolution histories.

  18. Excited complexes in oxidation-reduction photoreactions of pigments. I. Spectral detection of triplet state exciplex in the chlorophyll oxidation reaction.

    PubMed

    Andreeva, N E; Chibisov, A K

    1976-01-01

    Photooxidation of chlorophyll "a" with p-benzoquinone in toluene and dioxane is studied by the method of flash photolysis. It is shown that in nonpolar medium the triplet exiplex is the product of this reaction. The experiments on competitive quenching of chlorophyll triplet state with naphthacene prove the diffusion mechanism of exiplex formation. The spectrum of triplet-triplet absorption of the exiplex is presented and the rate constant of intercombination degradation equalling 1.103 sec(-1) is measured. Possible structure of the exiplex is discussed. PMID:1252529

  19. Spin-triplet supercurrent carried by quantum Hall edge states through a Josephson junction

    NASA Astrophysics Data System (ADS)

    van Ostaay, J. A. M.; Akhmerov, A. R.; Beenakker, C. W. J.

    2011-05-01

    We show that a spin-polarized Landau level in a two-dimensional electron gas can carry a spin-triplet supercurrent between two spin-singlet superconductors. The supercurrent results from the interplay of Andreev reflection and Rashba spin-orbit coupling at the normal-superconductor (NS) interface. We contrast the current-phase relationship and the Fraunhofer oscillations of the spin-triplet and spin-singlet Josephson effect in the lowest Landau level and find qualitative differences.

  20. Light Absorption by Secondary Organic Aerosol Produced from Aqueous Reaction of Phenols with an Organic Excited Triplet State and Hydroxyl Radical

    NASA Astrophysics Data System (ADS)

    Smith, J.; Yu, L.; George, K.; Ruthenburg, T. C.; Dillner, A. M.; Zhang, Q.; Anastasio, C.

    2012-12-01

    Although reactions in atmospheric condensed phases can form and transform secondary organic aerosol (SOA), these reactions are not well represented in many air quality models. Previous experiments have focused on hydroxyl radical-mediated oxidation of low molecular weight precursors such as gyloxal and methylglyoxal. In our work we are examining aqueous SOA formed from phenols, which are emitted from biomass burning and formed from the oxidation of anthropogenic aromatics such as benzene and toluene. In this work we examine aqueous SOA production from oxidation of three phenols (phenol, guaiacol, syringol) and three benzene-diols (catechol, resorcinol, 1,4-hydroquinone) by hydroxyl radical (OH) and the triplet excited state of 3,4-dimethoxybenzaldehyde (DMB). Our focus is on light absorption by the reaction products, which we characterized by measuring UV-Vis spectra and calculating mass absorption coefficients. To understand the elemental and molecular composition of the SOA, we also analyzed the samples with high resolution mass spectrometry and infrared spectroscopy. Our results indicate that aqueous oxidation of phenols and benzene-diols via OH and triplet excited states efficiently produce SOA that is highly absorbing in the UV-A wavelengths, consists of both small and large molecular weight products, and is highly oxidized.

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

    PubMed

    Kato, Daiki; Sakai, Hayato; Tkachenko, Nikolai V; Hasobe, Taku

    2016-04-18

    One of the major drawbacks of organic-dye-modified self-assembled monolayers on metal nanoparticles when employed for efficient use of light energy is the fact that singlet excited states on dye molecules can be easily deactivated by means of energy transfer to the metal surface. In this study, a series of 6,13-bis(triisopropylsilylethynyl)pentacene-alkanethiolate monolayer protected gold nanoparticles with different particle sizes and alkane chain lengths were successfully synthesized and were employed for the efficient generation of excited triplet states of the pentacene derivatives by singlet fission. Time-resolved transient absorption measurements revealed the formation of excited triplet states in high yield (172±26 %) by suppressing energy transfer to the gold surface. PMID:26997657

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

    PubMed

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

    2014-12-10

    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. PMID:24997445

  3. 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.

  4. Spin-free intermediate Hamiltonian Fock space coupled-cluster theory with full inclusion of triple excitations for restricted Hartree Fock based triplet states

    NASA Astrophysics Data System (ADS)

    Musial, Monika; Bartlett, Rodney J.

    2008-12-01

    The recently reported inclusion of the connected triples into the intermediate Hamiltonian realization of the Fock space coupled-cluster (IH-FS-CC) theory [M. Musial and R. J. Bartlett, J. Chem. Phys. 129, 044101 (2008)] is extended to produce the triplet states. This is done entirely in spatial orbitals on the basis of the double occupancy in the restricted Hartree Fock reference function. New equations for the triplet state amplitudes expressed in terms of the Goldstone diagrams are derived and implemented. Several applications show the usefulness of the IH-FS-CC scheme to describe the triplet states with the computational gains inherent to a spin-free implementation.

  5. Fullerene derivatives in poly(methyl methacrylate): An EPR and zero-field ODMR study of their photoexcited triplet states

    SciTech Connect

    Agostini, G.; Corvaja, C.; Maggini, M.; Pasimeni, L.; Prato, M.

    1996-08-01

    Samples of two fullerene derivatives, namely, C{sub 60}C{sub 2}H{sub 4}N(CH{sub 3}) and C{sub 60}C{sub 2}H{sub 4}N(Ph{sub 2}C{sub 6}H{sub 4}-4-OCH{sub 3}) in poly(methyl methacrylate) (PMMA), were prepared either by solvent evaporation from CHCl{sub 3} solutions or by thermal polymerization of methyl methacrylate monomers containing the fulleropyrrolidines. In the first case PMMA behaves as a neutral polymeric matrix, while in the second the material swells by absorption of the solvent and its glass transition temperature is shifted up by 8{degree}C with respect to undoped material. Both pieces of evidence are typical of cross-linking between the polymer chains that involves fulleropyrrolidines. EPR and ODMR spectroscopies are applied to the study of the cross-linked species. It is found its excited triplet state is characterized by unusually large electron dipolar splitting ({vert_bar}D{vert_bar} = 248x10{sup -4} cm{sup -1}). Calculations of D have been carried out using a model that considers {sup 3}C{sub 60} and the fullerene derivatives as a collection of fully localized double bonds. The experimental negative sign of D has been reproduced for {sup 3}C{sub 60}, and a positive sign of D is expected for cross-linked fulleropyrrolidine affected by cross-links in the equatorial region. Such a sign reversal can explain the different spin polarization patterns exhibited by their EPR spectra. 38 refs., 5 figs., 1 tab.

  6. Excitation wavelength-dependent EPR study on the influence of the conformation of multiporphyrin arrays on triplet state delocalization.

    PubMed

    Tait, Claudia E; Neuhaus, Patrik; Peeks, Martin D; Anderson, Harry L; Timmel, Christiane R

    2016-02-21

    The optoelectronic properties of conjugated porphyrin arrays render them excellent candidates for use in a variety of molecular electronic devices. Understanding the factors controlling the electron delocalization in these systems is important for further developments in this field. Here, we use transient EPR and ENDOR (Electron Nuclear Double Resonance) to study the extent of electronic delocalization in the photoexcited triplet states of a series of butadiyne-linked porphyrin oligomers. We are able to distinguish between planar and twisted arrangements of adjacent porphyrin units, as the different conformations are preferentially excited at different wavelengths in the visible range. We show that the extent of triplet state delocalization is modulated by the torsional angle between the porphyrins and therefore by the excitation wavelength. These results have implications for the design of supramolecular systems with fine-tuned excitonic interactions and for the control of charge transport. PMID:26814427

  7. Does electron-transfer theory explain large rate differences in singlet and triplet excited state electron-transfer reactions?

    SciTech Connect

    Zusman, L.D.; Kurnikov, I.V.; Beratan, D.N.

    1995-12-31

    Gray and coworkers have shown that intramolecular electron-transfer rates from singlet and triplet excited states in iridium(spacer)pyridinium complexes can be vastly different (>5 orders of magnitude). We have analyzed the possible sources of these differences, including effects that may arise from reorganization energies, free energies, and tunneling matrix elements. When distance dependent reorganization energies and energy dependent tunneling matrix elements are included, a systematic framework emerges to describe these electron-transfer reactions.

  8. 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.

  9. Dynamics of the cage effect in recombination of radical pairs originating in the triplet state. Effect of a magnetic field

    SciTech Connect

    Levin, P.P.; Khudyakov, I.V.; Kuz'min, V.A.

    1986-11-01

    The kinetics of recombination of radical pairs formed in transfer of a hydrogen atom from p-cresol and aniline to the triplet of benzophenone were studied in a pulsed laser photolysis system based on a nitrogen laser with a recording system resolving time of 10 nanoseconds. The dynamics of the cage effect in recombination of the radical pairs arising in the triplet state were recorded. The magnitude of the cage effect was found to increase with a decrease in the solution temperature. It was found necessary to consider the effects of proximity for a quantitative theoretical description of geminal recombination. Application of an external magnetic field was found to retard recombination. The magnetic effects should apparently be considered within the framework of a relaxation mechanism of spin dynamics.

  10. Thermally activated delayed fluorescence as a cycling process between excited singlet and triplet states: Application to the fullerenes

    NASA Astrophysics Data System (ADS)

    Baleizão, Carlos; Berberan-Santos, Mário N.

    2007-05-01

    In efficient thermally activated delayed fluorescence (TADF) the excited chromophore alternates randomly between the singlet and triplet manifolds a large number of times before emission occurs. In this work, the average number of cycles n¯ is obtained and is shown to have a simple experimental meaning: n¯+1 is the intensification factor of the prompt fluorescence intensity, owing to the occurrence of TADF. A new method of data analysis for the determination of the quantum yield of triplet formation, combining steady-state and time-resolved data in a single plot, is also presented. Application of the theoretical results to the TADF of [70]fullerenes shows a general good agreement between different methods of fluorescence analysis and allows the determination of several photophysical parameters.

  11. Triplet state magnetic resonance and fluorescence spectroscopy of metal-substituted hemoglobins.

    PubMed

    Polm, M W; Schaafsma, T J

    1997-01-01

    Fluorescence detected magnetic resonance (FDMR) spectra detected at 596 nm of zinc-substituted hemoglobins at 4.2 K show a split D-E transition, which is not observed for zinc protoporphyrins ligated by methylimidazole in glasses. Incorporation of the zinc heme into the globin pocket is also accompanied by a blue shift of the fluorescence of 20 nm at 4.2 K. FDMR spectra recorded at 576 nm do not show the D-E splitting. The D-E splitting and the huge blue shift are not observed for the magnesium-substituted hemoglobins. Fluorescence measurements at 4.2 K and 77 K, and EPR measurements at 110 K, were carried out to obtain information about the ligation states of the zinc and magnesium protoporphyrins in glasses and in hemoglobin. The results are explained by considering ligation effects and distortion of the porphyrin plane. PMID:8994622

  12. ESR in zero field of the photoinduced triplet state in isolated reaction centers of rhodopseudomonas sphaeroides R-26 detected by the singlet ground-state absorbance

    NASA Astrophysics Data System (ADS)

    Den Blanken, H. J.; Van Der Zwet, G. P.; Hoff, A. J.

    1982-01-01

    We have measured zero-field resonance transitions of the triplet state of the primary donor monitoring the transmittance at 890 nm at 1.2 K in isolated reaction centers of Rhodopseudomonas sphaeroides R-26. The transitions correspond to a decrease in transmittance, confirming the energy transfer model for the transitions detected via the antenna fluorescence in whole cells.

  13. The lowest triplet state of azulene- h8 and azulene- d8 in liquid solution. . II. Phosphorescence and E-type delayed fluorescence

    NASA Astrophysics Data System (ADS)

    Nickel, Bernhard; Klemp, Dieter

    1993-08-01

    In liquid isopentane the lowest triplet (T 1) state of azulene- h8 and azulene- d8 can be populated by triplet energy transfer from phenazine. At low temperatures (≲ 150 K) two delayed luminescences are observed: phosphorescence and E-type delayed S 1→ S 0 fluorescence (EDF) due to thermally activated intersystem crossing (ISC) T 1⇝S 1. At higher temperature (≳ 200 K) the EDF dominates. The temperature dependence of the EDF is in accord with ISC T 1⇝S 1 being the only temperature-dependent triplet decay process. Light-atom out-of-plane bending modes are likely to be the promoting modes. The literature on the lowest triplet state of azulene is reviewed.

  14. Generation of Phosphorescent Triplet States via Photoinduced Electron Transfer: Energy and Electron Transfer Dynamics in Pt Porphyrin-Rhodamine B Dyads

    PubMed Central

    Mani, Tomoyasu; Niedzwiedzki, Dariusz M.; Vinogradov, Sergei A.

    2012-01-01

    Control over generation and dynamics of excited electronic states is fundamental to their utilization in all areas of technology. We present the first example of multichromophoric systems in which emissive triplet states are generated via a pathway involving photoinduced electron transfer (ET), as opposed to local intrachromophoric processes. In model dyads, PtP-Phn-pRhB+ (1-3, n=1-3), comprising platinum(II) meso-tetraarylporphyrin (PtP) and rhodamine B piperazine derivative (pRhB+), linked by oligo-p-phenylene bridges (Phn), upon selective excitation of pRhB+ at a frequency below that of the lowest allowed transition of PtP, room-temperature T1→S0 phosphorescence of PtP was observed. The pathway leading to the emissive PtP triplet state includes excitation of pRhB+, ET with formation of the singlet radical pair, intersystem crossing within that pair and subsequent radical recombination. Due to the close proximity of the triplet energy levels of PtP and pRhB+, reversible triplet-triplet (TT) energy transfer between these states was observed in dyads 1 and 2. As a result, the phosphorescence of PtP was extended in time by the long decay of the pRhB+ triplet. Observation of ET and TT in the same series of molecules enabled direct comparison of the distance attenuation factors β between these two closely related processes. PMID:22400988

  15. Unraveling Triplet Excitons Photophysics in Hyper-Cross-Linked Polymeric Nanoparticles: Toward the Next Generation of Solid-State Upconverting Materials.

    PubMed

    Monguzzi, Angelo; Mauri, Michele; Frigoli, Michel; Pedrini, Jacopo; Simonutti, Roberto; Larpent, Chantal; Vaccaro, Gianfranco; Sassi, Mauro; Meinardi, Francesco

    2016-07-21

    The technological application of sensitized upconversion based on triplet-triplet annihilation (TTA) requires the transition from systems operating in liquid solutions to solid-state materials. Here, we demonstrate that the high upconversion efficiency reported in hyper-cross-linked nanoparticles does not originate from residual mobility of the embedded dyes as it happens in soft hosts. The hyper-reticulation from one side blocks the dyes in fixed positions, but on the other one, it suppresses the nonradiative spontaneous decay of the triplet excitons, reducing intramolecular relaxations. TTA is thus enabled by an unprecedented extension of the triplet lifetime, which grants long excitons diffusion lengths by hopping among the dye framework and gives rise to high upconversion yield without any molecular displacement. This finding paves the way for the design of a new class of upconverting materials, which in principle can operate at excitation intensities even lower than those requested in liquid or in rubber hosts. PMID:27388582

  16. Singlet and triplet state transitions of carotenoids in the antenna complexes of higher-plant photosystem I.

    PubMed

    Croce, Roberta; Mozzo, Milena; Morosinotto, Tomas; Romeo, Alessandro; Hienerwadel, Rainer; Bassi, Roberto

    2007-03-27

    In this work, the spectroscopic characteristics of carotenoids associated with the antenna complexes of Photosystem I have been studied. Pigment composition, absorption spectra, and laser-induced triplet-minus-singlet (T-S) spectra were determined for native LHCI from the wild type (WT) and lut2 mutant from Arabidopsis thaliana as well as for reconstituted individual Lhca WT and mutated complexes. All WT complexes bind lutein and violaxanthin, while beta-carotene was found to be associated only with the native LHCI preparation and recombinant Lhca3. In the native complexes, the main lutein absorption bands are located at 492 and 510 nm. It is shown that violaxanthin is able to occupy all lutein binding sites, but its absorption is blue-shifted to 487 and 501 nm. The "red" lutein absorbing at 510 nm was found to be associated with Lhca3 and Lhca4 which also show a second carotenoid, peaking around 490 nm. Both these xanthophylls are involved in triplet quenching and show two T-S maxima: one at 507 nm (corresponding to the 490 nm singlet absorption) and the second at 525 nm (with absorption at 510 nm). The "blue"-absorbing xanthophyll is located in site L1 and can receive triplets from chlorophylls (Chl) 1012, 1011, and possibly 1013. The red-shifted spectral component is assigned to a lutein molecule located in the L2 site. A 510 nm lutein was also observed in the trimers of LHCII but was absent in the monomers. In the case of Lhca, the 510 nm band is present in both the monomeric and dimeric complexes. We suggest that the large red shift observed for this xanthophyll is due to interaction with the neighbor Chl 1015. In the native T-S spectrum, the contribution of carotenoids associated with Lhca2 is visible while the one of Lhca1 is not. This suggests that in the Lhca2-Lhca3 heterodimeric complex energy equilibration is not complete at least on a fast time scale. PMID:17326666

  17. An apparatus for pulsed ESR and DNP experiments using optically excited triplet states down to liquid helium temperatures.

    PubMed

    Eichhorn, T R; Haag, M; van den Brandt, B; Hautle, P; Wenckebach, W Th; Jannin, S; van der Klink, J J; Comment, A

    2013-09-01

    In standard Dynamic Nuclear Polarization (DNP) electron spins are polarized at low temperatures in a strong magnetic field and this polarization is transferred to the nuclear spins by means of a microwave field. To obtain high nuclear polarizations cryogenic equipment reaching temperatures of 1 K or below and superconducting magnets delivering several Tesla are required. This equipment strongly limits applications in nuclear and particle physics where beams of particles interact with the polarized nuclei, as well as in neutron scattering science. The problem can be solved using short-lived optically excited triplet states delivering the electron spin. The spin is polarized in the optical excitation process and both the cryogenic equipment and magnet can be simplified significantly. A versatile apparatus is described that allows to perform pulsed dynamic nuclear polarization experiments at X-band using short-lived optically excited triplet sates. The efficient (4)He flow cryostat that cools the sample to temperatures between 4 K and 300 K has an optical access with a coupling stage for a fiber transporting the light from a dedicated laser system. It is further designed to be operated on a neutron beam. A combined pulse ESR/DNP spectrometer has been developed to observe and characterize the triplet states and to perform pulse DNP experiments. The ESR probe is based on a dielectric ring resonator of 7 mm inner diameter that can accommodate cubic samples of 5mm length needed for neutron experiments. NMR measurements can be performed during DNP with a coil integrated in the cavity. With the presented apparatus a proton polarization of 0.5 has been achieved at 0.3 T. PMID:23838526

  18. An apparatus for pulsed ESR and DNP experiments using optically excited triplet states down to liquid helium temperatures

    NASA Astrophysics Data System (ADS)

    Eichhorn, T. R.; Haag, M.; van den Brandt, B.; Hautle, P.; Wenckebach, W. Th.; Jannin, S.; van der Klink, J. J.; Comment, A.

    2013-09-01

    In standard Dynamic Nuclear Polarization (DNP) electron spins are polarized at low temperatures in a strong magnetic field and this polarization is transferred to the nuclear spins by means of a microwave field. To obtain high nuclear polarizations cryogenic equipment reaching temperatures of 1 K or below and superconducting magnets delivering several Tesla are required. This equipment strongly limits applications in nuclear and particle physics where beams of particles interact with the polarized nuclei, as well as in neutron scattering science. The problem can be solved using short-lived optically excited triplet states delivering the electron spin. The spin is polarized in the optical excitation process and both the cryogenic equipment and magnet can be simplified significantly. A versatile apparatus is described that allows to perform pulsed dynamic nuclear polarization experiments at X-band using short-lived optically excited triplet sates. The efficient 4He flow cryostat that cools the sample to temperatures between 4 K and 300 K has an optical access with a coupling stage for a fiber transporting the light from a dedicated laser system. It is further designed to be operated on a neutron beam. A combined pulse ESR/DNP spectrometer has been developed to observe and characterize the triplet states and to perform pulse DNP experiments. The ESR probe is based on a dielectric ring resonator of 7 mm inner diameter that can accommodate cubic samples of 5 mm length needed for neutron experiments. NMR measurements can be performed during DNP with a coil integrated in the cavity. With the presented apparatus a proton polarization of 0.5 has been achieved at 0.3 T.

  19. 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

    2015-03-01

    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. PMID:25686256

  20. Pi topology and spin alignment in unique photoexcited triplet and quintet states arising from four unpaired electrons of an organic spin system.

    PubMed

    Teki, Yoshio; Toichi, Tetuya; Nakajima, Satoru

    2006-03-01

    Syntheses, electronic structures in the ground state, unique photoexcited states, and spin alignment are reported for novel biradical 1, which was designed as an ideal model compound to investigate photoinduced spin alignment in the excited state. Electron spin resonance (ESR), time-resolved ESR (TRESR), and laser-excitation pulsed ESR experiments were carried out. The magnetic properties were examined with a SQUID magnetometer. In the electronic ground state, two radical moieties interact very weakly (almost no interaction) with each other through the closed-shell diphenylanthracene spin coupler. On photoirradiation, a novel lowest photoexcited state with the intermediate spin (S = 1) arising from four unpaired electrons with low-lying quintet (S = 2) photoexcited state was detected. The unique triplet state has an interesting electronic structure, the D value of which is reduced by antiferromagnetic spin alignment between two radical spins through the excited triplet spin coupler. The general theoretical predictions of the spin alignment and the reduction of the fine-structure splitting of the triplet bis(radical) systems are presented. The fine-structure splitting of the unique photoexcited triplet state of 1, as well as the existence of the low-lying quintet state, is interpreted well on the basis of theoretical predictions. Details of the spin alignment in the photoexcited states are discussed. PMID:16372362

  1. Geminate and Nongeminate Recombination of Triplet Excitons Formed by Singlet Fission

    NASA Astrophysics Data System (ADS)

    Bayliss, Sam L.; Chepelianskii, Alexei D.; Sepe, Alessandro; Walker, Brian J.; Ehrler, Bruno; Bruzek, Matthew J.; Anthony, John E.; Greenham, Neil C.

    2014-06-01

    We report the simultaneous observation of geminate and nongeminate triplet-triplet annihilation in a solution-processable small molecule TIPS-tetracene undergoing singlet exciton fission. Using optically detected magnetic resonance, we identify recombination of triplet pairs directly following singlet fission, as well as recombination of triplet excitons undergoing bimolecular triplet-triplet annihilation. We show that the two processes give rise to distinct magnetic resonance spectra, and estimate the interaction between geminate triplet excitons to be 60 neV.

  2. Triplet states as non-radiative traps in multichromophoric entities: single molecule spectroscopy of an artificial and natural antenna system

    NASA Astrophysics Data System (ADS)

    Hofkens, Johan; Schroeyers, Wouter; Loos, Davey; Cotlet, Mircea; Köhn, Fabian; Vosch, Tom; Maus, Michael; Herrmann, A.; Müllen, K.; Gensch, Thomas; De Schryver, F. C.

    2001-09-01

    Energy transfer in antenna systems, ordered arrays of chromophores, is one of the key steps in the photosynthetic process. The photophysical processes taking place in such multichromophoric systems, even at the single molecule level, are complicated and not yet fully understood. Instead of directly studying individual antenna systems, we have chosen to focus first on systems for which the amount of chromophores and the interactions among the chromophores can be varied in a systematic way. Dendrimers with a controlled number of chromophores at the rim fulfill those requirements perfectly. A detailed photophysical study of a second-generation dendrimer, containing eight peryleneimide chromophores at the rim, was performed 'J. Am. Chem. Soc., 122 (2000) 9278'. One of the most intriguing findings was the presence of collective on/off jumps in the fluorescence intensity traces of the dendrimers. This phenomenon can be explained by assuming a simultaneous presence of both a radiative trap (energetically lowest chromophoric site) and a non-radiative trap (triplet state of one chromophore) within one individual dendrimer. It was shown that an analogue scheme could explain the collective on/off jumps in the fluorescence intensity traces of the photosynthetic pigment B-phycoerythrin (B-PE) ( Porphyridium cruentum). The different values of the triplet lifetime that could be recovered for a fluorescence intensity trace of B-PE were correlated with different intensity levels in the trace, suggesting different chromophores acting as a trap as function of time.

  3. Collective modes, ac response, and magnetic properties of the three-dimensional Dirac semimetal in the triplet superconducting state

    NASA Astrophysics Data System (ADS)

    Rosenstein, B.; Shapiro, B. Ya.; Shapiro, I.

    2015-08-01

    It was recently shown that conventional phonon-electron interactions may induce a triplet pairing state in time-reversal invariant three-dimensional Dirac semimetals. Starting from the microscopic model of the isotropic Dirac semimetal, the Ginzburg-Landau equations for the vector order parameter is derived using the Gor'kov technique. The collective modes including gapless Goldstone modes and gapped Higgs modes of various polarizations are identified. They are somewhat analogous to the modes in the B phase of He3, although in the present case quantitatively there is a pronounced difference between longitudinal and transverse components. The difference is caused by the vector nature of the order parameter leading to two different coherence lengths or penetration depths. The system is predicted to be highly dissipative due to the Goldstone modes. The time-dependent Ginzburg-Landau model in the presence of external fields is used to investigate some optical and magnetic properties of such superconductors. The ac conductivity of a clean sample depends on the orientation of the order parameter. It is demonstrated that the difference between the penetration depths results in rotation of the polarization vector of microwave passing a slab made of this material. The upper critical magnetic field Hc 2 was found. It turns out that at fields close to Hc 2 the order parameter orients itself perpendicular to the field direction. In certain range of parameters the triplet superconducting phase persists at arbitrarily high magnetic field like in some p -wave superconductors.

  4. 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

  5. Theoretical study of the reaction of ethane with oxygen molecules in the ground triplet and singlet delta states.

    PubMed

    Sharipov, Alexander S; Starik, Alexander M

    2012-08-23

    Quantum chemical calculations are carried out to study the reaction of ethane with molecular oxygen in the ground triplet and singlet delta states. Transition states, intermediates, and possible products of the reaction on the triplet and singlet potential energy surfaces are identified on the basis of the coupled-cluster method. The basis set dependence of coupled-cluster energy values is estimated by the second-order perturbation theory. The values of energy barriers are also refined by using the compound CBS-Q and G3 techniques. It was found that the C(2)H(6) + O(2)(X(3)Σ(g)(-)) reaction leads to the formation of C(2)H(5) and HO(2) products, whereas the C(2)H(6) + O(2)(a(1)Δ(g)) process produces C(2)H(4) and H(2)O(2) molecules. The appropriate rate constants of these reaction paths are estimated on the basis of variational and nonvariational transition-state theories assuming tunneling and possible nonadiabatic transitions in the temperature range 500-4000 K. The calculations showed that the rate constant of the C(2)H(6) + O(2)(a(1)Δ(g)) reaction path is much greater than that of the C(2)H(6) + O(2)(X(3)Σ(g)(-)) one. At the same time, the singlet and triplet potential surface intersection is detected that leads to the appearance of the nonadiabatic quenching channel O(2)(a(1)Δ(g)) + C(2)H(6) → O(2)(X (3)Σ(g)(-)) + C(2)H(6). The rate constant of this process is estimated with the use of the Landau-Zener model. It is demonstrated that, in the case of the existence of thermal equilibrium in the distribution of molecules over the electronic states, at low temperatures (T < 1200 K) the main products of the reaction of C(2)H(6) with O(2) are C(2)H(4) and H(2)O(2), rather than C(2)H(5) and HO(2). At higher temperature (T > 1200 K) the situation is inverted. PMID:22823469

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

    NASA Astrophysics Data System (ADS)

    Glimsdal, Eirik; Westlund, Robert; Lindgren, Mikael

    2009-05-01

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

  7. Triplet State of the Semiquinone–Rieske Cluster as an Intermediate of Electronic Bifurcation Catalyzed by Cytochrome bc1

    PubMed Central

    2013-01-01

    Efficient energy conversion often requires stabilization of one-electron intermediates within catalytic sites of redox enzymes. While quinol oxidoreductases are known to stabilize semiquinones, one of the famous exceptions includes the quinol oxidation site of cytochrome bc1 (Qo), for which detection of any intermediate states is extremely difficult. Here we discover a semiquinone at the Qo site (SQo) that is coupled to the reduced Rieske cluster (FeS) via spin–spin exchange interaction. This interaction creates a new electron paramagnetic resonance (EPR) transitions with the most prominent g = 1.94 signal shifting to 1.96 with an increase in the EPR frequency from X- to Q-band. The estimated value of isotropic spin–spin exchange interaction (|J0| = 3500 MHz) indicates that at a lower magnetic field (typical of X-band) the SQo–FeS coupled centers can be described as a triplet state. Concomitantly with the appearance of the SQo–FeS triplet state, we detected a g = 2.0045 radical signal that corresponded to the population of unusually fast-relaxing SQo for which spin–spin exchange does not exist or is too small to be resolved. The g = 1.94 and g = 2.0045 signals reached up to 20% of cytochrome bc1 monomers under aerobic conditions, challenging the paradigm of the high reactivity of SQo toward molecular oxygen. Recognition of stable SQo reflected in g = 1.94 and g = 2.0045 signals offers a new perspective on understanding the mechanism of Qo site catalysis. The frequency-dependent EPR transitions of the SQo–FeS coupled system establish a new spectroscopic approach for the detection of SQo in mitochondria and other bioenergetic systems. PMID:23941428

  8. Triplet state of the semiquinone-Rieske cluster as an intermediate of electronic bifurcation catalyzed by cytochrome bc1.

    PubMed

    Sarewicz, Marcin; Dutka, Małgorzata; Pintscher, Sebastian; Osyczka, Artur

    2013-09-17

    Efficient energy conversion often requires stabilization of one-electron intermediates within catalytic sites of redox enzymes. While quinol oxidoreductases are known to stabilize semiquinones, one of the famous exceptions includes the quinol oxidation site of cytochrome bc1 (Qo), for which detection of any intermediate states is extremely difficult. Here we discover a semiquinone at the Qo site (SQo) that is coupled to the reduced Rieske cluster (FeS) via spin-spin exchange interaction. This interaction creates a new electron paramagnetic resonance (EPR) transitions with the most prominent g = 1.94 signal shifting to 1.96 with an increase in the EPR frequency from X- to Q-band. The estimated value of isotropic spin-spin exchange interaction (|J0| = 3500 MHz) indicates that at a lower magnetic field (typical of X-band) the SQo-FeS coupled centers can be described as a triplet state. Concomitantly with the appearance of the SQo-FeS triplet state, we detected a g = 2.0045 radical signal that corresponded to the population of unusually fast-relaxing SQo for which spin-spin exchange does not exist or is too small to be resolved. The g = 1.94 and g = 2.0045 signals reached up to 20% of cytochrome bc1 monomers under aerobic conditions, challenging the paradigm of the high reactivity of SQo toward molecular oxygen. Recognition of stable SQo reflected in g = 1.94 and g = 2.0045 signals offers a new perspective on understanding the mechanism of Qo site catalysis. The frequency-dependent EPR transitions of the SQo-FeS coupled system establish a new spectroscopic approach for the detection of SQo in mitochondria and other bioenergetic systems. PMID:23941428

  9. 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.

  10. Aromatic C-H Activation in the Triplet Excited State of Cyclometalated Platinum(II) Complexes Using Visible Light.

    PubMed

    Juliá, Fabio; González-Herrero, Pablo

    2016-04-27

    The visible-light driven cyclometalation of arene substrates containing an N-donor heteroaromatic moiety as directing group by monocyclometalated Pt(II) complexes is reported. Precursors of the type [PtMe(C^N)(N^CH)], where N^CH is 2-phenylpyridine (ppyH) or related compunds with diverse electronic properties and C^N is the corresponding cyclometalated ligand, afford homoleptic cis-[Pt(C^N)2] complexes upon irradiation with blue LEDs at room temperature with evolution of methane. Heteroleptic derivatives cis-[Pt(ppy)(C'^N')] are obtained analogously from [PtMe(ppy)(N'^C'H)], where N'^C'H represents an extended set of heteroaromatic compounds. Experimental and computational studies demonstrate an unprecedented C-H oxidative addition, which is initiated by a triplet excited state of metal-to-ligand charge-transfer (MLCT) character and leads to a detectable Pt(IV) methyl hydride intermediate. PMID:27058394

  11. Non-adiabatic and intersystem crossing dynamics in SO2. II. The role of triplet states in the bound state dynamics studied by surface-hopping simulations

    NASA Astrophysics Data System (ADS)

    Mai, Sebastian; Marquetand, Philipp; González, Leticia

    2014-05-01

    The importance of triplet states in the photorelaxation dynamics of SO2 is studied by mixed quantum-classical dynamics simulations. Using the SHARC method, standing for Surface Hopping including ARbitrary Couplings, intersystem crossing (ISC) processes caused by spin-orbit coupling are found occurring on an ultrafast time scale (few 100 fs) and thus competing with internal conversion. While in the singlet-only dynamics only oscillatory population transfer between the 1B1 and 1A2 states is observed, in the dynamics including singlet and triplet states we find additionally continuous ISC to the 3B2 state and to a smaller extent to the 3B1/3A2 coupled states. The populations obtained from the dynamics are discussed with respect to the overall nuclear motion and in the light of recent TRPEPICO studies [I. Wilkinson, A. E. Boguslavskiy, J. Mikosch, D. M. Villeneuve, H.-J. Wörner, M. Spanner, S. Patchkovskii, and A. Stolow, "Excited state dynamics in SO2. I. Bound state relaxation studied by time-resolved photoelectron-photoion coincidence spectroscopy," J. Chem. Phys. 140, 204301 (2014)].

  12. 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. PMID:27040752

  13. 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.

  14. Triplet-triplet absorption of 2-(2'-hydroxyphenyl) benzoxazole (HBO) in polar solvents

    NASA Astrophysics Data System (ADS)

    Yang, Guoqiang; Morlet-Savary, Fabrice; Peng, Zhaokui; Wu, Shikang; Fouassier, Jean-Pierre

    1996-07-01

    The transient TT absorption spectra of 2-(2'-hydroxyphenyl) benzoxazole (HBO) have been measured in liquid polar solvents and in polymethylthacrylate. In non-protonic polar solvents the main TT absorption is from the keto form of the compound ( 3K ∗). With a triplet sensitizer the compound just gives a TT absorption of its enol from ( 3E ∗) after triplet energy transfer from the sensitizer to HBO. The excited state intramolecular proton transfer (ESIPT) from the enol form to keto form occurs just in the singlet state. The protonic solvent can break the intramolecular hydrogen bond of HBO and decrease the ESIPT process. In solid solution both 3E ∗ and 3K ∗ can be formed and the TT absorptions were detected because of the inhibition of the rotational conformation transfer.

  15. 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. PMID:22891949

  16. 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. PMID:25603170

  17. 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.

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

    PubMed

    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 (3)P+ triplet ground state at strong confinements and the (5)S- quintet ground state at the weak ones, the energy crossing occurring at ω ≈ 0.0240919. PMID:25084902

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

    NASA Astrophysics Data System (ADS)

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

    2013-10-01

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

  20. Fine-Tuning of β-Substitution to Modulate the Lowest Triplet Excited States: A Bioinspired Approach to Design Phosphorescent Metalloporphyrinoids.

    PubMed

    Ke, Xian-Sheng; Zhao, Hongmei; Zou, Xiaoran; Ning, Yingying; Cheng, Xin; Su, Hongmei; Zhang, Jun-Long

    2015-08-26

    Learning nature's approach to modulate photophysical properties of NIR porphyrinoids by fine-tuning β-substituents including the number and position, in a manner similar to naturally occurring chlorophylls, has the potential to circumvent the disadvantages of traditional "extended π-conjugation" strategy such as stability, molecular size, solubility, and undesirable π-π stacking. Here we show that such subtle structural changes in Pt(II) or Pd(II) cis/trans-porphodilactones (termed by cis/trans-Pt/Pd) influence photophysical properties of the lowest triplet excited states including phosphorescence, Stokes shifts, and even photosensitization ability in triplet-triplet annihilation reactions with rubrene. Prominently, the overall upconversion capability (η, η = ε·Φ(UC)) of Pd or Pt trans-complex is 10(4) times higher than that of cis-analogue. Nanosecond time-resolved infrared (TR-IR) spectroscopy experiments showed larger frequency shift of ν(C═O) bands (ca. 10 cm(-1)) of cis-complexes than those of trans-complexes in the triplet excited states. These spectral features, combining with TD-DFT calculations, suggest the strong electronic coupling between the lactone moieties and the main porphyrin chromophores and thus the importance of precisely positioning β-substituents by mimicking chlorophylls, as an alternative to "extended π-conjugation", in designing NIR active porphyrinoids. PMID:26247480

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

    PubMed

    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

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

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

    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.

  3. DNA binding of Pd(TC3), a conformable cationic porphyrin with a long-lived triplet state.

    PubMed

    Ghimire, Srijana; Bork, Matthew A; Zhang, Hanyu; Fanwick, Phillip E; Zeller, Matthias; Choi, Jong Hyun; McMillin, David R

    2016-09-28

    The goal of this work has been to synthesize and investigate Pd(TC3), an intercalating porphyrin that has conformable substituents capable of groove binding to B-form DNA. (TC3 denotes the doubly deprotonated form of 5,10,15,20-tetra[3-(3'-methylimidazolium-1'-yl)prop-1-yl]porphyrin.) Palladium(ii) is an apt choice for the central metal ion because it remains strictly four-coordinate and provides for a luminescent triplet excited state with a long lifetime. The DNA hosts are hairpin-forming sequences programmed to differ in base composition. Luminescence, absorbance, and circular dichroism results are consistent with the idea that congruent structural reorganization takes place at the host and ligand during uptake. Photoexcitation of DNA-bound Pd(TC3) generates a comparatively modest steady state concentration of singlet oxygen, due to a relatively slow reaction with molecular oxygen in solution. The sheer size of the substituent groups disfavors quenching, but groove-binding interactions compound the problem by inhibiting mobility. The results show how ligand design affects adduct structure as well as function. PMID:27534907

  4. Microwave Spectra of Furazan. IV. Rotation Spectra of Vibrationally Excited States of Perdeuterated Furazan

    NASA Astrophysics Data System (ADS)

    Stiefvater, Otto L.

    1990-10-01

    The pure rotation spectra of molecules in 25 vibrationally excited states of perdeuterated furazan, C2D2N2O, have been studied by double resonance modulation (DRM) microwave spectroscopy. Twelve of these spectra have been correlated, -on the basis of relative intensity measurements under DRM -, with fundamental vibrations as previously established by IR spectroscopy. Rotational parameters for these 12 fundamental levels are reported, and the contributions to the effective rotational constants and to the inertia defect of the ground state of d2 -furazan have been determined for 10 modes of vibration.

  5. Low temperature pulsed EPR study at 34 GHz of the triplet states of the primary electron donor P865 and the carotenoid in native and mutant bacterial reaction centers of Rhodobacter sphaeroides†

    PubMed Central

    Marchanka, Aliaksandr; Paddock, Mark; Lubitz, Wolfgang; van Gastel, Maurice

    2008-01-01

    The photosynthetic charge separation in bacterial reaction centers occurs predominantly along one of two nearly symmetric branches of cofactors. Low temperature EPR spectra of the triplet states of the chlorophyll and carotenoid pigments in the reaction center of Rb. sphaeroides R-26.1, 2.4.1 and two double mutants GD(M203)/AW(M260) and LH(M214)/AW(M260) have been recorded at 34 GHz to investigate the relative activities of the ‘A’ and ‘B’ branches. The triplet states are found to derive from radical pair and intersystem crossing mechanisms and the rates of formation are anisotropic. The former mechanism is operative for Rb. sphaeroides R-26.1, 2.4.1 and mutant GD(M203)/AW(M260) and indicates that A-branch charge separation proceeds at temperatures down to 10 K. The latter mechanism, derived from the spin polarization and operative for mutant LH(M214)/AW(M260) indicates that no long-lived radical pairs are formed upon direct excitation of the primary donor and that virtually no charge separation at the B-branch occurs at low temperatures. When the temperature is raised above 30 K, B-branch charge separation is observed, which is at most 1% of A-branch charge separation. B-branch radical pair formation can be induced at 10 K with low yield by direct excitation of the bacteriopheophytin of the B-branch at 590 nm. The formation of a carotenoid triplet state is observed. The rate of formation depends on the orientation of the reaction center in the magnetic field and is caused by a magnetic field dependence of the oscillation frequency by which the singlet and triplet radical pair precursor states interchange. Combination of these findings with literature data provides strong evidence that the thermally activated transfer step on the B-branch occurs between the primary donor, P865, and the accessory bacteriochlorophyll, whereas this step is barrierless down to 10 K along the A-branch. PMID:18052205

  6. Low-temperature pulsed EPR study at 34 GHz of the triplet states of the primary electron Donor P865 and the carotenoid in native and mutant bacterial reaction centers of Rhodobacter sphaeroides.

    PubMed

    Marchanka, Aliaksandr; Paddock, Mark; Lubitz, Wolfgang; van Gastel, Maurice

    2007-12-25

    The photosynthetic charge separation in bacterial reaction centers occurs predominantly along one of two nearly symmetric branches of cofactors. Low-temperature EPR spectra of the triplet states of the chlorophyll and carotenoid pigments in the reaction center of Rhodobacter sphaeroides R-26.1, 2.4.1 and two double-mutants GD(M203)/AW(M260) and LH(M214)/AW(M260) have been recorded at 34 GHz to investigate the relative activities of the "A" and "B" branches. The triplet states are found to derive from radical pair and intersystem crossing mechanisms, and the rates of formation are anisotropic. The former mechanism is operative for Rb. sphaeroides R-26.1, 2.4.1, and mutant GD(M203)/AW(M260) and indicates that A-branch charge separation proceeds at temperatures down to 10 K. The latter mechanism, derived from the spin polarization and operative for mutant LH(M214)/AW(M260), indicates that no long-lived radical pairs are formed upon direct excitation of the primary donor and that virtually no charge separation at the B-branch occurs at low temperatures. When the temperature is raised above 30 K, B-branch charge separation is observed, which is at most 1% of A-branch charge separation. B-branch radical pair formation can be induced at 10 K with low yield by direct excitation of the bacteriopheophytin of the B-branch at 590 nm. The formation of a carotenoid triplet state is observed. The rate of formation depends on the orientation of the reaction center in the magnetic field and is caused by a magnetic field dependence of the oscillation frequency by which the singlet and triplet radical pair precursor states interchange. Combination of these findings with literature data provides strong evidence that the thermally activated transfer step on the B-branch occurs between the primary donor, P865, and the accessory bacteriochlorophyll, whereas this step is barrierless down to 10 K along the A-branch. PMID:18052205

  7. Generating Light from Upper Excited Triplet States: A Contribution to the Indirect Singlet Yield of a Polymer OLED, Helping to Exceed the 25% Singlet Exciton Limit

    PubMed Central

    Jankus, Vygintas; Aydemir, Murat; Dias, Fernando B.

    2016-01-01

    The mechanisms by which light is generated in an organic light emitting diode have slowly been elucidated over the last ten years. The role of triplet annihilation has demonstrated how the “spin statistical limit” can be surpassed, but it cannot account for all light produced in the most efficient devices. Here, a further mechanism is demonstrated by which upper excited triplet states can also contribute to indirect singlet production and delayed fluorescence. Since in a device the population of these TN states is large, this indirect radiative decay channel can contribute a sizeable fraction of the total emission measured from a device. The role of intra‐ and interchain charge transfer states is critical in underpinning this mechanism. PMID:27610333

  8. On implementing nondestructive triplet Toffoli gate with entanglement swapping operations via the GHZ state analysis

    NASA Astrophysics Data System (ADS)

    Guo, Ying; Zhao, Zhisheng; Wang, Yijun; Wang, Ping; Huang, Dazu; Lee, Moon Ho

    2014-09-01

    We investigate an novel implementation of a Toffoli gate using multiple independent auxiliary photons prepared beforehand in single-qubit states. This gate can be performed nondestructively with entanglement swapping via the Greenberger-Horne-Zeilinger state analysis. We evaluate the performance of the proposed Toffoli gate with the fidelity based on different computation bases. The multi-qubit-entanglement gate is no longer theoretical since it can be implemented in principle with single-qubit photons.

  9. 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.

  10. Twofold spin-triplet pairing states and tunneling conductance in ferromagnet/ferromagnet/iron pnictide superconductor heterojunctions

    SciTech Connect

    Yang, X.; Tao, Y.C.; Dong, Z.C.; Hu, J.G.

    2013-06-15

    By applying an extended eight-component Bogoliubov–de Gennes equation, we study theoretically the tunneling conductance in clean ferromagnet/ferromagnet/iron pnictide superconductor (FM/FM/iron-based SC) heterojunctions. Under the condition of noncollinear magnetizations, twofold novel Andreev reflections exist due to the existence of two bands in the SC, in which the incident electron and the two Andreev-reflected holes, belonging to the same spin subband, form twofold spin-triplet pairing states near the FM/iron-based SC interface. It is shown that the conversions of the conductance not only between the zero-bias peak and valley at zero energy but also between the peaks and dips at two gap energies are strongly dependent on both the interband coupling strength in the SC and the spin polarization in the FM. The qualitative differences from tunneling into a conventional s-wave SC are also presented, which may help with experimentally probing and identifying the antiphase s-wave pairing symmetry in the iron-based SC. -- Highlights: •An eight-component Bogoliubov–de Gennes (BDG) equation. •Twofold novel ARs and twofold usual ARs. •Conversions of conductance between the zero-bias peak and valley at zero energy. •Conversions of conductance between peaks and dips at two gap energies. •The importance of the interband coupling strength in the SC.

  11. 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

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

    NASA Astrophysics Data System (ADS)

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

    2002-04-01

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

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

    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

    2014-06-01

    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. PMID:26273880

  15. Multidimensional least-squares resolution of Raman spectra from intermediates in sensitized photochemical reactions

    SciTech Connect

    Fister, J.C. III; Harris, J.M.

    1995-12-01

    Transient resonance Raman spectroscopy is used to elicit reaction kinetics and intermediate spectra from sensitized photochemical reactions. Nonlinear least-squares analysis of Raman spectra of a triplet-state photosensitizer (benzophenone), acquired as a function of laser intensity and/or quencher concentration allow the Raman spectra of the sensitizer excited state and intermediate photoproducts to be resolved from the spectra of the ground state and solvent. In cases where physical models describing the system kinetics cannot be found, factor analysis techniques are used to obtain the intermediate spectra. Raman spectra of triplet state benzophenone and acetophenone, obtained as a function of laser excitation kinetics, and the Raman spectra of intermediates formed by energy transfer (triplet-state biacetyl) and hydrogen abstraction (benzhydrol radical) are discussed.

  16. 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.

  17. Quenching of the triplet state of Safranine-O by aliphatic amines in AOT reverse micelles studied by transient absorption spectroscopy.

    PubMed

    Porcal, Gabriela V; Chesta, Carlos A; Biasutti, M Alicia; Bertolotti, Sonia G; Previtali, Carlos M

    2012-02-01

    The photophysics of Safranine-O (3,6-diamino-2,7-dimethyl-5 phenyl phenazinium chloride) (SfH(+)Cl(-)) was investigated in reverse micelles (RMs) of AOT (sodium bis(2-ethylhexyl)sulfosuccinate) with special emphasis on the triplet state processes. The triplet is formed in its monoprotonated form, independently of the pH of the water used to prepare the RMs. While the intersystem crossing quantum yields in RMs are similar to those in organic solvents, the triplet lifetime is much longer. Since the pH in the water pool of AOT RMs is close to 5 and the triplet state of the dye is subjected to proton quenching, the long lifetime indicates that the dye resides in a region where it cannot be reached by protons during its lifetime. All the measurements indicate that the dye is localized in the interface, sensing a medium of micropolarity similar to EtOH : water (3:1) mixtures. The quenching by aliphatic amines was also investigated. While the quenching by the hydrophobic tributylamine is similar to that in methanol, the hydro-soluble triethanolamine is one order of magnitude more effective in RMs than in homogeneous solution. In the latter case the quenching process is interpreted by a very fast intramicellar quenching, the overall kinetics being controlled by the exchange of amine molecules between RMs. Semireduced dye is formed in the quenching process in RMs in the di-protonated state with a comparable quantum yield to the monoprotonated state formed in homogeneous solvents. The results point to the advantage of the reverse micellar system for the generation of active radicals for the initiation of vinyl polymerization, since a much lower concentration of amine can be employed with similar quantum yields. PMID:22105094

  18. Photochemistry on surfaces: Fluorescence emission of monomers and dimers and triplet state absorption of acridine orange adsorbed on microcrystalline cellulose

    NASA Astrophysics Data System (ADS)

    Wilkinson, F.; Worrall, D. R.; Ferreira, L. F. Vieira

    1992-02-01

    Prompt fluorescence as well as delayed fluorescence emission of acridine orange was detected at room temperature from samples where this dye is adsorbed on microcrystalline cellulose. Ground state absorption studies provided evidence for dimer formation of the dye when adsorbed on cellulose, and the equilibrium constant for dimerisation was determined as 1.6±0.1 × 10 6mol -1g. At low loadings of acridine orange on cellulose (<1 μmol g -1) the fluorescence emission is mainly due to the monomer and is similar to that observed in ethanolic solutions where little aggregation occurs, and peaks at 530 nm. A linear dependence of the fluorescence intensity on the amount of light absorbed by the dye was established for these "diluted" samples. However, at higher loadings (>20 μmol g -1), the fluorescence intensity decreases, and the emission is broad with its maximum at 620 nm, and is mainly due to the dimer. By assuming that the excited monomer and dimer of acridine orange are the only emitting species, it was possible to determine the fluorescence quantum yields for these two species when adsorbed on microcrystalline cellulose as 0.95±0.05 and 0.40±0.10, respectively. Pulsed emission studies at room temperature in the millisecond time-range also revealed monomer and dimer emissions on this longer time-scale. These are shown to be due to thermally activated delayed fluorescence arising from the triplet states of monomer and dimer acridine orange as confirmed by diffuse reflectance transient absorption studies.

  19. Narrow Energy Gap between Triplet and Singlet Excited States of Sn2+ in Borate Glass

    PubMed Central

    Masai, Hirokazu; Yamada, Yasuhiro; Suzuki, Yuto; Teramura, Kentaro; Kanemitsu, Yoshihiko; Yoko, Toshinobu

    2013-01-01

    Transparent inorganic luminescent materials have attracted considerable scientific and industrial attention recently because of their high chemical durability and formability. However, photoluminescence dynamics of ns2-type ions in oxide glasses has not been well examined, even though they can exhibit high quantum efficiency. We report on the emission property of Sn2+-doped strontium borate glasses. Photoluminescence dynamics studies show that the peak energy of the emission spectrum changes with time because of site distribution of emission centre in glass. It is also found that the emission decay of the present glass consists of two processes: a faster S1-S0 transition and a slower T1-S0 relaxation, and also that the energy difference between T1 and S1 states was found to be much smaller than that of (Sn, Sr)B6O10 crystals. We emphasize that the narrow energy gap between the S1 and T1 states provides the glass phosphor a high quantum efficiency, comparable to commercial crystalline phosphors. PMID:24345869

  20. Narrow energy gap between triplet and singlet excited states of Sn2+ in borate glass.

    PubMed

    Masai, Hirokazu; Yamada, Yasuhiro; Suzuki, Yuto; Teramura, Kentaro; Kanemitsu, Yoshihiko; Yoko, Toshinobu

    2013-01-01

    Transparent inorganic luminescent materials have attracted considerable scientific and industrial attention recently because of their high chemical durability and formability. However, photoluminescence dynamics of ns(2)-type ions in oxide glasses has not been well examined, even though they can exhibit high quantum efficiency. We report on the emission property of Sn(2+)-doped strontium borate glasses. Photoluminescence dynamics studies show that the peak energy of the emission spectrum changes with time because of site distribution of emission centre in glass. It is also found that the emission decay of the present glass consists of two processes: a faster S1-S0 transition and a slower T1-S0 relaxation, and also that the energy difference between T1 and S1 states was found to be much smaller than that of (Sn, Sr)B6O10 crystals. We emphasize that the narrow energy gap between the S1 and T1 states provides the glass phosphor a high quantum efficiency, comparable to commercial crystalline phosphors. PMID:24345869

  1. The effect of the structure and conformational dynamics on quenching of triplet states of porphyrins and their chemical dimers by molecular oxygen and on singlet oxygen generation

    NASA Astrophysics Data System (ADS)

    Ivashin, N. V.; Shchupak, E. E.; Sagun, E. I.

    2015-01-01

    Quantum-chemical calculations are performed to analyze the factors affecting rate constant k T of quenching of the lowest triplet state by molecular oxygen and quantum yield γΔ of singlet oxygen generation in chemical dimers of porphyrins bound by phenyl spacers at one of the meso positions (OEP)2-Ph, (TPP)2, and their Zn complexes. It is established that, for both types of dimers, the triplet excitation is localized on one of the macrocycles. The steric hindrance of macrocycles at the site of the phenyl ring of (OEP)2-Ph, (ZnOEP)2-Ph, and their monomeric analogues OEP-Ph and ZnOEP-Ph facilitates its rotation by 90° in the triplet state. The lowest triplet state energy in this ( U) conformation is lower than 7800 cm-1, which makes impossible electronic excitation energy transfer to molecular oxygen. The potential barrier of transformation to the U conformation is considerably lower for dimers than for monomers. Because of this, the rate of conformational transformations for dimers is higher and some of the (OEP)2-Ph and (ZnOEP)2-Ph molecules have time to transform into the new U conformation before diffusion collision with O2 molecules in solution. This leads to a noticeable decrease in γΔ in accordance with experimental data. It is shown that the behavior of k T in the series of the studied dimers, their monomeric analogues, and relative compounds corresponds to the model of dipole-dipole electronic excitation energy transfer 1(3M⋯3Σ{g/-}) → 1(1M0⋯1Δg) in collisional complexes.

  2. Secondary organic aerosol from aqueous reactions of green leaf volatiles with organic triplet excited states and singlet molecular oxygen.

    PubMed

    Richards-Henderson, Nicole K; Pham, Andrew T; Kirk, Benjamin B; Anastasio, Cort

    2015-01-01

    Vegetation emits a class of oxygenated hydrocarbons--the green leaf volatiles (GLVs)--under stress or damage. Under foggy conditions GLVs might be a source of secondary organic aerosol (SOA) via aqueous reactions with hydroxyl radical (OH), singlet oxygen ((1)O2*), and excited triplet states ((3)C*). To examine this, we determined the aqueous kinetics and SOA mass yields for reactions of (3)C* and (1)O2* with five GLVs: methyl jasmonate (MeJa), methyl salicylate (MeSa), cis-3-hexenyl acetate (HxAc), cis-3-hexen-1-ol (HxO), and 2-methyl-3-butene-2-ol (MBO). Second-order rate constants with (3)C* and (1)O2* range from (0.13-22) × 10(8) M(-1) s(-1) and (8.2-60) × 10(5) M(-1) s(-1) at 298 K, respectively. Rate constants with (3)C* are independent of temperature, while values with (1)O2* show significant temperature dependence (Ea = 20-96 kJ mol(-1)). Aqueous SOA mass yields for oxidation by (3)C* are (84 ± 7)%, (80 ± 9)%, and (38 ± 18)%, for MeJa, MeSa, and HxAc, respectively; we did not measure yields for other conditions because of slow kinetics. The aqueous production of SOA from GLVs is dominated by (3)C* and OH reactions, which form low volatility products at a rate that is approximately half that from the parallel gas-phase reactions of GLVs. PMID:25426693

  3. Phosphorescence study of chlorophyll d photophysics. Determination of the energy and lifetime of the photo-excited triplet state. Evidence of singlet oxygen photosensitization.

    PubMed

    Neverov, Konstantin V; Santabarbara, Stefano; Krasnovsky, Alexander A

    2011-09-01

    Chlorophyll d (Chl d) is the major pigment in both photosystems (PSI and II) of the cyanobacterium Acaryochloris marina, whose pigment composition represents an interesting alternative in oxygenic photosynthesis. While abundant information is available relative to photophysical properties of Chl a , the understanding of Chl d photophysics is still incomplete. In this paper, we present for the first time a characterization of Chl d phosphorescence, which accompanies radiative deactivation of the photoexcited triplet state of this pigment. Reliable information was obtained on the energy and lifetime of the Chl d triplet state in frozen solutions at 77 K using diethyl ether and aqueous dispersions of Triton X100 as solvents. It is shown that triplet Chl d is effectively populated upon photoexcitation of pigment molecules and efficiently sensitizes singlet oxygen phosphorescence in aerobic solutions under ambient conditions. The data obtained are compared with the previous results of the phosphorescence studies of Chl a and Pheo a, and their possible biological implications are discussed. PMID:21573948

  4. S-wave triplet doubly-excited states 3Se of Li+ below the N=2 excitation threshold of Li2+

    NASA Astrophysics Data System (ADS)

    Gien, T. T.

    2009-11-01

    The Harris-Nesbet variational method was considered for the determination of the series a and b of S-wave triplet doubly-excited-state resonances 3Se of Li+ below the N=2 excitation threshold of Li2+. Because of the high accuracy of our numerical method, we succeeded in determining a greatest number of these doubly-excited states below this threshold, including those lying very close to the threshold. Five of these high-lying doubly excited states were determined by us for the first time.

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

    NASA Astrophysics Data System (ADS)

    Pistol, M. E.; Monemar, B.

    1986-05-01

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

  6. 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.

  7. Electron transfer in the quenching of protonated triplet methylene blue by ground-state molecules of the dye

    SciTech Connect

    Kamat, P.V.; Lichtin, N.N.

    1981-04-02

    A Q-switched pulsed ruby laser emitting at 694.3 nm was used in an investigation by means of flash photolysis-kinetic spectrophotometry of the mechanism of quenching of the monoprotonated lowest triplet state of methylene blue, /sup 3/MBH/sup 2 +/, by the ground state of the dye, MB/sup +/. Quenching in 0.01 N acid is accompanied by electron transfer to give the half-oxidized and half-reduced ion radicals, MB/sup 2 +/. and MBH/sup +/.. The absorption spectrum of MB/sup 2 +/. has been characterized in several media from 360 to 600 nm. The rate constant for quenching, k/sub q/, varies with solvent, ionic strength, and nature of anions with values around 1 x 10/sup 8/ M/sup -1/ s/sup -1/ in water, aqueous CH/sub 3/CN, and aqueous EtOH. The efficiency of net electron transfer in quenching, F/sub 1/(= k/sub et//k/sub q/), varies with solvent but is independent of the ionic strength or the nature of the anions. F/sub 1/ varies inversely with polarity of the solvent from 0.055 in water to 0.48 in 90% (vol/vol) aqueous CH/sub 3/CN. On the basis of analogy to the behavior of a number of other quenchers and the observed linear variation of the function ln ((1/F/sub 1/)-1) with Kosower's polarity parameter Z, it is suggested that reversible electron transfer is the only significant mechanism of quenching of /sup 3/MBH/sup 2 +/ by MB/sup +/(S/sub 0/). Both MBH/sup +/. and MB/sup 2 +/. decay by second-order processes in solvents containing 75% (vol/vol) or less of organic component but the specific rates are different for the two species in most media. It is suggested that in the latter media both cross reaction of MBH/sup +/. with MB/sup 2 +/. and biomolecular reaction of two molecules of the same radical occur. This study shows that ground-state quenching can significantly reduce the sunlight engineering efficency of photogalvanic conversion in systems incorporating relatively concentrated dyes.

  8. Microwave Spectra of Furazan. III. Rotation Spectra of Vibrationally Excited States

    NASA Astrophysics Data System (ADS)

    Stiefvater, Otto L.

    1990-10-01

    The pure rotational spectra of molecules in 21 vibrationally excited states of the heterocyclic compound furazan (C2H2N2O) have been detected and studied by DRM microwave spectroscopy. Rotational parameters are reported for the 12 fundamental levels below 1500 cm-1 , and the contri-butions from 10 vibrational modes to the effective rotational constants and to the inertia defect of furazan are calculated.

  9. Raman spectra of selected transuranium trihalides in the solid state

    SciTech Connect

    Wilmarth, W.R.; Begun, G.M.; Haire, R.G.; Peterson, J.R.

    1988-10-15

    Raman spectral data have been obtained from a number of transuranium trihalides in the solid state. The Raman spectra of these actinide compounds are reported and compared to the published Raman spectra of isostructural compounds. Tentative symmetry assignments have been made for the observed Raman-active lattice vibrations based on nuclear site symmetry analysis of their respective crystal structures and comparisons to the symmetry assignments made for isostructural lanthanide compounds. The Raman spectral data obtained in this study represent a partial data base for the use of Raman spectroscopy for identifying the crystal structures exhibited by these and isostructural compounds.

  10. Electron paramagnetic resonance of the excited triplet state of metal-free and metal-substituted cytochrome c.

    PubMed Central

    Angiolillo, P J; Vanderkooi, J M

    1995-01-01

    The photoactivated metastable triplate states of the porphyrin (free-base, i.e., metal-free) zinc and tin derivatives of horse cytochrome c were investigated using electron paramagnetic resonance. Zero-field splitting parameters, line shape, and Jahn-Teller distortion in the temperature range 3.8-150 K are discussed in terms of porphyrin-protein interactions. The zero-field splitting parameters D for the free-base, Zn and Sn derivatives are 465 x 10(-4), 342 x 10(-4) and 353 x 10(-4) cm-1, respectively, and are temperature invariant over the temperature ranges studied. AN E value at 4 K of 73 x 10(-4) cm-1 was obtained for Zn cytochrome c, larger than any previously found for Zn porphyrins derivatives of hemeproteins, showing that the heme site of cytochrome c imposes an asymmetric field. Though the E value for Zn cytochrome c is large, the geometry of the site appears quite constrained, as indicated by a spectral line shape showing a single species. Intersystem crossing occurred predominantly to the T2 > zero-field spin sublevel. EPR line shape changes with respect to temperature of Zn cyt c are interpreted in terms of vibronic coupling, and a maximum Jahn-Teller crystal-field splitting of approximately 180 cm-1 is obtained. Sn cytochrome c in comparison with the Zn protein exhibits a photoactivated triplet line shape that is less well resolved in the X-Y region. The magnitude of E value is approximately 60 x 10(-4) cm-1 at 4 K; its value rapidly tends toward zero with increasing temperature, from which a value for the Jahn-Teller crystal-field splitting of > or = 40 cm-1 is estimated. In contrast to those for the metal cytochromes, the magnitude of E value for the free-base derivative was essentially zero at all temperatures studied. This finding is discussed as a consequence of an excited-state tautomerization process that occurs even at 4 K. PMID:7647253

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

    PubMed

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

    2016-02-01

    Time-resolved pump-probe photoelectron spectroscopy has been used to study the relaxation dynamics of gaseous [Pt2(μ-P2O5H2)4 + 2H](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 (1)A2u state and concomitant rise in population of the triplet (3)A2u 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 (1)A2u state takes only a few picoseconds, ESETD from the triplet (3)A2u 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. [Pt2(μ-P2O5H2)4 + 2H](2-) is the first example of a photoexcited multianion for which ESETD has been observed following ISC. PMID:26851919

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

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

    Time-resolved pump-probe photoelectron spectroscopy has been used to study the relaxation dynamics of gaseous [Pt2(μ-P2O5H2)4 + 2H]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 1A2u state and concomitant rise in population of the triplet 3A2u 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 1A2u state takes only a few picoseconds, ESETD from the triplet 3A2u 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. [Pt2(μ-P2O5H2)4 + 2H]2- is the first example of a photoexcited multianion for which ESETD has been observed following ISC.

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

    DOE PAGESBeta

    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

  14. 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. PMID:26233127

  15. 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.

  16. 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.

  17. 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.

  18. 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

    2015-12-01

    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

  19. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2014-02-01

    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.

  1. 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.

  2. Magnetism and experimental consequences of pz-wave spin triplet state in quasi-one-dimensional A2Cr3As3 superconductors

    NASA Astrophysics Data System (ADS)

    Wu, Xianxin; Yang, Fan; Le, Congcong; Yuan, Jing; Qin, Shengshan; Fan, Heng; Hu, Jiangping

    The recently discovered quasi-one dimensional superconductors A2Cr3As3(A=K,Rb,Cs), are found to possess strong frustrated magnetic fluctuations and are nearby a novel in-out co-planar magnetic ground state. Then, we find that the triplet pz-wave pairing is strongly favored. Finally, with pz wave pairing state, we obtain the specific heat, superfluid density, Knight shift and spin relaxation rate and find that all these properties at low temperature (T <state in this quasi-one dimensional system is anisotropic: the in-plane superfluid density varies as Δρ∥ ~ T but the out-plane one varies as Δρ⊥ ~T3 at low temperature. The anisotropic upper critical field reported in experiment is consistent with the Sz = 0 (i.e,(↑ ↓ + ↓ ↑)) pz-wave pairing state. We also suggest the phase-sensitive dc-SQUID measurements to pin down the triplet pz-wave pairing state.

  3. 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.

  4. Geminate and nongeminate recombination of triplet excitons formed by singlet fission.

    PubMed

    Bayliss, Sam L; Chepelianskii, Alexei D; Sepe, Alessandro; Walker, Brian J; Ehrler, Bruno; Bruzek, Matthew J; Anthony, John E; Greenham, Neil C

    2014-06-13

    We report the simultaneous observation of geminate and nongeminate triplet-triplet annihilation in a solution-processable small molecule TIPS-tetracene undergoing singlet exciton fission. Using optically detected magnetic resonance, we identify recombination of triplet pairs directly following singlet fission, as well as recombination of triplet excitons undergoing bimolecular triplet-triplet annihilation. We show that the two processes give rise to distinct magnetic resonance spectra, and estimate the interaction between geminate triplet excitons to be 60 neV. PMID:24972236

  5. Phasic Triplet Markov Chains.

    PubMed

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

    2014-11-01

    Hidden Markov chains have been shown to be inadequate for data modeling under some complex conditions. In this work, we address the problem of statistical modeling of phenomena involving two heterogeneous system states. Such phenomena may arise in biology or communications, among other fields. Namely, we consider that a sequence of meaningful words is to be searched within a whole observation that also contains arbitrary one-by-one symbols. Moreover, a word may be interrupted at some site to be carried on later. Applying plain hidden Markov chains to such data, while ignoring their specificity, yields unsatisfactory results. The Phasic triplet Markov chain, proposed in this paper, overcomes this difficulty by means of an auxiliary underlying process in accordance with the triplet Markov chains theory. Related Bayesian restoration techniques and parameters estimation procedures according to the new model are then described. Finally, to assess the performance of the proposed model against the conventional hidden Markov chain model, experiments are conducted on synthetic and real data. PMID:26353069

  6. Kinetic Monte Carlo study of triplet-triplet annihilation in organic phosphorescent emitters

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

    The triplet-triplet annihilation (TTA) rate in organic phosphorescent materials such as used in organic light-emitting diodes is determined predominantly either by the rate of single-step Förster-type triplet-triplet interactions, or by multi-step triplet diffusion. We show how kinetic Monte Carlo simulations may be used to analyze the role of both processes. Under steady state conditions, the effective triplet-triplet interaction rate coefficient, kTT, which is often regarded as a constant, is found to depend actually on the number of excitons lost upon a triplet-triplet interaction process and to show a significant higher-order dependence on the triplet volume density. Under the conditions encountered in transient photoluminescence (PL) studies, kTT is found to be effectively constant in the case of diffusion-dominated TTA. However, for the case of single-step TTA, a strongly different decay of the emission intensity is found, which also deviates from an analytic expression proposed in the literature. We discuss how the transient PL response may be used to make a distinction between both mechanisms. The simulations are applied to recently published work on the dye concentration dependence of the TTA rate in materials based on the archetypal green emitter tris[2-phenylpyridine]iridium (Ir(ppy)3).

  7. 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.

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

    SciTech Connect

    Dudek, Jozef J.; Edwards, Robert G.; Richards, David G.; Thomas, Christopher E.; Peardon, Michael J.

    2011-05-24

    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{pi}{pi} 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.

  9. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

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

  11. Auroral N{sub 2} emissions and the effect of collisional processes on N{sub 2} triplet state vibrational populations

    SciTech Connect

    Morrill, J.S.; Benesch, W.M.

    1996-01-01

    Previous model results have shown that the N{sub 2} 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 N{sub 2} collisions begin to play a more prominent part. The authors are developing a model which will yield steady state vibrational level populations for both the singlet and triplet valence states of N{sub 2}. The model currently provides results for the seven low-lying N{sub 2} triplet states (A {sup 3}{Sigma}{sub u}{sup +}, B {sup 3}{Pi}{sub g}, W {sup 3}{Delta}{sub u}, B{prime}{sup 3}{Sigma}{sub u}, C{sup 3}{Pi}{sub u}, D{sup 3}{Sigma}{sub u}{sup +}, and E{sup 3}{Sigma}{sub g}{sup +}). 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)). The authors 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{prime} states and vibrational redistribution within the A state vibrational manifold, both due to collisions with ground state N{sub 2}. The present work compares the current model results with those of a previous model as well as ground, airborne, and rocket observations. The comparison between N{sub 2}(A) (VK) and N{sub 2}(B) (1PG) vibrational level populations predicted by this model and a number of auroral observations indicate that the current model achieves a significant improvement in the fit between calculation and observation. 81 refs., 12 figs., 2 tabs.

  12. 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.

  13. Stochastic Liouville equation studies of FT-EPR spectra of singlet-triplet mixing photo-chemically generated radical pair system.

    PubMed

    Hanaishi, Ryuji

    2008-07-01

    A stochastic Liouville equation (SLE) was numerically solved to obtain pulsed Fourier-transform (FT) EPR spectra on a radical pair system created in a photo-induced chemical reaction. Numerical calculations were applied to the photo-chemical reaction of deuterated acetone and 2-propanol at low temperatures. In this reaction system, the antiphase structures of the EPR signals, so called spin-correlated radical pair (SCRP) signals of two identical isopropyl ketyl radicals and spin-polarized free isopropyl ketyl radicals were observed by FT-EPR and continuous wave time-resolved (CW TR) EPR techniques. In the present work, FT-EPR spectra of the antiphase structure signals of the radical pair themselves as well as spin-polarized free radical signals were simulated. Additionally, rising behavior of free radical signals polarized by the radical pair mechanism (RPM) was also clarified. Furthermore two-dimensional (2D) FT-EPR nutation spectra were simulated in the both cases with and without the radical pairs by the use of SLE. In these simulations, strong DC components in the nutation frequency dimension, were well reproduced as was obtained in experiments. It was shown that relaxation during the microwave pulse was essential for the appearance of the DC components. PMID:18486510

  14. On the solid-state NMR spectra of naproxen

    NASA Astrophysics Data System (ADS)

    Czernek, Jiří

    2015-01-01

    Two previous measurements of the 13C and 1H NMR isotropic chemical shifts in crystalline naproxen, which is an important pharmaceutical compound, are confronted with the results obtained from several theoretical approaches capable of the proper treatment of solid-phase effects. In the underlying geometrical optimizations, two crystal structures are considered. The agreement between the data sets is quantified, including an evaluation of the similarity between the experimental solid-state NMR spectra. The 13C-1H heteronuclear correlations are analyzed, and their various assignments are discussed employing the statistical treatment of the differences between the measured and theoretical isotropic chemical shifts.

  15. Direct evidence of complete charge separation in the excited triplet state of 1,2-( N-arylaziridino)-[60] fullerenes by means of time-resolved electron paramagnetic resonance

    NASA Astrophysics Data System (ADS)

    Yamauchi, Seigo; Iwasaki, Yohei; Ohba, Yasunori; Awen, Bahlul Z. S.; Ouchi, Akihiko

    2005-08-01

    Some of 1,6-( N-substituted) aza-[60] fulleroids ( 1) and their corresponding photochemical reaction products, 1,2-( N-substituted) aziridino-[60] fullerenes ( 2) showed peculiar transient absorption peaks depending on the N-substituents. Although these bands are considered to concern with very slow photochemical rearrangements 1 → 2 in the excited triplet state, no definitive evidence has been obtained yet. We report on the character of the excited triplet states in these compounds by means of a time-resolved electron paramagnetic resonance technique. Definitive evidence on the involvement of intra-molecular charge transfer states is shown in this Letter.

  16. Ab initio calculation of the NH(3sigma-)-NH(3sigma-) interaction potentials in the quintet, triplet, and singlet states.

    PubMed

    Dhont, Guillaume S F; van Lenthe, Joop H; Groenenboom, Gerrit C; van der Avoird, Ad

    2005-11-01

    We present the ab initio potential-energy surfaces of the NH-NH complex that correlate with two NH molecules in their 3sigma- electronic ground state. Three distinct potential-energy surfaces, split by exchange interactions, correspond to the coupling of the S(A) = 1 and S(B) = 1 electronic spins of the monomers to dimer states with S = 0, 1, and 2. Exploratory calculations on the quintet (S = 2), triplet (S = 1), and singlet (S = 0) states and their exchange splittings were performed with the valence bond self-consistent-field method that explicitly accounts for the nonorthogonality of the orbitals on different monomers. The potential surface of the quintet state, which can be described by a single Slater determinant reference function, was calculated at the coupled cluster level with single and double excitations and noniterative treatment of the triples. The triplet and singlet states require multiconfiguration reference wave functions and the exchange splittings between the three potential surfaces were calculated with the complete active space self-consistent-field method supplemented with perturbative configuration interaction calculations of second and third orders. Full potential-energy surfaces were computed as a function of the four intermolecular Jacobi coordinates, with an aug-cc-pVTZ basis on the N and H atoms and bond functions at the midpoint of the intermolecular vector R. An analytical representation of these potentials was given by expanding their dependence on the molecular orientations in coupled spherical harmonics, and representing the dependence of the expansion coefficients on the intermolecular distance R by the reproducing kernel Hilbert space method. The quintet surface has a van der Waals minimum of depth D(e) = 675 cm(-1) at R(e) = 6.6a0 for a linear geometry with the two NH electric dipoles aligned. The singlet and triplet surfaces show similar, slightly deeper, van der Waals wells, but when R is decreased the weakly bound NH dimer

  17. Complex Study of Electronic States and Spectra of 3-Nitroformazans

    NASA Astrophysics Data System (ADS)

    Valiev, R. R.; Drozdova, A. K.; Petunin, P. V.; Postnikov, P. S.; Trusova, M. E.; Cherepanov, V. N.

    2016-06-01

    A theoretical and experimental study of electronic states and the absorption spectra of 3-nitroformazan molecules was conducted. The results of the study show that the first electron transition is σ→π-transition, and the second one is π→π-transition. The energies of the transitions calculated using methods RI-CC2 and TDDFT correlate well with the experimental measurements. The dependence of the first electron transition wavenumber on the degree of electron donating and accepting of substitutituents was studied using empirical constants. High correlation between the constants of Hammett, Braun, and wavenumbers (TDDFT) of the first electron transition shows that the description of electronic states of the studied 3-nitroformazans is correct.

  18. Fetofetal transfusion in triplets.

    PubMed Central

    Rehan, V. K.; Menticoglou, S. M.; Seshia, M. M.; Bowman, J. M.

    1995-01-01

    A case of fetofetal transfusion syndrome (FFTS) in a monochorionic triplet pregnancy, in which all three fetuses shared a common circulation, is reported. All babies were born alive, although two died within two days of delivery. This case highlights the problem of FFTS with accompanying high perinatal morbidity and mortality in naturally occurring monochorionic triplet gestations. Images Figure 2 Figure 3 PMID:7552596

  19. Phenol transformation and dimerisation, photosensitised by the triplet state of 1-nitronaphthalene: A possible pathway to humic-like substances (HULIS) in atmospheric waters

    NASA Astrophysics Data System (ADS)

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

    2013-05-01

    The nitroderivatives of polycyclic aromatic hydrocarbons are potentially important photosensitisers in the atmospheric condensed phase. Here we show that the triplet state of 1-nitronaphthalene (31NN*) is able to directly react with phenol, causing its transformation upon irradiation of 1NN in aqueous solution. Additional but less important processes of phenol degradation are reactions with rad OH and 1O2, both photogenerated by irradiated 1NN. Dihydroxybiphenyls and phenoxyphenols were detected as main phenol transformation intermediates, likely formed by dimerisation of phenoxy radicals that would be produced upon phenol oxidation by 31NN*. Very interestingly, irradiation with 1NN shifted the fluorescence peaks of phenol (Ex/Em = 220-230/280-320 nm and 250-275/280-320 nm, with Ex/Em = excitation and emission wavelengths) to a region that overlaps with “M-like” fulvic substances (Ex/Em = 250-300/330-400 nm). Moreover, at longer irradiation times a further peak appeared (Ex/Em = 300-450/400-450 nm), which is in the region of HULIS fluorescence. Irradiated material was also able to photoproduce 1O2, thus showing photosensitisation properties. Therefore, compounds with fluorescence properties that closely resemble those of HULIS (they would be identified as HULIS by fluorescence if present in environmental samples) can be formed upon triplet-sensitised transformation of phenol by 1NN.

  20. Long-range supercurrents induced by the interference effect of opposite-spin triplet state in clean superconductor-ferromagnet structures

    NASA Astrophysics Data System (ADS)

    Meng, Hao; Wu, Jiansheng; Wu, Xiuqiang; Ren, Mengyuan; Ren, Yajie

    2016-07-01

    By now it is known that in an s-wave superconductor-ferromagnet-superconductor (SF S) structure the supercurrent induced by spin singlet pairs can only transmit a short distance of the order of magnetic coherence length. The long-range supercurrent, taking place on the length scale of the normal metal coherence length, will be maintained by equal-spin triplet pairs, which can be generated by magnetic inhomogeneities in the system. In this paper, we have shown an unusual long-range supercurrent, which can take place in clean {{SF}}1{F}2S junction with non-parallel orientation of magnetic moments. The mechanism behind the enhancement of Josephson current is provided by the interference of the opposite-spin triplet states deriving from S/{F}1 and {F}2/S interfaces when both ferromagnetic layers have the same values of the length and exchange field. This discovery can offer a natural explanation for recent experiments (Robinson et al 2010 Phys. Rev. Lett. 104 207001; Baek et al 2014 Nat. Commun. 5 3888).

  1. 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.

  2. 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.

  3. Luminescence and ODMR studies of X-traps for triplet excitons in organic crystals

    NASA Astrophysics Data System (ADS)

    Avdeenko, A. A.; Buravtseva, L. M.; Gorobchenko, V. S.; Eremenko, V. V.; Izvekov, S. V.; Kravchenko, A. E.; Pyshkin, O. S.; Sugakov, V. I.

    1997-03-01

    The excited triplet states of shallow X-traps in neat single crystals of 4,4-dichlorobenzophenone were studied at liquid helium temperature by luminescence spectroscopy and magnetic resonance with optical detection. The vibrational phosphorescence bands, the polarization of phosphorescence spectra, and the triplet zero-field splitting parameters of these traps have been analyzed. A specific model of the structure defect (a molecule is turned by 180° on its long axis) has been considered in organic crystals of benzophenone type which consist of molecules whose dipole moments compensate each other in a unit cell. The calculated depth of such a dipole X-trap for triplet excitons in 4,4-dichlorobenzophenone crystals at the account of a defect molecule relaxation upon its slewing was found to be comparable with the experimental one.

  4. Low-energy chlorophyll states in the CP43 antenna protein complex: simulation of various optical spectra. II.

    PubMed

    Reppert, Mike; Zazubovich, Valter; Dang, Nhan C; Seibert, Michael; Jankowiak, Ryszard

    2008-08-14

    redistribution of oscillator strength during the NPHB process helps to assign Chls contributing to the low-energy states. It is demonstrated that the 4.2 K asymmetric triplet-bottleneck (transient) hole is mostly contributed to by both A and B states, with the hole profile described by a subensemble of pigments, which are the lowest-energy pigments (B s- and A s-type) in their complexes. The same lowest-energy Chls contribute to the observed fluorescence spectra. On the basis of our excitonic calculations, the best Chl candidates that contribute to the low-energy A and B states are Chl 44 and Chl 37, respectively. PMID:18642950

  5. The Predicted Spectrum and Singlet-Triplet Interaction of the Hypermetallic Molecule SrOSr

    NASA Astrophysics Data System (ADS)

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

    2013-10-01

    In accordance with previous studies in our group on Be, Mg, and Ca hypermetallic oxides, we find that SrOSr has a linear X-1Σg+ ground electronic state and a very low lying first excited -3Σu+ 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 X-1Σg+ and -3Σu+ 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 X- and - electronic states and find them to be very small.

  6. 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.

  7. A multireference configuration interaction study of the hyperfine structure of the molecules CCO, CNN, and NCN in their triplet ground states

    NASA Astrophysics Data System (ADS)

    Suter, H. U.; Huang, M.-B.; Engels, B.

    1994-11-01

    The hyperfine structures of the isoelectronic molecules CCO, CNN, and NCN in their triplet ground states (X 3Σ-) are investigated by means of ab initio methods. The infrared frequencies and geometries are determined and compared with experiment. Configuration selected multireference configuration interaction calculations in combination with perturbation theory to correct the wave function (MRD-CI/BK) employing extended atomic orbital (AO) basis sets yielded very accurate hyperfine properties. The theoretical values for CCO are in excellent agreement with the experimental values determined by Smith and Weltner [J. Chem. Phys. 62, 4592 (1975)]. For CNN, the first assignment of Smith and Weltner for the two nitrogen atoms has to be changed. A qualitative discussion of the electronic structure discloses no simple relation between the structure of the singly occupied orbitals and the measured hyperfine coupling constants. Vibrational effects were found to be of little importance.

  8. Negative Polaron and Triplet Exciton Diffusion inOrganometallic “Molecular Wires”

    SciTech Connect

    Schanze, K.S.; Miller, J.; Keller, J.M.; Sean McIlroy, S.; Sreearuothai, P.; Danilov, E.O.; Jiang, H.; Glusac, K.D.; Miller, J.R.

    2011-07-27

    The dynamics of negative polaron and triplet exciton transport within a series of monodisperse platinum (Pt) acetylide oligomers is reported. The oligomers consist of Pt-acetylide repeats, [PtL{sub 2}-C {triple_bond} C-Ph-C {triple_bond} C-]{sub n} (where L = PBu{sub 3} and Ph = 1,4-phenylene, n = 2, 3, 6, and 10), capped with naphthalene diimide (NDI) end groups. The Pt-acetylide segments are electro- and photoactive, and they serve as conduits for transport of electrons (negative polaron) and triplet excitons. The NDI end groups are relatively strong acceptors, serving as traps for the carriers. Negative polaron transport is studied by using pulse radiolysis/transient absorption at the Brookhaven National Laboratory Laser-Electron Accelerator Facility (LEAF). Electrons are rapidly attached to the oligomers, with some fraction initially residing upon the Pt-acetylide chains. The dynamics of transport are resolved by monitoring the spectral changes associated with transfer of electrons from the chain to the NDI end group. Triplet exciton transport is studied by femtosecond-picosecond transient absorption spectroscopy. Near-UV excitation leads to rapid production of triplet excitons localized on the Pt-acetylide chains. The excitons transport to the chain ends, where they are annihilated by charge separation with the NDI end group. The dynamics of triplet transport are resolved by transient absorption spectroscopy, taking advantage of the changes in spectra associated with decay of the triplet exciton and rise of the charge-separated state. The results indicate that negative polarons and excitons are transported rapidly, on average moving distances of 3 nm in less than 200 ps. Analysis of the dynamics suggests diffusive transport by a site-to-site hopping mechanism with hopping times of 27 ps for triplets and <10 ps for electrons.

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

    PubMed

    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. PMID:25282507

  10. 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.

  11. Electronic states and spectra of BiH

    NASA Astrophysics Data System (ADS)

    Setzer, Klaus-Dieter; Fink, Ewald H.; Hill, Christian; Brown, John M.

    2015-06-01

    Emission spectra of bismuth monohydride (BiH) radicals excited by energy transfer from O2(a1Δg) or NF(a1Δ) or by a DC discharge in a mixture of bismuth vapor and hydrogen in a fast-flow system were studied in the wavenumber range from 4000 to 25 000 cm-1 with a Fourier-transform spectrometer. The X21 → X10+ transition between the spin components of the X3Σ- ground state was remeasured at high spectral resolution and signal/noise. Six bands of the Δv = 0 and +1 sequences near 4950 and 6600 cm-1 have been observed. The low-J lines of these bands are split into up to 10 hfs components due to magnetic hyperfine structure splitting of the X21 levels. In addition to the previously observed electric dipole lines, weak magnetic dipole lines show up in the Δv = 0 but not in the Δv = +1 bands. The intensities of the Δv = +1 bands are about a factor of 10 higher than expected from Franck-Condon factors indicating that the electric dipole transition moment μX2-X1 shows a strong dependence on internuclear distance. Near 5450 cm-1, the 0-0 and 1-1 bands of the transition a2 → X21 from the hitherto unknown first excited state a1Δ(a2) to the upper component of the ground state have been observed. The lines in these bands show the magnetic hfs splitting of both the a2 and X21 states. In the visible range near 21 300 and 16 300 cm-1, the 0-0 and 1-1 bands of the b0+ → X10+ system and the 0-0 band of the b0+ → X21 transition likewise have been measured at high resolution. The lines of the latter band also show the hfs splitting of the X21 state. Least-squares fits have yielded rotational and vibrational constants of the X10+, X21, a2, and b0+ states as well as hfs parameters of the X21 and a2 states and the electronic energy of the hitherto unknown a1Δ(a2) level.

  12. 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). PMID:26801214

  13. Application of equation-of-motion coupled-cluster methods to low-lying singlet and triplet electronic states of HBO and BOH

    NASA Astrophysics Data System (ADS)

    DeYonker, Nathan J.; Li, Se; Yamaguchi, Yukio; Schaefer, Henry F.; Crawford, T. Daniel; King, Rollin A.; Peterson, Kirk A.

    2005-06-01

    The equilibrium structures and physical properties of the X˜Σ+1 linear electronic states, linear excited singlet and triplet electronic states of hydroboron monoxide (HBO) (ÃΣ-1, B˜Δ1, ãΣ+3, and b˜Δ3) and boron hydroxide (BOH) (ÃΣ+1, B˜Π1, and b˜Π3), and their bent counterparts (HBO ãA'3, b˜A″3, ÃA″1, B˜A'1 and BOH X˜A'1, b˜A'3, c˜A″3, ÃA'1, B˜A'1, C˜A″1) are investigated using excited electronic state ab initio equation-of-motion coupled-cluster (EOM-CC) methods. A new implementation of open-shell EOM-CC including iterative partial triple excitations (EOM-CC3) was tested. Coupled-cluster wave functions with single and double excitations (CCSD), single, double, and iterative partial triple excitations (CC3), and single, double, and full triple excitations (CCSDT) are employed with the correlation-consistent quadruple and quintuple zeta basis sets. The linear HBO X˜Σ+1 state is predicted to lie 48.3kcalmol-1 (2.09eV) lower in energy than the BOH X˜Σ+1 linear stationary point at the CCSDT level of theory. The CCSDT BOH barrier to linearity is predicted to lie 3.7kcalmol-1 (0.16eV). With a harmonic zero-point vibrational energy correction, the HBO X˜Σ+1-BOHX˜A'1 energy difference is 45.2kcalmol-1 (1.96eV). The lowest triplet excited electronic state of HBO, ãA'3, has a predicted excitation energy (Te) of 115kcalmol-1 (4.97eV) from the HBO ground state minimum, while the lowest-bound BOH excited electronic state, b˜A'3, has a Te of 70.2kcalmol-1 (3.04eV) with respect to BOH X˜A'1. The Te values predicted for the lowest singlet excited states are ÃA″1←X˜Σ+1=139kcalmol-1 (6.01eV) for HBO and ÃA'1←X˜A'1=102kcalmol-1 (4.42eV) for BOH. Also for BOH, the triplet vertical transition energies are b˜A'3←X˜A'1=71.4kcalmol-1 (3.10eV) and c˜A″3←X˜A'1=87.2kcalmol-1 (3.78eV).

  14. Theoretical Insights into the Photo-Deactivation of Emitting Triplet Excited State of (C^N)Pt(O^O) Complexes: Radiative and Nonradiative Decay Processes.

    PubMed

    Xu, Yanyan; Luo, Yafei; Li, Ming; He, Rongxing; Shen, Wei

    2016-09-01

    In this study, density functional theory (DFT) and time-dependent DFT were employed to elucidate the photo-deactivation mechanisms of (C^N)Pt(O^O) complexes 1-4 (where C^N = 2-phenylpyridine derivatives, O^O = dipivolylmethanoate). To make thorough understanding of the radiative decay, the singlet-triplet splitting energies ΔE(Sn-T1) (n = 1, 2, 3, 4, ...), transition dipole moment μ(Sn) for S0-Sn transitions and the spin-orbit coupling (SOC) matrix elements ⟨T1|HSOC|Sn⟩ were all calculated. Moreover, the spin-orbit coupling between T1 and S0 ⟨T1|HSOC|S0⟩ and Huang-Rhys factors were calculated to estimate the temperature-independent nonradiative decay processes. Meanwhile, the thermal deactivation via metal-centered (3)MC was described to analyze the temperature-dependent nonradiative decay processes. As a result, the effective SOC interaction between the lowest triplet and singlet excited states successfully rationalize why complexes 1 and 3 have higher radiative decay rate constant than that of complex 2, while the larger ⟨T1|HSOC|S0⟩ and lower energy barrier for thermal deactivation in 3 reasonably explains why 3 has larger nonradiative rate than that of 1 and 2. Consequently, it can be concluded that it is the ⟨T1|HSOC|S0⟩ and thermal population of (3)MC that account for the nonemissive behavior of (C^N)Pt(O^O) complexes, and controlling π-conjugation is an efficient method for tuning phosphorescence properties of transition-metal complexes. PMID:27517617

  15. 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. PMID:25681916

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

    NASA Astrophysics Data System (ADS)

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

    2015-05-01

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

  17. Poly methyl methacrylate films containing metallophthalocyanines in the presence of CdTe quantum dots: Non-linear optical behaviour and triplet state lifetimes

    NASA Astrophysics Data System (ADS)

    Britton, Jonathan; Durmuş, Mahmut; Chauke, Vongani; Nyokong, Tebello

    2013-12-01

    Non-linear optical (NLO) parameters were determined for phthalocyanine complexes containing In, Ga and Zn as central metals when embedded in poly (methyl methacrylate) polymer in the absence and presence of quantum dots (QDs) in an effort to create the most optimal optical limiting material. The QDs employed were CdTe-TGA (TGA = thioglylcolic acid). Triplet lifetimes generally increased as the value of the ratio of absorption cross sections of the excited state to that of the ground state (k) decreased on addition of CdTe-TGA to the phthalocyanines. The saturation energy density (Fsat) values were generally smaller in the films when compared to the solutions. Fsat, Ilim, Im[χ(3)]/α and γ all gave values which were of optimal range (i.e. the Im[χ(3)]/α and γ values were high enough to ensure adequate optical limiting but not too high to make the compounds behave like optical filters. Also, the Fsat and Ilim values were small enough to mean that the optical limiting process started at an intensity which was not too high) for complex 10 containing Zn central metal and tetrasubstituted with amino groups.

  18. 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.

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

    PubMed

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

    2016-01-22

    Triplet excitons are pervasive in both organic and inorganic semiconductors but generally remain confined to the material in which they originate. We demonstrated by transient absorption spectroscopy that cadmium selenide semiconductor nanoparticles, selectively excited by green light, engage in interfacial Dexter-like triplet-triplet energy transfer with surface-anchored polyaromatic carboxylic acid acceptors, extending the excited-state lifetime by six orders of magnitude. Net triplet energy transfer also occurs from surface acceptors to freely diffusing molecular solutes, further extending the lifetime while sensitizing singlet oxygen in an aerated solution. The successful translation of triplet excitons from semiconductor nanoparticles to the bulk solution implies that such materials are generally effective surrogates for molecular triplets. The nanoparticles could thereby potentially sensitize a range of chemical transformations that are relevant for fields as diverse as optoelectronics, solar energy conversion, and photobiology. PMID:26798011

  20. Visible light-absorbing rhenium(I) tricarbonyl complexes as triplet photosensitizers in photooxidation and triplet-triplet annihilation upconversion.

    PubMed

    Yi, Xiuyu; Zhao, Jianzhang; Sun, Jifu; Guo, Song; Zhang, Hongli

    2013-02-14

    We prepared N^N Re(I) tricarbonyl chloride complexes (Re-1 and Re-2) that give very strong absorption of visible light. To this end, it is for the first time that boron dipyrimethane (Bodipy) was used to prepare Re(I) tricarbonyl chloride complexes. The π-conjugation linker between the π-conjugation framework of the antenna Bodipy and the Re(I) coordination centre ensures efficient intersystem crossing (ISC). Re-0 without visible light-harvesting ligand was prepared as a model complex in the photophysical studies. Re-1 (with Bodipy) and Re-2 (with carbazole-ethynyl Bodipy) show unprecedented strong absorption of visible light at 536 nm (ε = 91700 M(−1) cm(−1)) and 574 nm (ε = 64,600 M(−1) cm(−1)), respectively. Interestingly, different from Re-0, Re-1 and Re-2 show fluorescence of the ligand, not the phosphorescence of the Re(I) coordination centre. However, long-lived triplet excited states were observed upon visible light excitation (τ(T) = 104.0 μs for Re-1; τ(T) = 127.2 μs for Re-2) vs. the short lifetime of Re-0 (τ(T) = 26 ns). With nanosecond time-resolved transient absorption spectroscopy and DFT calculations, we proved that the triplet excited states of Re-1 and Re-2 are localized on the Bodipy ligands. The complexes were used as triplet photosensitizers for two triplet–triplet-energy-transfer (TTET) processes, i.e.(1)O(2) mediated photooxidation and triplet–triplet annihilation (TTA) upconversion. With the strong visible light-harvesting ability, Re-1 proved to be a better (1)O(2) photosensitizer than the conventional triplet photosensitizer tetraphenylporphyrin (TPP). Significant upconversion was observed with Re-1 as the triplet photosensitizer. Our result is useful for preparation of Re(I) tricarbonyl chloride complexes that show strong absorption of visible light and long-lived triplet excited states and for the application of these complexes as triplet photosensitizers in photocatalysis, photodynamic therapy and TTA upconversion

  1. Highly Efficient Triplet Photosensitizers: A Systematic Approach to the Application of Ir(III) Complexes containing Extended Phenanthrolines.

    PubMed

    Lu, Yue; McGoldrick, Niamh; Murphy, Frances; Twamley, Brendan; Cui, Xiaoneng; Delaney, Colm; Máille, Gearóid M Ó; Wang, Junsi; Zhao, Jianzhang; Draper, Sylvia M

    2016-08-01

    A series of Ir(III) complexes, based on 1,10-phenanthroline featuring aryl acetylene chromophores, were prepared and investigated as triplet photosensitizers. The complexes were synthesized by Sonogashira cross-coupling reactions using a "chemistry-on-the-complex" method. The absorption properties and luminescence lifetimes were successfully tuned by controlling the number and type of light-harvesting group. Intense UV/Vis absorption was observed for the Ir(III) complexes with two light-harvesting groups at the 3- and 8-positions of the phenanthroline. The asymmetric Ir(III) complex (with a triphenylamine (TPA) and a pyrene moiety attached) exhibited the longest lifetime. Red emission was observed for all the complexes in deaerated solutions at room temperature. Their emission at low temperature (77 K) and nanosecond time-resolved transient difference absorption spectra revealed the origin of their triplet excited states. The singlet-oxygen ((1) O2 ) sensitization and triplet-triplet annihilation (TTA)-based upconversion were explored. Highly efficient TTA upconversion (ΦUC =28.1 %) and (1) O2 sensitization (ΦΔ =97.0 %) were achieved for the asymmetric Ir(III) complex, which showed intense absorption in the visible region (λabs =482 nm, ϵ=50900 m(-1)  cm(-1) ) and had a long-lived triplet excited state (53.3 μs at RT). PMID:27374317

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

    SciTech Connect

    Turro, N.J.; Khudyakov, I.V.; Bossmann, S.H. ); Dwyer, D.W. )

    1993-02-11

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

  3. 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. PMID:24487942

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

    PubMed

    Rosado-Lausell, Sahid L; Wang, Hanting; Gutiérrez, Leonardo; Romero-Maraccini, Ofelia C; Niu, Xi-Zhi; Gin, Karina Y H; Croué, Jean-Philippe; Nguyen, Thanh H

    2013-09-15

    Inactivation of bacteriophage MS2 by reactive oxygen species (ROS) and triplet excited state of dissolved organic matter ((3)DOM*) produced by irradiation of natural and synthetic sensitizers with simulated sunlight of wavelengths greater than 320 nm was investigated. Natural sensitizers included purified DOM isolates obtained from wastewater and river waters, and water samples collected from Singapore River, Stamford Canal, and Marina Bay Reservoir in Singapore. Linear correlations were found between MS2 inactivation rate constants (kobs) and the photo-induced reaction rate constants of 2,4,6-trimethylphenol (TMP), a probe compound shown to react mainly with (3)DOM*. Linear correlations between MS2 kobs and singlet oxygen ((1)O2) concentrations were also found for both purified DOM isolates and natural water samples. These correlations, along with data from quenching experiments and experiments with synthetic sensitizers, Rose Bengal (RB), 3'-methoxyacetophenone (3'-MAP), and nitrite [Formula: see text] , suggest that (1)O2, (3)DOM*, and hydroxyl radicals ((•)OH) could inactivate bacteriophage MS2. Linear correlations between MS2 kobs and Specific Ultraviolet Absorption determined at 254 nm (SUVA254) were also found for both purified DOM isolates and natural samples. These results suggest the potential use of TMP as a chemical probe and SUVA254 as an indicator for virus inactivation in natural and purified DOM water samples. PMID:23866126

  5. Saturable absorption dynamics in the triplet system and triplet excitation induced singlet fluorescence of some organic molecules

    NASA Astrophysics Data System (ADS)

    Gratz, H.; Penzkofer, A.

    2001-01-01

    The triplet saturable absorption behaviour of the xanthene dyes eosin Y, erythrosin B, and rose bengal and of the fullerene molecule C 70 is studied. The molecules are excited to the S 1-state by intense picosecond pulses (wavelength λP=527 nm). They relax dominantly to the triplet system by intersystem crossing. The triplet-triplet saturable absorption is investigated with time-delayed intense picosecond pulses (wavelength λL=1054 nm) in the transparency region of the molecules in the singlet ground state. Higher excited-state triplet absorption cross-sections and higher excited-state triplet relaxation times are determined by numerical simulation of the experimental results. Time-resolved fluorescence measurements reveal higher excited-state triplet to singlet back-intersystem-crossing and multi-step triplet photoionization. Additionally the two-photon absorption cross-sections at λL=1054 nm are determined by measurement of the fundamental pulse two-photon induced fluorescence relative to the second-harmonic pulse single-photon induced fluorescence.

  6. 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.

  7. 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. PMID:24329403

  8. 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.

  9. 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.

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

    NASA Astrophysics Data System (ADS)

    Yu, L.; Smith, J.; Laskin, A.; Anastasio, C.; Laskin, J.; Zhang, Q.

    2014-12-01

    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 (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 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 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.

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

    NASA Astrophysics Data System (ADS)

    Yu, L.; Smith, J.; Laskin, A.; Anastasio, C.; Laskin, J.; Zhang, Q.

    2014-08-01

    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 (\\centerdot 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, 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 \\centerdot 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.

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

    DOE PAGESBeta

    Yu, L.; Smith, J.; Laskin, A.; Anastasio, C.; Laskin, J.; Zhang, Q.

    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

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

    DOE PAGESBeta

    Yu, L.; Smith, J.; Laskin, A.; Anastasio, C.; Laskin, J.; Zhang, Q.

    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

  14. 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.

  15. Excited state mass spectra of Λc+ baryon

    NASA Astrophysics Data System (ADS)

    Shah, Zalak; Thakkar, Kaushal; Rai, Ajay Kumar; Vinodkumar, P. C.

    2016-05-01

    The radial and orbital excited state masses of singly charmed Λc+ baryon is calculated using the Hypercentral Constituent Quark Model (hCQM). The first order correction is applied to the confinement coulomb plus power potential. The ground and excited state masses for JP=3/2+ are calculated. Our results are in good agreement with experimental and other theoretical predictions.

  16. Dynamics and configurations of galaxy triplets

    NASA Technical Reports Server (NTRS)

    Anosova, Joanna P.; Orlov, Victor V.; Chernin, Arthur D.; Ivanov, Alexei V.; Kiseleva, Ljudmila G.

    1990-01-01

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

  17. Anharmonicity Effects in IR Spectra of [Re(X)(CO)3(α-diimine)] (α-diimine = 2,2'-bipyridine or pyridylimidazo[1,5-a]pyridine; X = Cl or NCS) Complexes in Ground and Excited Electronic States.

    PubMed

    Kvapilová, Hana; Vlček, Antonín; Barone, Vincenzo; Biczysko, Malgorzata; Záliš, Stanislav

    2015-10-01

    Infrared spectra of [Re(X)(CO)(3)(α-diimine)] (α-diimine = 2,2'-bipyridine, X = Cl, NCS, or pyridylimidazo[1,5-a]pyridine, X = Cl) in the ground and the lowest triplet electronic states were calculated by a global hybrid density functional going beyond the harmonic level by means of second-order vibrational perturbation theory (VPT2) and including bulk solvent effects by the polarizable continuum model (PCM). The full-dimensionality (FD) VPT2 is compared with the reduced-dimensionality (RD) model, where only selected vibrational modes are calculated anharmonically. The simulated difference IR spectra (excited state minus ground state) in the ν(CO) region closely match experimental time-resolved infrared (TRIR) spectra. Very good agreement was also obtained for ground-state spectra in the fingerprint region. In comparison with the harmonic simulated spectra, the calculated anharmonic frequencies are closer to experimental values and do not require scaling when the B3LYP functional is used. Several spectral features due to combination bands have been identified by VPT2 simulations in the ν(CO) spectral region, which are of importance for a correct interpretation of TRIR experiments. PMID:26367031

  18. Localization length scales of triplet excitons in singlet fission materials

    NASA Astrophysics Data System (ADS)

    Bayliss, Sam L.; Thorley, Karl J.; Anthony, John E.; Bouchiat, Hélène; Greenham, Neil C.; Chepelianskii, Alexei D.

    2015-09-01

    We measure the dielectric confinement length scales of triplet excitons in organic semiconductors by jointly measuring their microwave-domain electric and magnetic susceptibilities. We apply this technique to characterize triplet excitons in two singlet fission materials with distinct solid-state packing and correlate the extracted localization length scales with the role of the excitonic environment. By using the magnetic susceptibility simultaneously determined through our experiments, we compare the independently extracted dielectric and spin-spin localization length scales, highlighting the role of local anisotropy on the properties of excitonic triplet states.

  19. Thermally induced excited-state coherent raman spectra of solids

    NASA Astrophysics Data System (ADS)

    Andrews, J. R.; Hochstrasser, R. M.

    1981-09-01

    A difference frequency resonance has been observed for the 747 cm -1 vibration in the first excited singlet state of pentacene in benzoic acid. The resonance is absent at low temperature (4.5 K) and its appearance is exponentially activated with an activation energy of 13.8 cm -1. These observations are compared to theoretical expectations.

  20. Singlet-triplet energy splitting between 1D and 3D (1s2 2s nd), n = 3, 4, 5, and 6, Rydberg states of the beryllium atom (9Be) calculated with all-electron explicitly correlated Gaussian functions

    NASA Astrophysics Data System (ADS)

    Sharkey, Keeper L.; Bubin, Sergiy; Adamowicz, Ludwik

    2014-11-01

    Accurate variational nonrelativistic quantum-mechanical calculations are performed for the five lowest 1D and four lowest 3D states of the 9Be isotope of the beryllium atom. All-electron explicitly correlated Gaussian (ECG) functions are used in the calculations and their nonlinear parameters are optimized with the aid of the analytical energy gradient determined with respect to these parameters. The effect of the finite nuclear mass is directly included in the Hamiltonian used in the calculations. The singlet-triplet energy gaps between the corresponding 1D and 3D states, are reported.

  1. 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.

  2. State flip at exceptional points in atomic spectra

    NASA Astrophysics Data System (ADS)

    Menke, Henri; Klett, Marcel; Cartarius, Holger; Main, Jörg; Wunner, Günter

    2016-01-01

    We study the behavior of nonadiabatic population transfer between resonances at an exceptional point in the spectrum of the hydrogen atom. It is known that, when the exceptional point is encircled, the system always ends up in the same state, independent of the initial occupation within the two-dimensional subspace spanned by the states coalescing at the exceptional point. We verify this behavior for a realistic quantum system, viz., the hydrogen atom in crossed electric and magnetic fields. It is also shown that the nonadiabatic hypothesis can be violated when resonances in the vicinity are taken into account. In addition, we study nonadiabatic population transfer in the case of a third-order exceptional point, in which three resonances are involved.

  3. Time-resolved CIDEP study of the photogenerated camphorquinone radical anion: a case of dual singlet and triplet precursors

    SciTech Connect

    Depew, M.C.; Wan, J.K.S.

    1986-12-04

    Photoreduction of camphorquinone in 2-propanol produced electron spin polarized camphorquinone radical anions. The time-resolved electron spin resonance spectra of the spin-polarized radical anions provided the first evidence of dual singlet and triplet precursors in the CIDEP phenomenon. With the results from fluorescence quenching experiments, the time dependence of the CIDEP spectra can be accounted for qualitatively by the changes of the relative contributions to the polarization among the singlet pair, F and triplet pairs, and the triplet mechanisms.

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

    NASA Astrophysics Data System (ADS)

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

    2013-01-01

    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.

  5. 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

  6. Singlet-Triplet Splittings in the Luminescent Excited States of Colloidal Cu(+):CdSe, Cu(+):InP, and CuInS2 Nanocrystals: Charge-Transfer Configurations and Self-Trapped Excitons.

    PubMed

    Knowles, Kathryn E; Nelson, Heidi D; Kilburn, Troy B; Gamelin, Daniel R

    2015-10-14

    The electronic and magnetic properties of the luminescent excited states of colloidal Cu(+):CdSe, Cu(+):InP, and CuInS2 nanocrystals were investigated using variable-temperature photoluminescence (PL) and magnetic circularly polarized luminescence (MCPL) spectroscopies. The nanocrystal electronic structures were also investigated by absorption and magnetic circular dichroism (MCD) spectroscopies. By every spectroscopic measure, the luminescent excited states of all three materials are essentially indistinguishable. All three materials show very similar broad PL line widths and large Stokes shifts. All three materials also show similar temperature dependence of their PL lifetimes and MCPL polarization ratios. Analysis shows that this temperature dependence reflects Boltzmann population distributions between luminescent singlet and triplet excited states with average singlet-triplet splittings of ∼1 meV in each material. These similarities lead to the conclusion that the PL mechanism in CuInS2 NCs is fundamentally different from that of bulk CuInS2 and instead is the same as that in Cu(+)-doped NCs, which are known to luminesce via charge-transfer recombination of conduction-band electrons with copper-localized holes. The luminescence of CuInS2 nanocrystals is explained well by invoking exciton self-trapping, in which delocalized photogenerated holes contract in response to strong vibronic coupling at lattice copper sites to form a luminescent excited state that is essentially identical to that of the Cu(+)-doped semiconductor nanocrystals. PMID:26389577

  7. 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.

  8. Exciton interactions in reaction centers of the photosynthetic bacterium Rhodopseudomonas viridis probed by optical triplet-minus-singlet polarization spectroscopy at 1.2 K monitored through absorbance-detected magnetic resonance.

    PubMed

    Lous, E J; Hoff, A J

    1987-09-01

    Linear dichroic triplet-minus-singlet [LD-(T - S)] spectra of isolated reaction centers of the photosynthetic bacterium Rhodopseudomonas viridis have been measured at 1.2 K with the linear dichroic absorbance-detected magnetic resonance (LD-ADMR) technique for two mutually perpendicular directions of the preferred axis. The LD-(T - S) spectra have been calibrated with respect to the corresponding (T - S) spectra as a function of applied microwave power and quantitatively interpreted using the formalism of photoselection. The transition moment of the optical transition at 1007 nm makes angles of 72 degrees +/- 5 degrees and 15 degrees +/- 5 degrees with the triplet x and y spin axes, respectively. The experimental spectra have been simulated employing exciton theory and using the atomic coordinates of the resolved crystal structure of the reaction center. The spectral interpretation yields the angles between the transition moments of the various absorption bands of the (T - S) spectra and the triplet axes, and between the moments themselves, with the triplet state of the primary donor (3)P localized on the P-bacteriochlorophyll b in the "active" (L) chain. PMID:16578814

  9. Triplet exciton transport in the benzophenone-fluorene-naphthalene molecule

    NASA Astrophysics Data System (ADS)

    McElfresh, Duncan C.

    Incoherent triplet-triplet energy transfer through the benzophenone-fluorene-naphthalene system is computationally investigated to determine triplet hopping rates. These rates have been previously measured experimentally and have also been estimated computationally. There are many complex steps associated with such a computational analysis, though, and earlier efforts resorted to a variety of semi-empirical modifications to the methods used in order to obtain results consistent with the experimental data. This has motivated an investigation in which best practice methods are applied to the system without any empirical adjustments. The calculation of triplet excitation energy and triplet-triplet electronic coupling are examined in detail using a range of computational methods from simple Density Functional Theory to the many-body Green function approach embodied in the Bethe-Salpeter Equation. This analysis includes an evaluation of the robustness of each method considered. Significantly, the investigation identifies the excited states of benzophenone as being extremely difficult to calculate using even the most advanced excitation methods, and a theory is presented as to why the molecule is both interesting and troublesome. The final rate estimates, without any empirical adjustments, are one to two orders of magnitude greater than those measured experimentally. This data, and the detailed methodological study supporting it, is expected to be helpful in future efforts to computationally scrutinize triplet exciton hopping.

  10. Synthesis of triplet emitters and hosts for electrophosphorescence

    NASA Astrophysics Data System (ADS)

    Chan, Khai Leok; Mak, Chris S. K.; Evans, Nicholas R.; Watkins, Scott E.; Pascu, Sofia I.; Holmes, Andrew B.; Hayer, Anna; Köhler, Anna; Sudha Devi, Lekshmi; Friend, Richard H.

    2005-10-01

    Electroluminescence from conjugated polymers can be significantly improved by harnessing the energy of their nonemissive triplet states. Poly(2,7-dibenzosilole) has been prepared and its triplet energy has been measured as 2.14 eV, a figure that is slightly higher than that of polyfluorene (2.09 eV). Two new tris-cyclometalated iridium complexes with blue-to-green emission properties have been prepared and characterized.

  11. Peculiarity of triplet-triplet energy transfer from 2-(2'-hydroxy-phenyl)benzoxazole to diacetyl. Evidence for radiative keto-enol transitions 3K∗→ 1E and 1E→ 1K∗

    NASA Astrophysics Data System (ADS)

    Nickel, Bernhard; Walla, Peter J.

    1998-10-01

    In the triplet-triplet energy transfer (TTET) from a donor D to an acceptor A, 3D∗+ 1A→ 1D+ 3A∗, the maximum transferable energy is equal to the maximum energy that can be emitted as phosphorescence 3D∗→ 1D. A peculiarity was expected for the TTET from 2-(2'-hydroxyphenyl)benzoxazole (HBO), which has two isoenergetic lowest triplet states, an enol triplet state 3E∗ and a keto triplet state 3K∗, with completely different phosphorescence spectra: 3E∗→ 1E (origin at 22400 cm -1) and 3K∗→ 1K (origin at ˜17500 cm -1). If the triplet energy of an acceptor A is between these two origin values, like in the case of diacetyl (19700 cm -1), then the TTET from HBO to A should be predominantly due to the process 3E∗+ 1A→ 1E+ 3A∗. The TTET from HBO, meta-methyl-HBO ( m-MeHBO, 3K∗≳300 cm -1 above 3E∗) and ortho-methyl-HBO ( o-MeHBO, 3K∗≳600 cm -1 below 3E∗) to diacetyl was studied in 3-methylpentane from 110 to 280 K, which corresponds to a viscosity range of more than three orders of magnitude. The postulated peculiarity of TTET was observed at low viscosity. At low temperature and high viscosity, however, the kinetic differences in the TTET from the three donors disappear. The TTET from o-MeHBO to diacetyl at low temperature is assigned to the process 3K∗+ 1A→ 1E+ 3A∗, which corresponds to a keto-enol phosphorescence 3K→ 1E. The temperature dependence of the second-order rate constant for TTET can be satisfactorily described with a kinetic model, whose distinctive feature is a finite rate of the triplet-state tautomerization 3K∗⇌ 3E∗. The only essentially donor-specific parameter is the energy difference between 3E∗ and 3K∗. The principal possibility of radiative keto-enol or enol-keto transitions has been verified: The phosphorescence excitation spectrum of m-MeHBO in a xenon matrix exhibits in the near UV a weak band that can be assigned to the transition 1E→ 1K∗.

  12. Identification of the sites of chlorophyll triplet quenching in relation to the structure of LHC-II from higher plants. Evidence from EPR spectroscopy.

    PubMed

    Di Valentin, Marilena; Biasibetti, Federico; Ceola, Stefano; Carbonera, Donatella

    2009-10-01

    The Chlorophyll a (Chl a) molecules involved in the triplet-triplet energy transfer to the central luteins in trimeric LHC-II are identified by time-resolved and pulse EPR techniques. The concept of spin angular momentum conservation during triplet-triplet energy transfer is exploited for the calculation of the spin polarization of the carotenoid triplet states. The sites with the highest probability of forming triplet states, which are quenched by the central luteins, result to be Chl603 and Chl612. "Unquenched" Chl triplet states are produced by photoexcitation in the LHC-II complex. Putative sites of these triplet states are Chl614, Chl611, Chl604, and Chl613 since they do not contribute to the formation of the observed carotenoid triplet states. PMID:19725570

  13. 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.

  14. 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. PMID:25299940

  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. 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.

  17. Dimethyl ether: laboratory spectra up to 2.1 THz. Torsion-rotational spectra within the vibrational ground state

    NASA Astrophysics Data System (ADS)

    Endres, C. P.; Drouin, B. J.; Pearson, J. C.; Müller, H. S. P.; Lewen, F.; Schlemmer, S.; Giesen, T. F.

    2009-09-01

    Dimethyl ether (CH_3OCH_3) is one of the largest organic molecules detected in the interstellar medium. As an asymmetric top molecule with two methyl groups which undergo large amplitude motions and a dipole moment of μ=1.3 D, it conveys a dense spectrum throughout the terahertz region and contributes to the spectral line confusion in astronomical observations at these frequencies. In this paper, we present rotational spectra of dimethyl ether in its ground vibrational states, which have been measured in the laboratory and analyzed covering frequencies up to 2.1 THz. The analysis is based on an effective Hamiltonian for a symmetric two-top rotor and includes experimental data published so far. Frequency predictions are presented up to 2.5 THz for astronomical applications with accuracies better than 1 MHz. Table A.1 is only available in electronic form at the CDS via anonymous ftp to cdsarc.u-strasbg.fr (130.79.128.5) or via http://cdsweb.u-strasbg.fr/cgi-bin/qcat?J/A+A/504/635

  18. 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). PMID:18648707

  19. Triplet-Triplet Annihilation Photon Upconversion in Polymer Thin Film: Sensitizer Design.

    PubMed

    Jiang, Xinpeng; Guo, Xinyan; Peng, Jiang; Zhao, Dahui; Ma, Yuguo

    2016-05-11

    Efficient visible-to-UV photon upconversion via triplet-triplet annihilation (TTA) is accomplished in polyurethane (PU) films by developing new, powerful photosensitizers fully functional in the solid-state matrix. These rationally designed triplet sensitizers feature a bichromophoric scaffold comprising a tris-cyclometalated iridium(III) complex covalently tethered to a suitable organic small molecule. The very rapid intramolecular triplet energy transfer from the former to the latter is pivotal for achieving the potent sensitizing ability, because this process out-competes the radiative and nonradiative decays inherent to the metal complex and produces long-lived triplet excitons localized with the acceptor moiety readily available for intermolecular transfer and TTA. Nonetheless, compared to the solution state, the molecular diffusion is greatly limited in solid matrices, which even creates difficulty for the Dexter-type intramolecular energy transfer. This is proven by the experimental results showing that the sensitizing performance of the bichromophoric molecules strongly depends on the spatial distance separating the donor (D) and acceptor (A) units and that incorporating a longer linker between the D and A evidently curbs the TTA upconversion efficiency in PU films. Using a rationally optimized sensitizer structure in combination with 2,7-di-tert-butylpyrene as the annihilator/emitter, the doped polyurethane (PU) films demonstrate effective visible-to-UV upconverted emission signal under noncoherent-light irradiation, attaining an upconversion quantum yield of 2.6%. Such quantum efficiency is the highest value so far reported for the visible-to-UV TTA systems in solid matrices. PMID:27082767

  20. Spectroscopic Characterization and Reactivity of Triplet and Quintet Iron(IV) Oxo Complexes in the Gas Phase

    PubMed Central

    Andris, Erik; Jašík, Juraj; Gómez, Laura

    2016-01-01

    Abstract Closely structurally related triplet and quintet iron(IV) oxo complexes with a tetradentate aminopyridine ligand were generated in the gas phase, spectroscopically characterized, and their reactivities in hydrogen‐transfer and oxygen‐transfer reactions were compared. The spin states were unambiguously assigned based on helium tagging infrared photodissociation (IRPD) spectra of the mass‐selected iron complexes. It is shown that the stretching vibrations of the nitrate counterion can be used as a spectral marker of the central iron spin state. PMID:26878833

  1. Photosensitized reactions initiated by 6-carboxypterin: singlet and triplet reactivity.

    PubMed

    Tinel, L; Rossignol, S; Ciuraru, R; Dumas, S; George, C

    2016-06-22

    Pterins, derivatives of 2-aminopteridin-4(3H)-one, are natural photosensitizers, common to many biological systems. Indications that these photosensitizers are also present in the sea-surface microlayer motivated the study of the photophysical and photochemical properties of 6-carboxypterin (CPT), which was chosen as a model for this group of photoactive compounds. The kinetics of excited CPT in the singlet and triplet state in the presence of halides and organics were studied in aqueous solutions at neutral pH by means of steady-state fluorescence and laser-flash photolysis. The fluorescence of CPT was efficiently quenched by two halides (iodide and bromide) and by four carboxylic acids (lactic, malonic, propionic and citric acid) with reaction rates close to the diffusion-controlled limit. In the triplet state, the triplet absorption spectrum was measured and its pH dependence was studied. The triplet state of CPT showed relatively high reactivity towards iodide, but no reaction with bromide or chloride could be observed. No singlet or triplet state quenching in the presence of limonene could be measured. A reaction mechanism is proposed, initiated by electron transfer from the quencher to the excited photosensitizer. This type of photo-induced reaction in the sea-surface microlayer has the potential to trigger the production of many oxidized species, including halogen atoms, in the bulk and gaseous phases. PMID:27296228

  2. Photo-induced electron transfer in a diamino-substituted Ru(bpy)3[PF6]2 complex and its application as a triplet photosensitizer for nitric oxide (NO)-activated triplet-triplet annihilation upconversion.

    PubMed

    Xu, Kejing; Zhao, Jianzhang; Moore, Evan G

    2016-08-01

    A system demonstrating Nitric Oxide (NO) activated Triplet-Triplet Annihilation (TTA) upconversion has been devised, based on a substituted [Ru(II)(bpy)3](PF6)2 complex (bpy = 2,2'-dipyridine) bearing a single 1,2-diaminophenyl moiety as an NO activatable triplet photosensitizer (Ru-1), and 9,10-diphenylanthracene (DPA) as a triplet acceptor/emitter. The excited triplet state of Ru-1 is significantly quenched (ΦT∼ 22%) by a Photoinduced Electron Transfer (PET) reaction, as confirmed by steady state phosphorescence and transient absorption spectroscopy, and hence Ru-1 does not function as a TTA upconversion sensitizer. However, in the presence of NO/O2, the 1,2-diaminophenyl group of Ru-1 is transformed into a benzotriazole. This inhibits PET, and the triplet state quantum yield is increased to ca. 85%, switching on the TTA upconversion process which increases by 10-fold. These processes were studied using a combination of steady state and time-resolved luminescence together with transient absorption spectroscopy on the nanosecond and femtosecond timescales. The energy level of the charge transfer state (CTS) for Ru-1 was also obtained electrochemically, supporting the PET mechanism of triplet state quenching and hence the lack of TTA upconversion with Ru-1. PMID:27387268

  3. Wide range double photoionisation spectra of N2 and CO2

    NASA Astrophysics Data System (ADS)

    Eland, J. H. D.; Plogmaker, S.; Lablanquie, P.; Penent, F.; Palaudoux, J.; Nicolas, C.; Robert, E.; Miron, C.; Feifel, R.

    2016-02-01

    Using a magnetic bottle time-of-flight electron spectrometer we have measured double photoionisation spectra of N2 and CO2 covering the range from threshold up to the triple ionisation energies. The experiments demonstrate the use of a new asynchronous chopper in eight-bunch mode of the synchrotron radiation source SOLEIL. For CO22+ some broad bands in the Auger spectra are found to have multiple resolved counterparts in the photoionisation spectrum. All the bands in the Auger spectra have counterparts in the photoionisation spectra, where extra bands attributed to triplet states are present. In the spectrum of N22+ we suggest reassignment of one band.

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

    PubMed

    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

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

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

    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.

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

    PubMed

    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

  8. 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

  9. 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

  10. Binding energies of the ground triplet state a{sup 3}Σ{sub u}{sup +} of Rb{sub 2} and Cs{sub 2} in terms of the generalized Le Roy–Bernstein near-dissociation expansion

    SciTech Connect

    Sovkov, V. B.; Ivanov, V. S.

    2014-04-07

    Formulae of Le Roy–Bernstein near-dissociation theory are derived in a general isotope–invariant form, applicable to any term in the rotational expansion of a diatomic ro-vibrational term value. It is proposed to use the generalized Le Roy–Bernstein expansion to describe the binding energies (ro-vibrational term values) of the ground triplet state a{sup 3}Σ{sub u}{sup +} of alkali metal dimers. The parameters of this description are determined for Rb{sub 2} and Cs{sub 2} molecules. This approach gives a recipe to calculate the whole variety of the binding energies with characteristic accuracies from ∼1 × 10{sup −3} to 1 × 10{sup −2} cm{sup −1} using a relatively simple algebraic equation.

  11. Impact of Diradical Spin State (Singlet vs Triplet) and Structure (Puckered vs Planar) on the Photodenitrogenation Stereoselectivity of 2,3-Diazabicyclo[2.2.1]heptanes.

    PubMed

    Abe, Manabu; Tada, Saori; Mizuno, Takemi; Yamasaki, Katsuyoshi

    2016-07-28

    Versatile transformations of azo compounds are utilized not only in synthetic organic chemistry but also in materials science. In this study, a hitherto unknown stereoselectivity was observed by low-temperature in situ NMR spectroscopy for the photochemical denitrogenation of a cyclic azoalkane (2,3-diazabicyclo[2.2.1]heptane) derivative. Direct (singlet) photodenitrogenation at 188 K afforded two products, the configurationally retained ring-closed compound (ret-CP) and the inverted compound (inv-CP), in a ratio of 82/18 (±3) (ret-CP/inv-CP), with an overall yield of >95%. Triplet-sensitized denitrogenation at 199 K using benzophenone ((3)BP*) or xanthone ((3)Xan*) selectively produced inv-CP, with a ret-CP/inv-CP ratio of 7/93 (±3). Thermal isomerization of inv-CP into ret-CP was observed by low-temperature NMR spectroscopy. Transient absorption spectroscopy revealed that two distinct singlet diradicals are involved in the formation of CP during direct photodenitrogenation, that is, puckered puc-(1)DR and planar pl-(1)DR diradicals. The former produces ret-CP, whereas the latter affords inv-CP. Kinetic analysis using the integrated profiles method was used to determine the molecular absorption coefficient of pl-(1)DR (ε560 = 4900 ± 250 M(-1) cm(-1)) for the first time. The involvement of the puckered singlet diradical resolves the mechanistic puzzle of stereoselective denitrogenation of diazabicycloheptane-type azoalkanes. PMID:27353594

  12. '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.

  13. Metallophthalocyanines as triplet sensitizers for highly efficient photon upconversion based on sensitized triplet-triplet annihilation.

    PubMed

    Han, J L; You, J; Yonemura, H; Yamada, S; Wang, S R; Li, X G

    2016-08-01

    Soluble palladium and platinum phthalocyanines with coumarin moieties were synthesized with Q bands in the red and near-IR regions, in which the molar extinction coefficients were up to 1.01 × 10(5) cm(-1) mol(-1). These metallophthalocyanines were coupled with rubrene and applied in photon upconversion systems based on triplet-triplet annihilation. The highest upconversion efficiency of the palladium phthalocyanine was 5.6%, which is higher than that of the platinum phthalocyanine-rubrene system. The larger molar extinction coefficient resulted in high upconversion capability (>10(5) cm(-1) mol(-1)) and low saturation incident power (<20 mW cm(-2)). PMID:27431880

  14. ELECTRONIC SOLUTION SPECTRA FOR URANIUM AND NEPTUNIUM IN OXIDATION STATES (III) TO (VI) IN ANHYDROUS HYDROGEN FLUORIDE

    SciTech Connect

    Baluka, M.; Edelstein, N.; O'Donnell, T. A.

    1980-10-01

    Spectra have been recorded for solutions in anhydrous hydrogen fluoride (AHF) of uranium and neptunium in oxidation states (III) to (VI). The spectra for U(III), Np(III) and Np(IV) in AHF are very similar to those in acidified aqueous solution, but that for U(IV) suggests that the cationic species is UF{sub 2}{sup 2+}. The AHF spectra for the elements in oxidation states (V) and (VI) are not comparable with those of the formally analogous aqueous solutions, where the elements exist as well-defined dioxo-cations. However, the AHF spectra can be related to spectra in the gas phase, in the solid state or in non-aqueous solvents for each element in its appropriate oxidation state.

  15. Non-Markovian Quantum State Diffusion for temperature-dependent linear spectra of light harvesting aggregates

    SciTech Connect

    Ritschel, Gerhard; Möbius, Sebastian; Eisfeld, Alexander; Suess, Daniel; Strunz, Walter T.

    2015-01-21

    Non-Markovian Quantum State Diffusion (NMQSD) has turned out to be an efficient method to calculate excitonic properties of aggregates composed of organic chromophores, taking into account the coupling of electronic transitions to vibrational modes of the chromophores. NMQSD is an open quantum system approach that incorporates environmental degrees of freedom (the vibrations in our case) in a stochastic way. We show in this paper that for linear optical spectra (absorption, circular dichroism), no stochastics is needed, even for finite temperatures. Thus, the spectra can be obtained by propagating a single trajectory. To this end, we map a finite temperature environment to the zero temperature case using the so-called thermofield method. The resulting equations can then be solved efficiently by standard integrators.

  16. N2 triplet band emissions in the dayglow of Venus, Mars, and Titan

    NASA Astrophysics Data System (ADS)

    Jain, Sonal Kumar; Bhardwaj, Anil

    2012-07-01

    Vegard-Kaplan (VK) and Second Positive emissions of N_2 are common features in the terrestrial dayglow and aurora and have been studied extensively. Recent discoveries of N_2 triplet band emissions on Mars by SPICAM/Mars-Express and on Titan by Cassini UVIS have led planetary scientists to look for the processes governing the N_2 triplet band emissions in different planetary atmospheres. Present work deals with the modeling of N_2 triplet band emission on Mars, Venus, and Titan. A model for N_2 triplet band emissions has been developed and used to explain the recent observations of N_2 Vegard-Kaplan (VK) (A^3Σ_u^+ - X^1Σ^+_g ) band on Mars and Titan. Steady state photoelectron fluxes and volume excitation rates have been calculated using the Analytical Yield Spectra technique. Since interstate cascading is important for triplet states of N_2, the population of any given level of N_2 triplet states is calculated under statistical equilibrium considering direct excitation, cascading, and quenching effects. Relative population of all vibrational levels of each triplet state is calculated in the model. Line of sight intensities and height-integrated overhead intensities have been calculated for VK, First Positive ( B^3Π_g - A^3Σ^+_u ), Second Positive ( C^3Π_u - B^3Π_g ), Wu-Benesch (W^3Δ_u - B^3Π_g), Reverse First Positive, Herman--Kaplan (E → A), E → B, and E → C bands of N_2. The N_2 VK band span wavelength range from far ultraviolet to visible, and some transitions even originate at wavelength more than 1000 nm . Our calculations show that the overhead intensity of VK bands in the wavelength range 400--800, 300--190, 200--300, and 150--200 nm are 22%, 39%, 35%, and 4% of the total VK band emission. Emissions between 600 and 800 nm wavelength consist of about 50% of the total First Positive band system. Major portion of Second Positive band emissions lie in wavelengths between 300 and 400 nm, which is more than 90% of the total Second Positive band

  17. Twins, Triplets, Multiple Births

    MedlinePlus

    ... alone. Multiple births are up in the United States. More women are having babies after age 30 ... support groups for parents of multiples can help. Dept. of Health and Human Services Office on Women's ...

  18. Fluorescence excitation spectra of all-trans-1,6-diphenylhexatriene conformers: Adiabatic conformer equilibration in the 21Ag state

    NASA Astrophysics Data System (ADS)

    Turek, Andrzej M.; Krishna, Tallapragada S. R.; Brela, Mateusz; Saltiel, Jack

    2016-03-01

    Fluorescence spectra of all-trans-1,6-diphenyl-1,3,5-hexatriene were measured in n-hexadecane at 99 °C by varying λexc in the 294-404 nm range. Resolution of this spectral matrix into s-trans,s-trans and s-cis,s-trans conformer fluorescence spectra yields the λexc dependence of fractional contributions which are converted to conformer specific fluorescence excitation spectra. Conformer absorption spectra obtained from the fluorescence excitation spectra are remarkably similar, but differ significantly from absorption spectra derived from a spectrothermal absorption spectral matrix measured in n-alkanes under isopolarizability conditions. The results reveal substantial conformer equilibration in the excited state. Theory is consistent with adiabatic conformer equilibration in the 21Ag state.

  19. Electronic state-lifetime interference in resonant Auger spectra: a tool to disentangle overlapping core-excited states.

    PubMed

    Goldsztejn, Gildas; Marchenko, Tatiana; Céolin, Denis; Journel, Loïc; Guillemin, Renaud; Rueff, Jean-Pascal; Kushawaha, Rajesh K; Püttner, Ralph; Piancastelli, Maria Novella; Simon, Marc

    2016-06-01

    We have measured resonant-Auger decay following Cl 1s(-1) excitations in HCl and CH3Cl molecules, and extracted the pseudo-cross sections of different Cl 2p(-2) final states. These cross sections show clear evidence of shake processes as well as contributions of electronic state-lifetime interference (ELI). To describe the spectra we developed a fit approach that takes into account ELI contributions and ultrafast nuclear dynamics in dissociative core-excited states. Using this approach we utilized the ELI contributions to obtain the intensity ratios of the overlapping states Cl 1s(-1)4pπ/1s(-1)4pσ in HCl and Cl 1s(-1)4pe/1s(-1)4pa1 in CH3Cl. The experimental value for HCl is compared with theoretical results showing satisfactory agreement. PMID:27199185

  20. 6-Aminouracil: Geometries and spectra in the isolated state and in the solid state simulation. A comparison with 5-aminouracil

    NASA Astrophysics Data System (ADS)

    Palafox, M. Alcolea; Rastogi, V. K.

    2016-03-01

    FT-IR and FT-Raman spectra of 6-aminouracil were recorded in the solid state in the regions 3500-0 cm-1 and 4000-400 cm-1, respectively. The unit cell reported by X-ray in the crystal was reproduced theoretically by density functional theoretical calculations as a tetramer form. To correct the overestimation of the theoretical wavenumbers of 6-aminouracil were used specific scaling equations determined from the molecule of uracil. These scaled frequencies obtained were employed in the reassignment of several Raman and Infrared experimental bands. In the comparison of these experimental values the percentage of error is very small in most of the wavenumbers. A correlation between the geometric parameters, charge distribution and vibrational spectra of 6-aminouracil and 5-aminouracil molecules was shown.

  1. 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. PMID:26060309

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

    PubMed Central

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

    2015-01-01

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

  3. Twins, Triplets, Multiple Births

    MedlinePlus

    ... from alone. Multiple births are up in the United States. More women are having babies after age 30 and more are taking fertility drugs. Both boost the chance of carrying more than one baby. A family history of twins also makes multiples more likely. Years ...

  4. 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.

  5. 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.

  6. 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

  7. Aromaticity effects on the profiles of the lowest triplet-state potential-energy surfaces for rotation about the C=C bonds of olefins with five-membered ring substituents: an example of the impact of Baird's rule.

    PubMed

    Zhu, Jun; Fogarty, Heather A; Möllerstedt, Helene; Brink, Maria; Ottosson, Henrik

    2013-08-01

    A density functional theory study on olefins with five-membered monocyclic 4n and 4n+2 π-electron substituents (C4H3X; X=CH(+), SiH(+), BH, AlH, CH2, SiH2, O, S, NH, and CH(-)) was performed to assess the connection between the degree of substituent (anti)aromaticity and the profile of the lowest triplet-state (T1) potential-energy surface (PES) for twisting about olefinic C=C bonds. It exploited both Hückel's rule on aromaticity in the closed-shell singlet ground state (S0) and Baird's rule on aromaticity in the lowest ππ* excited triplet state. The compounds CH2=CH(C4H3X) were categorized as set A and set B olefins depending on which carbon atom (C2 or C3) of the C4H3X ring is bonded to the olefin. The degree of substituent (anti)aromaticity goes from strongly S0 -antiaromatic/T1 -aromatic (C5H4 (+)) to strongly S0 -aromatic/T1- antiaromatic (C5H4(-)). Our hypothesis is that the shapes of the T1 PESs, as given by the energy differences between planar and perpendicularly twisted olefin structures in T1 [ΔE(T1)], smoothly follow the changes in substituent (anti)aromaticity. Indeed, correlations between ΔE(T1) and the (anti)aromaticity changes of the C4 H3 X groups, as measured by the zz-tensor component of the nucleus-independent chemical shift ΔNICS(T1;1)zz , are found both for sets A and B separately (linear fits; r(2) =0.949 and 0.851, respectively) and for the two sets combined (linear fit; r(2) =0.851). For sets A and B combined, strong correlations are also found between ΔE(T1) and the degree of S0 (anti)aromaticity as determined by NICS(S0,1)zz (sigmoidal fit; r(2) =0.963), as well as between the T1 energies of the planar olefins and NICS(S0,1)zz (linear fit; r(2) =0.939). Thus, careful tuning of substituent (anti)aromaticity allows for design of small olefins with T1 PESs suitable for adiabatic Z/E photoisomerization. PMID:23794153

  8. Tough Decisions for Premature Triplets.

    PubMed

    Hurst, Ashley; Vergales, Brooke D; Paget-Brown, Alix; Mercurio, Mark; Lantos, John D

    2016-02-01

    When infants are born at the borderline of viability, doctors and parents have to make tough decisions about whether to institute intensive care or provide only palliative care. Often, these decisions are made in moments of profound emotional turmoil, and parents receive different information from different health professionals. Communication can become garbled. It may be difficult to tell when and whether the patient's clinical condition has changed enough so that certain choices that had once been permissible become impermissible. In this "Ethics Rounds," we present a case of triplets born at the borderline of viability. We sought comments from the triplets' parents, the doctors and ethicist who were caring for the infants, and a bioethicist/neonatologist from another hospital. PMID:26738882

  9. 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.

  10. Multi-state extrapolation of UV/Vis absorption spectra with QM/QM hybrid methods

    NASA Astrophysics Data System (ADS)

    Ren, Sijin; Caricato, Marco

    2016-05-01

    In this work, we present a simple approach to simulate absorption spectra from hybrid QM/QM calculations. The goal is to obtain reliable spectra for compounds that are too large to be treated efficiently at a high level of theory. The present approach is based on the extrapolation of the entire absorption spectrum obtained by individual subcalculations. Our program locates the main spectral features in each subcalculation, e.g., band peaks and shoulders, and fits them to Gaussian functions. Each Gaussian is then extrapolated with a formula similar to that of ONIOM (Our own N-layered Integrated molecular Orbital molecular Mechanics). However, information about individual excitations is not necessary so that difficult state-matching across subcalculations is avoided. This multi-state extrapolation thus requires relatively low implementation effort while affording maximum flexibility in the choice of methods to be combined in the hybrid approach. The test calculations show the efficacy and robustness of this methodology in reproducing the spectrum computed for the entire molecule at a high level of theory.

  11. Multi-state extrapolation of UV/Vis absorption spectra with QM/QM hybrid methods.

    PubMed

    Ren, Sijin; Caricato, Marco

    2016-05-14

    In this work, we present a simple approach to simulate absorption spectra from hybrid QM/QM calculations. The goal is to obtain reliable spectra for compounds that are too large to be treated efficiently at a high level of theory. The present approach is based on the extrapolation of the entire absorption spectrum obtained by individual subcalculations. Our program locates the main spectral features in each subcalculation, e.g., band peaks and shoulders, and fits them to Gaussian functions. Each Gaussian is then extrapolated with a formula similar to that of ONIOM (Our own N-layered Integrated molecular Orbital molecular Mechanics). However, information about individual excitations is not necessary so that difficult state-matching across subcalculations is avoided. This multi-state extrapolation thus requires relatively low implementation effort while affording maximum flexibility in the choice of methods to be combined in the hybrid approach. The test calculations show the efficacy and robustness of this methodology in reproducing the spectrum computed for the entire molecule at a high level of theory. PMID:27179466

  12. 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.

  13. 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.

  14. Stratospheric mean state: modelling the sensitivity to different solar irradiance spectra

    NASA Astrophysics Data System (ADS)

    Misios, Stergios; Tourpali, Klairie; Habbereiter, Margit

    2016-04-01

    The sensitivity of the stratospheric mean state to four different reference solar irradiance spectra describing a quite Sun (year 2008) is investigated using a chemistry climate model. Simulations show that the mean thermal state of the stratosphere depends considerably on the specified spectrum given that the annual mean temperature in tropical stratopause varies by more than 3 K, in some cases. Temperature anomalies are stronger in boreal winter and the polar night westerlies strengthen by about 15%. The simulated ozone climatology is also influenced by the choice of the reference spectrum and our model simulates concentration changes up to 6-7% in the middle stratosphere. Given that net effect of the ozone response is to dump temperature anomalies, we find an amplified temperature perturbation of about 20-30% in twin simulations without interactive chemistry coupling. Using a 2-D chemistry climate model we trace the spectral regions that contribute the most to the simulated changes in the stratosphere.

  15. Investigating Velocity Spectra at the Hugoniot State of Shock Loaded Heterogeneous Materials

    NASA Astrophysics Data System (ADS)

    Lajeunesse, Jeff; Borg, John; Stewart, Sarah; Thadhani, Naresh

    2015-06-01

    Hugoniot states achieved in heterogeneous materials have shown oscillations in particle velocity about an averaged state for both experimental and simulated data. These oscillations 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 different types of shock-loaded materials are compared such as sand, concrete, aluminum foam, and layered composites. I would like to acknowledge the AFOSR under grant: FA9550-12-1-0128, ``Dynamic High-Pressure Behavior of Hierarchical Heterogenous Geological Granular Materials'' and the D.o.D. Supercomputing Resource Center.

  16. The singlet-triplet absorption and photodissociation of the HOCl, HOBr, and HOI molecules calculated by the MCSCF quadratic response method

    SciTech Connect

    Minaev, B.F.

    1999-09-09

    The molecular absorption spectra of hypochlorous, hypobromous, and hypoiodous acids have been studied by multiconfiguration self-consistent field (MCSCF) calculations with linear and quadratic response techniques. The complete form of the spin-orbit coupling (SOC) operator is accounted. The singlet-triplet transition to the lowest triplet state {sup 3}A{double{underscore}prime} {l{underscore}arrow} X{sup 1}A{prime} is shown to be responsible for the weak long-wavelength tail absorption and photodissociation in these molecules. The transition is polarized along the O-X bond (X = Cl, Br, I) and has an oscillator strength equal 6 x 10{sup {minus}6}, 8 x 10{sup {minus}5}, and 2 x 10{sup {minus}4} for hypochlorous, hypobromous, and hypoiodous acids, respectively. The second singlet-triplet transition {sup 3}A{prime} {l{underscore}arrow} X{sup 1}A{prime} comes to the region of the first singlet-singlet {sup 1}A{double{underscore}prime} {l{underscore}arrow} X{sup 1}A{prime} absorption and contributes significantly to the total cross-section at wavelengths {lambda} {approx} 300--320 nm (X = Cl), {lambda} {approx} 340--360 nm (X = Br), and {lambda} {approx} 400 nm (X = I). In the last case the singlet-triplet transition {sup 3}A{prime} {l{underscore}arrow} X{sup 1}A{prime} produces predominant contribution to HOI absorption in the visible region. All states are dissociative, so the singlet-triplet absorption contributes to the yield of photolysis in the important near-UV and visible region close to the intense solar actinic flux. Contributions to the removal mechanisms for atmospheric HOCl, HOBr, and HOI species are shortly discussed. The minor loss process of ozone in troposphere because of the HOI reservoir sink is getting evident on the ground of this calculations. The importance of SOC accounting for atmospheric photochemistry problems is stressed.

  17. Triplet excitations in graphene-based systems

    NASA Astrophysics Data System (ADS)

    Posvyanskiy, V.; Arnarson, L.; Hedegård, P.

    2015-02-01

    In this paper we investigate the excitations in a single graphene layer and in a single-walled carbon nanotube, i.e. the spectrum of magnetic excitations is calculated. In the absence of interactions in these systems there is a unique gap in the electron-hole continuum. We show that in the presence of Coulomb correlations bound states, magnons, appear in this forbidden region. The Coulomb interaction is examined in the context of the Pariser-Parr-Pople (PPP) model which takes into account the long-range nature of the interaction. The energy of the new bound states depends on the strength of the Coulomb forces. The calculations are performed for arbitrary electron-hole (e\\text-h) momentum q . In the end, this work finally settles the discussion sabout the existence of triplet excitations in graphene which has been lasting for a decade in the literature.

  18. A singlet - triplet T+ based qubit

    NASA Astrophysics Data System (ADS)

    Ribeiro, Hugo; Petta, Jason; Burkard, Guido

    2010-03-01

    We theoretically show that the electronic two-spin states singlet and triplet T+ are promising candidates for the implementation of a qubit in GaAs double quantum dots (DQD). A coherent superposition of the two-spin states is obtained by finite time Landau-Zener-St"uckelberg interferometry [1] and the single qubit rotations are performed by means of an external magnetic field with a typical amplitude of about 100 mT. In such a system, the coherent manipulation of the qubit takes place in a time scale of about 1 ns. We also study the nuclear induced decoherence, mainly due to hyperfine contact coupling between the electronic and nuclear spins, and compute the decoherence time T2^* ˜10 ns. [4pt] [1] H. Ribeiro and G. Burkard, Phys. Rev. Lett. 102, 216802 (2009)

  19. Magnetic chains on a triplet superconductor.

    PubMed

    Sacramento, P D

    2015-11-11

    The topological state of a two-dimensional triplet superconductor may be changed by an appropriate addition of magnetic impurities. A ferromagnetic magnetic chain at the surface of a superconductor with spin-orbit coupling may eliminate the edge states of a finite system giving rise to localized zero modes at the edges of the chain. The coexistence/competition between the two types of zero modes is considered. The reduction of the system to an effective 1d system gives partial information on the topological properties but the study of the two sets of zero modes requires a two-dimensional treatment. Increasing the impurity density from a magnetic chain to magnetic islands leads to a finite Chern number. At half-filling small concentrations are enough to induce chiral modes. PMID:26459719

  20. Understanding Singlet and Triplet Excitons in Acene Crystals from First Principles

    NASA Astrophysics Data System (ADS)

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

    2014-03-01

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

  1. Circadian-effect engineering of solid-state lighting spectra for beneficial and tunable lighting.

    PubMed

    Dai, Qi; Shan, Qifeng; Lam, Hien; Hao, Luoxi; Lin, Yi; Cui, Zhe

    2016-09-01

    Optimization of solid-state lighting spectra is performed to achieve beneficial and tunable circadian effects. First, the minimum spectral circadian action factor (CAF) of 2700 K white light-emitting diodes (LEDs) is studied for applications where biologically active illumination is undesirable. It is found that white-LEDs based on (i) RGB chips, (ii) blue & red chips plus green phosphor, and (iii) blue chip plus green & red phosphors are the corresponding minimum-CAF solutions at color-rendering index (CRI) requirements of 80, 90, and 95, respectively. Second, maximum CAF tunability of LED clusters is studied for dynamic daylighting applications. A dichromatic phosphor-converted blue-centered LED, a dichromatic phosphor-converted green-centered LED, and a monochromatic red LED are grouped to obtain white spectra between 2700 K and 6500 K. A maximum CAF tunability of 3.25 times is achieved with CRI above 90 and luminous efficacy of radiation of 313 - 373 lm/W. We show that our approaches have advantages over previously reported solutions on system simplicity, minimum achievable CAF value, CAF tunability range, and light source efficacy. PMID:27607613

  2. Particle diffusion and localized acceleration in inhomogeneous AGN jets - I. Steady-state spectra

    NASA Astrophysics Data System (ADS)

    Chen, Xuhui; Pohl, Martin; Böttcher, Markus

    2015-02-01

    We study the acceleration, transport, and emission of particles in relativistic jets. Localized stochastic particle acceleration, spatial diffusion, and synchrotron as well as synchrotron self-Compton (SSC) emission are considered in a leptonic model. To account for inhomogeneity, we use a 2D axisymmetric cylindrical geometry for both relativistic electrons and magnetic field. In this first phase of our work, we focus on steady-state spectra that develop from a time-dependent model. We demonstrate that small isolated acceleration region in a much larger emission volume are sufficient to accelerate particles to high energy. Diffusive escape from these small regions provides a natural explanation for the spectral form of the jet emission. The location of the acceleration regions within the jet is found to affect the cooling break of the spectrum in this diffusive model. Diffusion-caused energy-dependent inhomogeneity in the jets predicts that the SSC spectrum is harder than the synchrotron spectrum. There can also be a spectral hardening towards the high-energy section of the synchrotron spectrum, if particle escape is relatively slow. These two spectral hardening effects indicate that the jet inhomogeneity might be a natural explanation for the unexpected hard γ-ray spectra observed in some blazars.

  3. Interaction of triplet sensitizers with chlorophyll: Formation of singlet chlorophyll

    SciTech Connect

    Bohne, C.; Scaiano, J.C. )

    1989-03-29

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

  4. Ultrafast dissociation of triplets in pentacene induced by an electric field

    NASA Astrophysics Data System (ADS)

    Srimath Kandada, Ajay Ram; Petrozza, Annamaria; Lanzani, Guglielmo

    2014-08-01

    Singlet fission into a pair of triplet excitons in pentacene is envisaged to be a potential carrier multiplication route in organic photovoltaics. In order to shed light on the dissociation dynamics of the triplet states we performed electric field induced pump-probe experiments on polycrystalline films of pentacene. We find that the nascent triplet pair formed immediately after the fission process is susceptible to dissociation in the presence of the electric field. By measuring the temporal dynamics of the dissociation, we estimate its binding energy to be approximately 320 meV. After about 2 ps the triplets diffuse away from each other and the field assisted dissociation is substantially reduced. Our results suggest that if the nascent triplet pairs could be harvested at the interface in a device, the efficiency of the process would be higher.

  5. Triplet energy transfers in electrostatic host-guest assemblies of unsaturated organometallic cluster cations and carboxylate-containing porphyrin pigments.

    PubMed

    Aly, Shawkat M; Ayed, Charfedinne; Stern, Christine; Guilard, Roger; Abd-El-Aziz, Alaa S; Harvey, Pierre D

    2008-11-01

    The unsaturated cyclic [M3(dppm)3(CO)](2+) clusters (M = Pt, Pd; dppm = Ph2PCH2PPh2; such as PF6(-) salt) exhibit a cavity formed by the six dppm-phenyl groups placed like a picket fence above the unsaturated triangular M3 dicationic center. Electrostatic interactions of the M(3+) units inside this cavity with the carboxylate anion RCO2(-) [R = tetraphenylporphyrinatozinc(II), ZnTPP; p-phenyltritolylporphyrinatozinc(II), ZnTTPP; p-phenyltritolylporphyrinatopalladium(II), PdTTPP] form dyads for through-space triplet energy transfers. The binding constants are on the order of 20,000 M(-1) in all six cases (298 K). The energy diagram built upon absorption and emission spectra at 298 and 77 K places the [Pt3(dppm)3(CO)](2+) and [Pd3(dppm)3(CO)](2+) as triplet energy donors, respectively, with respect to the ZnTPPCO2(-), ZnTTPPCO2(-), and PdTTPPCO2(-) pigments, which act as acceptors. Evidence for energy transfer is provided by the transient absorption spectra at 298 K, where triplet-triplet absorption bands of the metalloporphyrin chromophores are depicted at all time (at 298 K) with total absence of the charge-separated state in the nanosecond to microsecond time scale. Rates for energy transfer (ranging in the 10(4) s(-1) time scale) are extracted from the emission lifetimes of the [Pt3(dppm)3(CO)](2+) donor in the free chromophore and the host-guest assemblies. The emission intensity of [Pd3(dppm)3(CO)](2+) is too weak to measure its spectrum and emission lifetime in the presence of the strongly luminescent metalloporphyrin-containing materials. For the [Pd3(dppm)3(CO)](2+)...metalloporphyrin dyads, evidence for fluorescence and phosphorescence lifetime quenching of the porphyrin chromophore at 298 K is provided. These quenchings, exhibiting rates of 10(4) (triplet) and 10(8) s(-1) (singlet), are attributed to a photoinduced electron transfer from the metalloporphyrin to the cluster due to the low reduction potential. PMID:18844340

  6. Observation of Singlet-Triplet Transitions in Capacitive Photocurrent Spectroscopy of Organic Solar Cells

    NASA Astrophysics Data System (ADS)

    Liu, Hui; Liu, Jinjun; Shah, Hemant M.; Alphenaar, Bruce W.

    2012-06-01

    Fullerene derivatives such as [6,6]-phenyl-C61-butyric acid methyl ester (PC60BM) and [6,6]-phenyl-C71-butyric acid methyl ester (PC70BM) are promising electron acceptors for use in efficient organic solar cells. Capacitive photocurrent spectra of both PC60BM and PC70BM in conjunction with indium tin oxide (ITO) reveal peaks with wavelengths longer than the S_1 ←S_0 transitions. The energies of low-lying triplet states of both molecules calculated using the ZINDO/S method agree with the experimentally observed transition frequencies. An excitation mechanism that involves collisions between the photoinduced free electrons in ITO and the organic molecules on the interface is proposed to explain the experimental observation. Tests on other organic solar cells are in process. Possibilities of improving the conversion efficiency of organic solar cells utilizing this mechanism will be discussed. Hemant M. Shah and Bruce W. Alphenaar, unpublished result.

  7. Formation of ultracold (7)Li(85)Rb molecules in the lowest triplet electronic state by photoassociation and their detection by ionization spectroscopy.

    PubMed

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

    2015-03-21

    We report the formation of ultracold (7)Li(85)Rb molecules in the a(3)Σ(+) 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(-1) below the (7)Li 2s (2)S1/2 + (85)Rb 5p (2)P1/2 asymptote. In addition, we use REMPI spectroscopy to probe the a(3)Σ(+) state and excited electronic 3(3)Π and 4(3)Σ(+) states and identify a(3)Σ(+) (v″ = 7-13), 3(3)Π (vΠ' = 0-10), and 4(3)Σ(+) (vΣ' = 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. PMID:25796252

  8. 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.

  9. GAS-PHASE ELECTRONIC SPECTRA OF POLYACETYLENE CATIONS: RELEVANCE OF HIGHER EXCITED STATES

    SciTech Connect

    Rice, C. A.; Rudnev, V.; Dietsche, R.; Maier, J. P.

    2010-07-15

    Transitions to higher electronic states of polyacetylene cations (HC{sub 2n}H{sup +}, n = 4, 5, 6) have been measured in the gas phase at {approx}20 K. The absorption spectra were obtained using a resonant two-color, two-photon fragmentation technique in an ion trap, allowing a direct comparison between laboratory and astrophysical data. The purpose was to investigate the relevance of such transitions to astronomical observations because the general expectation is that the bands could be too broad due to fast intramolecular processes. It is shown that the origin bands are still narrow enough (1-10 cm{sup -1}) to be considered, especially as the higher-lying transitions often possess large oscillator strengths.

  10. 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.

  11. Experimental and theoretical study of the electronic states and spectra of BiLi

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

    Gas phase emission spectra of the hitherto unknown free radical BiLi were measured in the NIR range with a Fourier-transform spectrometer. The emissions were observed from a fast-flow system in which bismuth vapor in argon carrier gas was passed through a microwave discharge and mixed with lithium vapor in an observation tube. Two systems of blue-degraded bands observed in the range 6900-9800 cm-1 are assigned to the transitions A3Π(A20+) → X3Σ-(X10+, X21). The Δv = 0, +1, and -1 sequences of both systems were measured at high spectral resolution. Rotational and vibrational analyses of 12 bands have yielded the spectroscopic parameters of the X10+, X21, and A20+ states including a hfs splitting parameter of the X21 state. In order to aid in the analysis of the experimental data, a series of relativistic configuration interaction calculations has been carried out to obtain spectroscopic parameters and potential curves for the low-lying states of BiLi and also electric dipole transition moments connecting them.

  12. 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.

  13. 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

  14. 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.

  15. The Rotational Spectra of Propyne in the Ground, V(10) = 1, V(10) = 2, and V(9) = 1 Vibrational States

    NASA Astrophysics Data System (ADS)

    Ware, John Matthew

    The problem of a vibrating-rotating polyatomic molecule is treated, with emphasis given to the case of molecules with C(,3V) sym- metry. It is shown that several of the gross features of the rotational spectra of polyatomic molecules in excited vibrational states can be predicted by group theoretical considerations. Expressions for the rotational transition frequencies of molecules of C(,3V) symmetry in the ground vibrational state, singly excited degenerate vibrational states, and doubly excited degenerate vibrational states are given. The deri- vation of these expressions by fourth order perturbation theory as given by Amat, Nielsen, and Tarrago is discussed. The ground and V(,10) = 1 rotational spectra of propyne have been investigated in the 17 to 70 GHz, and 17 to 53 GHz regions, respec- tively, and compared with predictions based on higher frequency measurements. The V(,9) = 1 and V(,10) = 2 rotational spectra of propyne have been investigated and assigned for the first time. A perturbation of the V(,9) = 1 rotational spectra for K = -L has been discovered and discussed. Methods of assignment for excited vibrational state spectra are discussed in detail. The methods of assignment given here allow the analysis of spectra where only a relatively small number of experi- mental points are available. A discrepancy has been found in the interpretation of recently reported infrared results on the rotational spectra of propyne in the V(,10) = 1, 2, 3, and 4 vibrational states. The constants of anharmoni- city which describe the change of the rotational constant, B, with the level of excitation of the V(,10) vibrational mode are rederived from microwave data. It is shown that microwave measurements increase the accuracy of one of these constants by over an order of magnitude.

  16. 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 +.

  17. 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.

  18. 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.

  19. 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

  20. 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.

  1. Probing the quantum ground state of a spin-1 Bose-Einstein condensate with cavity transmission spectra

    SciTech Connect

    Zhang, J. M.; Cui, S.; Jing, H.; Zhou, D. L.; Liu, W. M.

    2009-10-15

    We propose to probe the quantum ground state of a spin-1 Bose-Einstein condensate with the transmission spectra of an optical cavity. By choosing a circularly polarized cavity mode with an appropriate frequency, we can realize coupling between the cavity mode and the magnetization of the condensate. The cavity transmission spectra then contain information of the magnetization statistics of the condensate and thus can be used to distinguish the ferromagnetic and antiferromagnetic quantum ground states. This technique may also be useful for continuous observation of the spin dynamics of a spinor Bose-Einstein condensate.

  2. Exact evaluation of triplet photoproduction

    NASA Astrophysics Data System (ADS)

    Endo, I.; Kobayashi, T.

    1993-05-01

    The differential cross section of the triplet photoproduction (TPP), i.e., the pair production on an electron, has been evaluated by using the computer code HELAS in which all the eight lowest order Feynman graphs can be numerically treated without any approximation. It has been shown that the calculation with only two diagrams, called Borsellino diagrams, agrees very well with the full calculation in a wide kinematical region for photon energies between 50 and 550 MeV. For a possible application of TPP to the polarimetry of high energy linearly polarized photons, we show that the analyzing power can be enhanced by restricting the opening angle of the forward going e +e - pair.

  3. 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.

  4. Singlet and triplet instability theorems

    NASA Astrophysics Data System (ADS)

    Yamada, Tomonori; Hirata, So

    2015-09-01

    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.

  5. Singlet and triplet instability theorems.

    PubMed

    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. PMID:26395692

  6. 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

  7. Acquiring impedance spectra from diode-coupled primary batteries to determine health and state of charge

    NASA Astrophysics Data System (ADS)

    Christophersen, Jon P.; Morrison, John L.; Morrison, William H.

    The U.S. Army uses BA5590 Lithium Sulfur Dioxide primary batteries for portable electronic systems. There remains a need, however, for technology that can rapidly assess these batteries and estimate their remaining state of health after being used without degrading them to determine if there is remaining useful life for additional missions. This allows the full range of charge to be consumed before the battery is recycled or disposed. Impedance spectroscopy measurements have been shown to be a useful diagnostic tool, but standard methods cannot be applied to the BA5590 batteries because of the up-front electronics. The BA5590 module is diode-coupled and a charge-neutral excitation signal would be half-wave rectified and completely corrupt the results. However, a rapid impedance spectrum measurement technique has been developed that can be used for the BA5590s based on the addition of a small discharge bias load super-imposed on the sinusoidal excitation signal. The feasibility of this approach was initially simulated and then successfully applied to cell strings on four fresh BA5590 modules. The results clearly showed consistent and repeatable impedance spectra with no significant impact on the SOC as a result of the measurement. Details of this measurement technique and discussion of the preliminary results are presented.

  8. 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

  9. Equation of state of strongly interacting matter: spectra for thermal particles and intensity correlation of thermal photons

    NASA Astrophysics Data System (ADS)

    De, Somnath; Srivastava, Dinesh K.; Chatterjee, Rupa

    2010-11-01

    We find that an equation of state for hot hadronic matter consisting of all baryons having M < 2 GeV and all mesons having M < 1.5 GeV, along with Hagedorn resonances in thermal and chemical equilibrium, matches rather smoothly with the lattice equation of state (p4 action, Nτ = 8) for T up to ≈200 MeV, when corrected for the finite volume of hadrons. Next we construct two equations of state for strongly interacting matter; one, HHL, in which the above is matched to the lattice equation of state at T = 165 MeV and the other, HHB, where we match it to a bag model equation of state with critical temperature Tc = 165 MeV. We compare particle spectra, thermal photon spectra and histories of evolution of the quark-gluon plasma produced in the central collision of gold (lead) nuclei at RHIC (LHC) energies, considering ideal hydrodynamical expansion of the system. The particle and thermal photon spectra are seen to differ only marginally for the two equations of state. The history of evolution shows differences in the evolution of temperature and radial velocity, as one might expect. We calculate intensity interferometry of thermal photons and find it to be quite distinct for the two equations of state, especially for the outward correlation. The longitudinal correlation also shows a dependence on the equation of state, though, to a smaller extent.

  10. Mechanism of the Decay of Thymine Triplets in DNA Single Strands.

    PubMed

    Pilles, Bert M; Bucher, Dominik B; Liu, Lizhe; Clivio, Pascale; Gilch, Peter; Zinth, Wolfgang; Schreier, Wolfgang J

    2014-05-01

    The decay of triplet states and the formation of cyclobutane pyrimidine dimers (CPDs) after UV excitation of the all-thymine oligomer (dT)18 and the locked dinucleotide TLpTL were studied by nanosecond IR spectroscopy. IR marker bands characteristic for the CPD lesion and the triplet state were observed from ∼1 ns (time resolution of the setup) onward. The amplitudes of the CPD marker bands remain constant throughout the time range covered (up to 10 μs). The triplet decays with a time constant of ∼10 ns presumably via a biradical intermediate (lifetime ∼60 ns). This biradical has often been invoked as an intermediate for CPD formation via the triplet channel. The present results lend strong support to the existence of this intermediate, yet there is no indication that its decay contributes significantly to CPD formation. PMID:26270105

  11. Exchange Interaction Makes Superconductivity in 3D Dirac Semi-metal Triplet

    NASA Astrophysics Data System (ADS)

    Rosenstein, B.; Shapiro, B. Ya.; Li, Dingping; Shapiro, I.

    2015-04-01

    Conventional electron-phonon coupling induces either odd (triplet) or even (singlet) pairing states in a time reversal and inversion invariant Dirac semi-metal. In a certain range of the chemical potential and parameters characterizing the pairing attraction (effective electron-electron coupling constant and the Debye energy ) the energy of the singlet although always lower, prevails by a very slim margin over the triplet. This means that interactions that are small but discriminate between the spin singlet and the spin triplet determine the nature of the superconducting order there. It is shown that in materials close enough to the Dirac point ( ) a moderate exchange constant (below Stoner instability to ferromagnetism) stabilizes the odd pairing superconducting state. The 3D quantum critical point at of transition to the triplet superconductivity governs the physics of the superconductor.

  12. Singlet-Triplet Gaps of Cobalt Nitrosyls: Insights from Tropocoronand Complexes.

    PubMed

    Hopmann, Kathrin H; Conradie, Jeanet; Tangen, Espen; Tonzetich, Zachary J; Lippard, Stephen J; Ghosh, Abhik

    2015-08-01

    A density functional theory (DFT) study of {CoNO}(8) cobalt nitrosyl complexes containing the [n,n]tropocoronand ligand (TC-n,n) has revealed a sharp reduction of singlet-triplet gaps as the structures change from near-square-pyramidal (for n = 3) to trigonal-bipyramidal with an equatorial NO (for n = 5, 6). An experimental reinvestigation of [Co(TC-3,3)(NO)] has confirmed that it is not paramagnetic, as originally reported, but diamagnetic, like all other {CoNO}(8) complexes. Furthermore, DFT calculations indicate a substantial singlet-triplet gap of about half an eV or higher for this complex. At the other end of the series, low-energy, thermally accessible triplet states are predicted for [Co(TC-6,6)(NO)]. Enhanced triplet-state reactivity may well provide a partial explanation for the failure to isolate this compound as a stable species. PMID:26203786

  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

    2016-04-01

    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 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. PMID:26802538

  14. 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.

  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. An analysis of the methyl rotation dynamics in the S0 (X˜ 1A1) and T1 (ã 3A2) states of thioacetone, (CH3)2CS and (CD3)2CS from pyrolysis jet spectra

    NASA Astrophysics Data System (ADS)

    Moule, D. C.; Smeyers, Y. G.; Senent, M. L.; Clouthier, D. J.; Karolczak, J.; Judge, R. H.

    1991-09-01

    Jet-cooled, laser-induced phosphorescence excitation spectra (LIP) of thioacetone (CH3)2CS/(CD3)2CS have been recorded over the region 16 800-18 500 cm-1 using the pyrolysis jet spectroscopic technique. The responsible electronic transition, T1←S0, ã 3A`←X˜ 1A1, results from an n→π* electron promotion and gives rise to a pattern of vibronic bands that were attributed to activity of the methyl torsion and the sulphur out-of-plane wagging modes. The intensities of the torsional and wagging progressions in the excitation spectra were interpreted in terms of a C2v-Cs molecular distortion of the triplet molecule from its singlet ground state equilibrium structure. A complete unrestricted Hartree-Fock (UHF) ab initio molecular orbital (MO) structural optimization of the T1 state predicted that the sulphur was displaced by 27.36° from the molecular plane and the methyl groups were rotated by 10.93° in clockwise-counterclockwise directions. Restricted Hartree-Fock (RHF) calculations were used to generate the V(θ1,θ2) potential surface governing methyl rotation for the S0 state. This was incorporated into a two-dimensional Hamiltonian, symmetrized for the G36 point group and solved variationally for the torsional frequencies. The calculated frequencies of 159.97/118.94 for the ν17(b1) mode of S0 (CH3)2CS/(CD3)2CS were found to agree with the experimental values, 153.2/114.7 cm-1.

  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. 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. PMID:26471446

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

    PubMed

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

    2008-03-01

    In this work the photoprotective role of all xanthophylls in LHCII, Lhcb4, and Lhcb5 is investigated by laser-induced Triplet-minus-Singlet (TmS) spectroscopy. The comparison of native LHCII trimeric complexes with different carotenoid composition shows that the xanthophylls in sites V1 and N1 do not directly contribute to the chlorophyll triplet quenching. The largest part of the triplets is quenched by the lutein bound in site L1, which is located in close proximity to the chlorophylls responsible for the low energy state of the complex. The lutein in the L2 site is also active in triplet quenching, and it shows a longer triplet lifetime than the lutein in the L1 site. This lifetime difference depends on the occupancy of the N1 binding site, where neoxanthin acts as an oxygen barrier, limiting the access of O(2) to the inner domain of the Lhc complex, thereby strongly contributing to the photostability. The carotenoid triplet decay of monomeric Lhcb1, Lhcb4, and Lhcb5 is mono-exponential, with shorter lifetimes than observed for trimeric LHCII, suggesting that their inner domains are more accessible for O(2). As for trimeric LHCII, only the xanthophylls in sites L1 and L2 are active in triplet quenching. Although the chlorophyll to carotenoid triplet transfer is efficient (95%) in all complexes, it is not perfect, leaving 5% of the chlorophyll triplets unquenched. This effect appears to be intrinsically related to the molecular organization of the Lhcb proteins. PMID:18079125

  20. 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.

  1. Effects of the Hydration State on the Mid-Infrared Spectra of Urea and Creatinine in Relation to Urine Analyses.

    PubMed

    Oliver, Katherine V; Maréchal, Amandine; Rich, Peter R

    2016-06-01

    When analyzing solutes by Fourier transform infrared (FT-IR) spectroscopy in attenuated total reflection (ATR) mode, drying of samples onto the ATR crystal surface can greatly increase solute band intensities and, therefore, aid detection of minor components. However, analysis of such spectra is complicated by the existence of alternative partial hydration states of some substances that can significantly alter their infrared signatures. This is illustrated here with urea, which is a dominant component of urine. The effects of hydration state on its infrared spectrum were investigated both by incubation in atmospheres of fixed relative humidities and by recording serial spectra during the drying process. Significant changes of absorption band positions and shapes were observed. Decomposition of the CN antisymmetric stretching (νas) band in all states was possible with four components whose relative intensities varied with hydration state. These correspond to the solution (1468 cm(-1)) and dry (1464 cm(-1)) states and two intermediate (1454 cm(-1) and 1443 cm(-1)) forms that arise from specific urea-water and/or urea-urea interactions. Such intermediate forms of other compounds can also be formed, as demonstrated here with creatinine. Recognition of these states and their accommodation in analyses of materials such as dried urine allows more precise decomposition of spectra so that weaker bands of diagnostic interest can be more accurately defined. PMID:27170705

  2. Vigilance states, EEG spectra, and cortical temperature in the guinea pig.

    PubMed

    Tobler, I; Franken, P; Jaggi, K

    1993-06-01

    Vigilance states, electroencephalogram (EEG) power spectra (0.25-25.0 Hz), and cortical temperature (TCRT) were obtained in nine guinea pigs for 24 h in a 12:12-h light-dark (LD 12:12) schedule. Sleep was markedly polyphasic and fragmented and amounted to 32% of recording time, which is a low value compared with sleep in other rodents. There was 6.8% more sleep in the light period than in the dark period. EEG power density in non-rapid eye movement (NREM) sleep showed no significant temporal trend within the light or the dark period. The homeostatic aspects of sleep regulation, as proposed in the two-process model, can account for the slow-wave activity (SWA) pattern also in the guinea pig: The small 24-h amplitude of the sleep-wakefulness pattern resulted in a small, 12% decline of SWA within the light period. In contrast to more distinctly nocturnal rodents, SWA in the dark period was not higher than in the light period. TCRT showed no difference between the light and the dark period. TCRT in REM sleep and waking was higher than TCRT in NREM sleep. TCRT increased after the transition from NREM sleep to either REM sleep or waking, and decreased in the last minute before the transition and after the transition from waking to NREM sleep. Motor activity measured in six animals for 11 days in constant darkness showed no apparent rhythm in three animals and a significant circadian rhythm in three others. Our data support the notion that guinea pigs exhibit only a weak circadian rest-activity rhythm. PMID:8322965

  3. Abundances, charge states, and energy spectra of helium and heavy ions during solar particle events

    NASA Technical Reports Server (NTRS)

    Gloeckler, G.; Sciambi, R.; Fan, C. Y.; Hovestadt, D.

    1975-01-01

    Carbon and oxygen energy spectra observed during several solar events indicate a systematic deviation of these spectra from a simple power law: the spectra bend down below about 100 keV/nuc and the amount of this bending is highly correlated with the size of the flare, as measured by the 'event averaged' flux of 130-220 keV protons. The energy spectra of helium computed for the same time periods do not show a similar feature. A large variability of the alpha/CNO ratio is found from event to event (from 2 to about 20 at 40 keV/nuc), and in all cases examined the carbon and oxygen nuclei are nearly fully stripped. These results are interpreted as evidence for storage of energetic ions in hot coronal regions, followed by strong adiabatic deceleration.

  4. Boron Subphthalocyanines as Triplet Harvesting Materials within Organic Photovoltaics.

    PubMed

    Castrucci, Jeffrey S; Josey, David S; Thibau, Emmanuel; Lu, Zheng-Hong; Bender, Timothy P

    2015-08-01

    Singlet fission, the generation of two excited triplet states from a single absorbed photon, is currently an area of significant interest to photovoltaic researchers. In this Letter, we outline how a polychlorinated boron subphthalocyanine, previously hypothesized to be an effective harvester of singlet fission derived triplets from pentacene, is relatively efficient at facilitating the process. As expected, we found a major increase in photocurrent generation at the expense of device voltage. For a direct point of comparison, we also have paired the same polychlorinated boron subphthalocyanine with α-sexithiophene to probe the alternative technique of complementary absorption engineering. The sum of these efforts have let us present new guidelines for the molecular design of boron subphthalocyanine for organic photovoltaic applications. PMID:26267212

  5. 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

  6. Triplet-quadruplet dark matter

    NASA Astrophysics Data System (ADS)

    Tait, Tim M. P.; Yu, Zhao-Huan

    2016-03-01

    We explore a dark matter model extending the standard model particle content by one fermionic SU(2) L triplet and two fermionic SU(2) L quadruplets, leading to a minimal realistic UV-complete model of electroweakly interacting dark matter which interacts with the Higgs doublet at tree level via two kinds of Yukawa couplings. After electroweak symmetry-breaking, the physical spectrum of the dark sector consists of three Majorana fermions, three singly charged fermions, and one doubly charged fermion, with the lightest neutral fermion χ 1 0 serving as a dark matter candidate. A typical spectrum exhibits a large degree of degeneracy in mass between the neutral and charged fermions, and we examine the one-loop corrections to the mass differences to ensure that the lightest particle is neutral. We identify regions of parameter space for which the dark matter abundance is saturated for a standard cosmology, including coannihilation channels, and find that this is typically achieved for {m}_{χ_1^0}˜ 2.4 TeV. Constraints from precision electroweak measurements, searches for dark matter scattering with nuclei, and dark matter annihilation are important, but leave open a viable range for a thermal relic.

  7. TRIO (Triplet Ionospheric Observatory) Mission

    NASA Astrophysics Data System (ADS)

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

    2009-12-01

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

  8. 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.

  9. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2003-08-01

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

  11. Entanglement and Metrology with Singlet-Triplet Qubits

    NASA Astrophysics Data System (ADS)

    Shulman, Michael Dean

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

  12. Theoretical Studies of Singlet and Triplet Formation in Polymer LEDs.

    NASA Astrophysics Data System (ADS)

    Mazumdar, Sumit

    2002-03-01

    Spin statistics for electron-hole recombination in polymer LEDs suggest that the singlet excited state is formed with a probability of only 0.25. Recent experiments by several groups, however, indicate, that the probability of formation of the singlet is considerably larger than this. We present a comprehensive theory of the formation cross-sections of the singlet and triplet excitons in conjugated polymers. Within our model, electron correlations influence the relative yields of the singlet and triplet excitons in a profound manner. We have carried out the dynamics of the electron-hole recombination in pair of simple conjugated organic molecules, both with noninteracting electrons and within the Pariser-Parr-Pople model with interacting electrons. The formation cross-section for the singlet exciton is considerably larger than the triplet for the correlated electron case. Numerical results as well as simple physical interpretations of theoretical and experimental results will be presented. This work was supported in part by NSF DMR-0101659 and CSIR, India.

  13. Scalar triplet flavored leptogenesis: a systematic approach

    SciTech Connect

    Sierra, D. Aristizabal; Dhen, Mikaël; Hambye, Thomas E-mail: mikadhen@ulb.ac.be

    2014-08-01

    Type-II seesaw is a simple scenario in which Majorana neutrino masses are generated by the exchange of a heavy scalar electroweak triplet. When endowed with additional heavy fields, such as right-handed neutrinos or extra triplets, it also provides a compelling framework for baryogenesis via leptogenesis. We derive in this context the full network of Boltzmann equations for studying leptogenesis in the flavored regime. To this end we determine the relations which hold among the chemical potentials of the various particle species in the thermal bath. This takes into account the standard model Yukawa interactions of both leptons and quarks as well as sphaleron processes which, depending on the temperature, may be classified as faster or slower than the Universe Hubble expansion. We find that when leptogenesis is enabled by the presence of an extra triplet, lepton flavor effects allow the production of the B-L asymmetry through lepton number conserving CP asymmetries. This scenario becomes dominant as soon as the triplets couple more to leptons than to standard model scalar doublets. In this case, the way the B-L asymmetry is created through flavor effects is novel: instead of invoking the effect of L-violating inverse decays faster than the Hubble rate, it involves the effect of L-violating decays slower than the Hubble rate. We also analyze the more general situation where lepton number violating CP asymmetries are present and actively participate in the generation of the B-L asymmetry, pointing out that as long as L-violating triplet decays are still in thermal equilibrium when the triplet gauge scattering processes decouple, flavor effects can be striking, allowing to avoid all washout suppression effects from seesaw interactions. In this case the amount of B-L asymmetry produced is limited only by a universal gauge suppression effect, which nevertheless goes away for large triplet decay rates.

  14. Intramolecular charge transfer of push-pull pyridinium salts in the triplet manifold.

    PubMed

    Carlotti, Benedetta; Consiglio, Giuseppe; Elisei, Fausto; Fortuna, Cosimo G; Mazzucato, Ugo; Spalletti, Anna

    2014-09-11

    The solvent effect on the triplet state properties of the iodides of three trans (E) isomers of 2-D-vinyl-1-methylpyridinium, where D is a donor group (4-(dimethylamino)phenyl, 3,4,5-trimethoxyphenyl, and 1-pyrenyl), was studied by nanosecond transient absorption techniques. The results obtained allowed us to complete a previous study on the negative solvatochromism and the role of the solvent-controlled intramolecular charge transfer (ICT) relaxation pathways in the excited singlet state, carried out by ultrafast absorption techniques and DFT calculations (J. Phys. Chem. A 2014, 118, 3580-3592 ). The solvent effect on the intersystem crossing to the triplet manifold gave information on the competition of the relaxation processes in the singlet and triplet states and the extent and mechanism of the photoreactive deactivation, particularly operative for the pyrenyl derivative. For the latter the results showed that the ICT process also occurs in the triplet manifold. In fact, the formation of two triplet states with different nature and affected differently by oxygen was observed for the pyrenyl derivative in water and assigned to the (3)LE* and (3)ICT* states. The related structure and solvent effects on the trans → cis photoisomerization are briefly discussed. PMID:25146975

  15. Automated charge state determination of complex isotope-resolved mass spectra by peak-target Fourier transform.

    PubMed

    Chen, Li; Yap, Yee Leng

    2008-01-01

    This study describes a new algorithm for charge state determination of complex isotope-resolved mass spectra. This algorithm is based on peak-target Fourier transform (PTFT) of isotope packets. It is modified from the widely used Fourier transform method because Fourier transform may give ambiguous charge state assignment for low signal-to-noise ratio (S/N) or overlapping isotopic clusters. The PTFT algorithm applies a novel "folding" strategy to enhance peaks that are symmetrically spaced about the targeted peak before applying the FT. The "folding" strategy multiplies each point to the high-m/z side of the targeted peak by its counterpart on the low-m/z side. A Fourier transform of this "folded" spectrum is thus simplified, emphasizing the charge state of the "chosen" ion, whereas ions of other charge states contribute less to the transformed data. An intensity-dependent technique is also proposed for charge state determination from frequency signals. The performance of PTFT is demonstrated using experimental electrospray ionization Fourier transform ion cyclotron resonance mass spectra. The results show that PTFT is robust for charge state determination of low S/N and overlapping isotopic clusters, and also useful for manual verification of potential hidden isotopic clusters that may be missed by the current analysis algorithms, i.e., AID-MS or THRASH. PMID:18293485

  16. 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. PMID:25233377

  17. 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.

  18. Actinometry in monochromatic flash photolysis: the extinction coefficient of triplet benzophenone and quantum yield of triplet zinc tetraphenyl porphyrin

    SciTech Connect

    Hurley, J.K.; Sinai, N.; Linschitz, H.

    1982-11-15

    The extinction coefficient epsilon/sub T/, of triplet benzophenone in benzene has been directly determined by absolute measurements of absorbed energy and triplet absorbance, ..delta..D/sup 0//sub T/, under demonstrably linear conditions where incident excitation energy, E/sub 0/, and ground state absorbance, A/sub 0/, are both extrapolated to zero. The result, 7220 +- 320 M/sup -1/ cm/sup -1/ at 530 nm, validates and corrects many measurements of triplet and radical extinctions and yields, using the energy-transfer method. As E/sub 0/ and A/sub 0/ both decrease, ..delta..D/sup 0//sub T/ becomes proportional to their product. In this situation, the ratio R = (1/A/sub 0/) (d..delta..D/sup 0//sub T//dE/sub 0/) = (epsilon/sub T/ /sup -/ epsilon/sub G/)phi/sub T/. Measurements of R, referred to benzophenone, give (epsilon/sub T/ - epsilon/sub G/)phi/sub T/ for any substance, without necessity for absolute energy calibration. Both absolute and relative laser flash measurements on zinc tetraphenyl porphyrin (epsilon/sub T/ - epsilon/sub G/ at 470 nm = 7.3 x 10/sup 4/ M/sup -1/ cm/sup -1/) give phi/sub T/ = 0.83 +- 0.04. 6 figures, 2 tables.

  19. Restricted active space calculations of L-edge X-ray absorption spectra: From molecular orbitals to multiplet states

    SciTech Connect

    Pinjari, Rahul V.; Delcey, Mickaël G.; Guo, Meiyuan; Lundberg, Marcus; Odelius, Michael

    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{sup 5}) model systems with well-known electronic structure, viz., atomic Fe{sup 3+}, high-spin [FeCl{sub 6}]{sup 3−} with ligand donor bonding, and low-spin [Fe(CN){sub 6}]{sup 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.

  20. Second-law irreversibility and phase-space dimensionality loss from time-reversible nonequilibrium steady-state Lyapunov spectra

    NASA Astrophysics Data System (ADS)

    Hoover, W. G.; Posch, H. A.

    1994-03-01

    We consider steady-state nonequilibrium many-body flows of mass and momentum. For several such diffusive and viscous flows we estimate the phase-space strange-attractor Lyapunov dimensions from the complete spectrum of Lyapunov exponents. We vary the number of particles and the number of thermostated degrees of freedom, as well as the deviation from equilibrium. The resulting Lyapunov spectra provide numerical evidence that the fractal dimensionality loss in such systems remains extensive in a properly defined nonequilibrium analog of the equilibrium large-system thermodynamic limit. The data also suggest a variational principle in the vicinity of nonequilibrium steady states.

  1. Charge-state resolved energy spectra of swift 22Ne ions passing through thin carbon foils

    NASA Astrophysics Data System (ADS)

    Blazevic, A.; Bohlen, H. G.; von Oertzen, W.; Balashov, V. V.; Stysin, A. V.

    2006-04-01

    The method of coupled kinetic equations for a unified description of charge exchange and excitation of ions passing through matter is applied to calculate energy-loss spectra of swift 22Ne ions in carbon foils in the non-equilibrium regime. Good agreement is obtained for these calculations with the results of recent measurements, performed at the ISL-facility at the Hahn-Meitner Institute.

  2. Triplet lifetime and delayed fluorescence of azulene

    NASA Astrophysics Data System (ADS)

    Kray, Hans-Joachim; Nickel, Bernhard

    1980-11-01

    With solutions of azulene (Az) and fluoranthene (Fl) in isopentane a delayed fluorescence (DF) S 2(Az) → S 0(Az), resulting from hetero-triplet—triplet annihilation T 1(Az) + T 1(Fl) → S 2(Az) + S 0(Fl), can be observed. From the time-dependence of this DF after laser flash excitation the triplet lifetime of azulene can be calculated. The triplet lifetime has been determined in the temperature range from 131 K to 201 K. The temperature-dependence of the triplet lifetime is explained by thermally activated intersystem crossing (ISC) T 1 ⇝ S 1, followed by internal conversion S 1 ⇝ S 0; the corresponding activation energy approximately equals the difference of the excitation energies of S 1 and T 1. The extrapolated low-temperature value of the triplet lifetime (48 ± 2) μs. The quantum efficiency of the ISC S 1 ⇝ T 1 is estimated to be of the order of magnitude of 4 × 10 -6, and for the quantum efficiency of the ISC S 2 ⇝ T 1 an upper bound of 0.04 is obtained. The experimental conditions for the observation of the phosphorescence T 1 ⇝ S 0 and the E-type DF S 1 → S 0 are discussed.

  3. Excited state dipole moments of chloroanilines and chlorophenols from solvatochromic shifts in electronic absorption spectra: Support for the concept of excited state group moments

    NASA Astrophysics Data System (ADS)

    Prabhumirashi, L. S.; Satpute, R. S.

    The dipole moments of isomeric o-, m- and p-chloroanilines and chlorophenols in electronically excited L a and L b states are estimated from solvent induced polarization shifts in electronic absorption spectra. It is observed that μ e( L a) > μ e( L b) > μ g, which is consistent with the general theory of polarization red shift. The μ es are found to be approximately co-linear with the corresponding μ gs. The concept of group moments is extended to aromatic molecules in excited states. This approach is found to be useful in understanding correlations among the excited states of mono- and disubstituted benzenes.

  4. Singlet-triplet annihilation in single LHCII complexes.

    PubMed

    Gruber, J Michael; Chmeliov, Jevgenij; Krüger, Tjaart P J; Valkunas, Leonas; van Grondelle, Rienk

    2015-08-14

    In light harvesting complex II (LHCII) of higher plants and green algae, carotenoids (Cars) have an important function to quench chlorophyll (Chl) triplet states and therefore avoid the production of harmful singlet oxygen. The resulting Car triplet states lead to a non-linear self-quenching mechanism called singlet-triplet (S-T) annihilation that strongly depends on the excitation density. In this work we investigated the fluorescence decay kinetics of single immobilized LHCIIs at room temperature and found a two-exponential decay with a slow (3.5 ns) and a fast (35 ps) component. The relative amplitude fraction of the fast component increases with increasing excitation intensity, and the resulting decrease in the fluorescence quantum yield suggests annihilation effects. Modulation of the excitation pattern by means of an acousto-optic modulator (AOM) furthermore allowed us to resolve the time-dependent accumulation and decay rate (∼7 μs) of the quenching species. Inspired by singlet-singlet (S-S) annihilation studies, we developed a stochastic model and then successfully applied it to describe and explain all the experimentally observed steady-state and time-dependent kinetics. That allowed us to distinctively identify the quenching mechanism as S-T annihilation. Quantitative fitting resulted in a conclusive set of parameters validating our interpretation of the experimental results. The obtained stochastic model can be generalized to describe S-T annihilation in small molecular aggregates where the equilibration time of excitations is much faster than the annihilation-free singlet excited state lifetime. PMID:26156159

  5. Theoretical Study of the Luminescent States and Electronic Spectra of UO2Cl2 in an Argon Matrix

    SciTech Connect

    Su, Jing; Wang, Yi-Lei; Wei, Fan; Schwarz, W H E.; Li, Jun

    2011-08-25

    The electronic absorption and emission spectra of freeUO2Cl2 and its Ar-coordinated complexes below 27 000 cm-1 are investigated at the levels of ab initio complete active space second-order perturbation theory (CASPT2) and coupled-cluster singles and doubles and perturbative triples [CCSD(T)] using valence 3ζ-polarized basis sets. The influence of the argon matrix in the 12K experiment on the electronic spectra is explored by investigating the excited states of argon complexes ArnUO2Cl2. The calculated two most stable complexes with n = 2, 3 can explain the observed two matrix sites corresponding to the experimental twocomponent luminescence decay. In these uranyl complexes, Ar-coordination is found to have little influence on the 3Φ (Ω = 2g) character of the luminescent state and on the electronic spectral shape. The calculations yield a coherent assignment of the experimental excitation spectra that improves on previous assignments. The simulated luminescence spectral curves based on the calculated spectral parameters of UO2Cl2 from both CASPT2 and CCSD(T) agree well with experiment.

  6. 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.

  7. 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.

  8. Solid state photochemistry of polycarbonates

    NASA Technical Reports Server (NTRS)

    Gupta, A.; Rembaum, A.; Moacanin, J.

    1978-01-01

    The quantum yield of photoFries rearrangement in a polycarbonate film has been analyzed as a function of temperature and humidity on the basis of previously reported (Koyler and Mann, 1977) experimental data. Results indicate that in the homogeneous amorphous phase, photoFries rearrangement is a concerted process proceeding either from the pi star reversed arrow n singlet, in which case it must be subject to considerable self quenching, or from a triplet, presumably the first triplet since the lifetime of higher triplets is expected to be very short in the solid phase. If the parent excited state is the first triplet, chain scission is possibly an independent process, probably occurring from the pi star reversed arrow n singlet. Evidence of chain scission on photodegradation in the solid state includes loss of C-O and C-C bond intensities revealed in the Fourier transform infrared spectra, gel permeation chromotography elution profiles of degraded film samples dissolved in CHCl3, and a decrease in tensile strength and T sub g as photodegradation proceeds. Chain scission is apparently inhibited as photoFries products accumulate.

  9. Magnetic dipolar interaction between correlated triplets created by singlet fission in tetracene crystals

    NASA Astrophysics Data System (ADS)

    Wang, Rui; Zhang, Chunfeng; Zhang, Bo; Liu, Yunlong; Wang, Xiaoyong; Xiao, Min

    2015-10-01

    Singlet fission can potentially break the Shockley-Queisser efficiency limit in single-junction solar cells by splitting one photoexcited singlet exciton (S1) into two triplets (2T1) in organic semiconductors. A dark multiexciton state has been proposed as the intermediate connecting S1 to 2T1. However, the exact nature of this multiexciton state, especially how the doubly excited triplets interact, remains elusive. Here we report a quantitative study on the magnetic dipolar interaction between singlet-fission-induced correlated triplets in tetracene crystals by monitoring quantum beats relevant to the multiexciton sublevels at room temperature. The resonances of multiexciton sublevels approached by tuning an external magnetic field are observed to be avoided, which agrees well with the theoretical predictions considering a magnetic dipolar interaction of ~0.008 GHz. Our work quantifies the magnetic dipolar interaction in certain organic materials and marks an important step towards understanding the underlying physics of the multiexciton state in singlet fission.

  10. 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.

  11. 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).

  12. Improved Cell Typing by Charge-State Deconvolution of matrix-assisted laser desorption/ionization Mass Spectra

    SciTech Connect

    Wilkes, Jon G.; Buzantu, Dan A.; Dare, Diane J.; Dragan, Yvonne P.; Chiarelli, M. Paul; Holland, Ricky D.; Beaudoin, Michael; Heinze, Thomas M.; Nayak, Rajesh; Shvartsburg, Alexandre A.

    2006-05-30

    Robust, specific, and rapid identification of toxic strains of bacteria and viruses, to guide the mitigation of their adverse health effects and optimum implementation of other response actions, remains a major analytical challenge. This need has driven the development of methods for classification of microorganisms using mass spectrometry, particularly matrix-assisted laser desorption ionization MS (MALDI) that allows high throughput analyses with minimum sample preparation. We describe a novel approach to cell typing based on pattern recognition of MALDI spectra, which involves charge-state deconvolution in conjunction with a new correlation analysis procedure. The method is applicable to both prokaryotic and eukaryotic cells. Charge-state deconvolution improves the quantitative reproducibility of spectra because multiply-charged ions resulting from the same biomarker attaching a different number of protons are recognized and their abundances are combined. This allows a clearer distinction of bacterial strains or of cancerous and normal liver cells. Improved class distinction provided by charge-state deconvolution was demonstrated by cluster spacing on canonical variate score charts and by correlation analyses. Deconvolution may enhance detection of early disease state or therapy progress markers in various tissues analyzed by MALDI.

  13. The First Chromium-53 Solid-State Nuclear Magnetic Resonance Spectra of Diamagnetic Chromium(0) and Chromium(VI) Compounds

    SciTech Connect

    Bryce, David L.; Wasylishen, Roderick E.

    2001-01-01

    Chromium-53 is a spin-3/2 nucleus with a relatively small magnetic moment, low natural abundance, and large quadrupole moment. These properties have severely hampered the development of 53Cr NMR, especially in the solid state. In this Communication, the first 53Cr solid-state NMR spectra of prototypal diamagnetic chromium(0) and chromium(VI) compounds are presented. Specifically, analyses of 53Cr NMR spectra of solid hexacarbonylchromium(0), caesium chromate(VI), and potassium chromate(VI) have allowed for the determination of 53Cr quadrupolar coupling parameters and the first chromium chemical shift (CS) tensors. This work demonstrates the potential of 53Cr solid-state NMR, in particular the extreme sensitivity of the 53Cr quadrupolar coupling constant to the local chromium environment. Comparisons are made to known 53Cr NMR parameters available from solution studies, and to the 95Mo solid-state NMR parameters of analogous molybdenum compounds. The influence of crystal symmetry present in isomorphic Cr(CO)6 and Mo(CO)6 is strongly reflected in the magnitudes of the metal nuclei CS tensors and in their orientation with respect to their corresponding electric field gradient tensors.

  14. Iridium-Based High-Sensitivity Oxygen Sensors and Photosensitizers with Ultralong Triplet Lifetimes.

    PubMed

    Jiang, Xinpeng; Peng, Jiang; Wang, Jianchun; Guo, Xinyan; Zhao, Dahui; Ma, Yuguo

    2016-02-17

    The photophysics of a series of bichromophoric molecules featuring an intramolecular triplet energy transfer between a triscyclometalated iridium(III) complex and covalently linked organic group are studied. By systematically varying the energy gap (0.1-0.3 eV) between the donor (metal complex) and acceptor (pyrene unit), reversible triplet energy transfer processes with equilibrium constant K ranging from ca. 500 to 40 000 are established. Unique photophysical consequences of such large K values are observed. Because of the highly imbalanced forward and backward energy transfer rates, triplet excitons dominantly populate the acceptor moiety in the steady state, giving rise to ultralong luminescence lifetimes up to 1-4 ms. Because the triscyclometalated Ir and triplet pyrene groups both impart relatively small nonradiative energy loss, decent phosphorescence quantum yields (Φ = 0.1-0.6) are attained in spite of the exceptionally prolonged excited states. By virtue of such precious combination of long-lived triplet state and high Φ, these bichromophoric molecules can serve as highly sensitive luminescent sensors for detecting trace amount of O2 and as potent photosensitizers for producing singlet oxygen even under low-oxygen content conditions. PMID:26592255

  15. Ultrabright fluorescent OLEDS using triplet sinks

    DOEpatents

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

    2013-06-04

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

  16. Electron energy spectra of H{sup {minus}} autodetaching states resulting from collisions of H{sup {minus}} with He at 1 keV

    SciTech Connect

    Kimura, M.; Sato, H. |; Hino, K.; Matsuzawa, M.

    1995-06-01

    Electron energy spectra for H{sup {minus}} autodetaching states resulting from collisions H{sup {minus}} with He at 1 keV are rigorously calculated by including couplings between doubly excited states and continuum states and their interference with direct detachment processes. An energy sampling procedure, based on the Gauss quadratures, is used to discretize continuum states. The present theoretical result, for the first time, clarifies mechanisms of excitation to doubly excited states, quantitatively reproduces the experimental spectra first observed by Risley and Geballe in 1974, separates the contributions from each of three autodetaching states, and identifies the cause of the interference between autodetaching and direct-detaching excitation channels.

  17. Pyrolysis of sulfur tetrafluoride over boron: Excited-state rotational spectra and equilibrium structure of fluorothioborine (FBS)

    NASA Astrophysics Data System (ADS)

    Bizzocchi, L.; Esposti, C. Degli

    2001-10-01

    The unstable FBS molecule has been produced in the gas phase by a high-temperature reaction between crystalline boron and sulfur tetrafluoride. Its rotational spectrum has been observed in the millimeter-wave region, from 75 to 460 GHz, for different isotopic species and vibrational states. All the excited states which approximately lie below 1700 cm-1, that are 1000 (F-B stretch), 0110 (FBS bend), 0001 (B=S stretch), 2000, 0200, 0220, 0310, 0330, 0400, 0420, 0440, 1110, 1200, and 1220, have been investigated for the most abundant isotopomer F11B32S. The analysis of the spectra has been performed taking simultaneously into account the Fermi interaction which couples the states ν1,ν2,ν3 with ν1-1, ν2+2,ν3, and l-type resonances between different sublevels of a given vibrational bending state. This procedure allowed us to calculate directly deperturbed parameters and, in addition, yielded reliable estimates of the vibrational energy difference between the interacting levels and of the normal coordinate cubic force constant k122. Rotational spectra in the ground and various excited states have been also recorded and analyzed for the less abundant isotopic species F10B32S, F11B34S, F10B34S, F11B33S, and F10B33S. The very weak spectrum in the 0001 state was successfully observed for the pair of isotopomers F11B32S and F10B32S, whose equilibrium rotational constants could be accurately calculated yielding the first evaluation of the equilibrium structure of fluorothioborine: re(F-B)=1.2762±0.0002 Å and re(B=S)=1.6091±0.0002 Å.

  18. AssignFit: A program for simultaneous assignment and structure refinement from solid-state NMR spectra

    NASA Astrophysics Data System (ADS)

    Tian, Ye; Schwieters, Charles D.; Opella, Stanley J.; Marassi, Francesca M.

    2012-01-01

    AssignFit is a computer program developed within the XPLOR-NIH package for the assignment of dipolar coupling (DC) and chemical shift anisotropy (CSA) restraints derived from the solid-state NMR spectra of protein samples with uniaxial order. The method is based on minimizing the difference between experimentally observed solid-state NMR spectra and the frequencies back calculated from a structural model. Starting with a structural model and a set of DC and CSA restraints grouped only by amino acid type, as would be obtained by selective isotopic labeling, AssignFit generates all of the possible assignment permutations and calculates the corresponding atomic coordinates oriented in the alignment frame, together with the associated set of NMR frequencies, which are then compared with the experimental data for best fit. Incorporation of AssignFit in a simulated annealing refinement cycle provides an approach for simultaneous assignment and structure refinement (SASR) of proteins from solid-state NMR orientation restraints. The methods are demonstrated with data from two integral membrane proteins, one α-helical and one β-barrel, embedded in phospholipid bilayer membranes.

  19. 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

  20. 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

  1. Multiple coherent states semiclassical initial value representation spectra calculations of lateral interactions for CO on Cu(100).

    PubMed

    Ceotto, Michele; Dell'Angelo, David; Tantardini, Gian Franco

    2010-08-01

    Lateral interactions between carbon monoxide molecules adsorbed on a copper Cu(100) surface are investigated via semiclassical initial value representation (SC-IVR) molecular dynamics. A previous analytical potential is extended to include long-range dipole interactions between coadsorbed molecules and preliminary classical simulations were performed to tune the potential parameters. Then, the spectra for several coadsorbed molecules are calculated using the multiple coherent states approximation of the time-averaging representation of the SC-IVR propagator. Results show strong resonances between coadsorbed molecules as observed by past experiments. Resonances turn into dephasing when isotopical substitutions are performed. PMID:20707543

  2. 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. PMID:27351464

  3. MEASUREMENTS OF MECHANICAL TRIPLET VIBRATIONS IN RHIC.

    SciTech Connect

    MONTAG,C.; BRENNAN,M.; BUTLER,J.; BONATI,R.; KOELLO,P.

    2002-06-02

    Mechanical vibrations of the RHIC interaction region triplets has been identified as the dominant source of orbit jitter for frequencies up to 20 Hz. We report the results of detailed measurements that were performed to characterize these effects. We discuss the impact on beam dynamics and possible cures.

  4. 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.

  5. Spectra and Autoionization Lifetimes of Long-Range Rydberg Molecular States of 85 Rb2

    NASA Astrophysics Data System (ADS)

    Carollo, Ryan; Eyler, Edward; Gould, Phillip; Stwalley, William

    2016-05-01

    We present high-resolution autoionization data and modeling of the 7 p long-range Rydberg molecular states in 85 Rb2. Our process excites a photoassociation resonance in the 1 (0g-) state which decays to v'' = 35 and 36 long-range levels of the a3Σu+ state and to the continuum. These bound molecules are then excited via a single UV photon to target states below the 5 s + 7 p asymptote by a frequency-doubled pulse-amplified CW laser with narrow linewidth, ~ 150 MHz. The long-range portion of the bonding potential is formed by the scattering interaction of the Rydberg electron of a perturbed 7 p atom scattering from a nearby ground-state atom. We use time-of-flight to selectively measure molecular ions, which are formed via autoionization. Using a hyperfine model of the a3Σu+ and its coupling to the X1Σg+ state, we are able to place an upper limit on the autoionization linewidth of 450 MHz, corresponding to a lifetime >= 3 . 5 ×10-10 s. Excited-state hyperfine structure suggests a still-lower linewidth (and thus longer lifetime), but its contribution is not yet fully understood. This work is supported by NSF and AFOSR.

  6. The influence of the beam charge state on the analytical calculation of RBS and ERDA spectra

    NASA Astrophysics Data System (ADS)

    Barradas, Nuno P.; Kosmata, Marcel; Hanf, Daniel; Munnik, Frans

    2016-03-01

    Analytical codes dedicated to the analysis of Ion Beam Analysis data rely on the accuracy of both the calculations and of basic data such as scattering cross sections and stopping powers. So far, the effect of the beam charge state of the incoming beam has been disregard by general purpose analytical codes such as NDF. In fact, the codes implicitly assume that the beam always has the equilibrium charge state distribution, by using tabulated stopping power values e.g. from SRIM, which are in principle valid for the effective charge state. The dependence of the stopping power with the changing charge state distribution is ignored. This assumption is reasonable in most cases, but for high resolution studies the actual change of the charge state distribution from the initial beam charge state towards equilibrium as it enters and traverses the sample must be taken into account, as it influences the shape of the observed data. In this work, we present an analytical calculation, implemented in NDF, that takes this effect into account. For elastic recoil detection analysis (ERDA), the changing charge state distribution of the recoils can also be taken into account. We apply the calculation to the analysis of experimental high depth resolution ERDA data for various oxide layers collected using a magnetic spectrometer.

  7. Probing high-lying N2 ++ and CO++ states via energy-selective fragment spectra

    NASA Astrophysics Data System (ADS)

    Pandey, A.; Saha, K.; Bapat, B.; Kumar, P.; Banerjee, S. B.; Subramanian, K. P.

    2016-07-01

    Dissociation of molecular ions from highly excited states is difficult to probe, so our knowledge of their dynamical evolution and the parameters governing the dissociation is limited. The main complication is due to the large density of high-lying states and crossing of states. The latter may change the kinematics of the fragments, but in general, the contributions from different states to the fragment kinetic energy distributions cannot be separated. Consequently, the exact nature of the evolution remains elusive. In the present work, we have performed kinematic analysis of the dissociation dynamics of di-cations of N2 and CO formed by photoionization, aiming to probe their highly excited states. Correlated fragment ion momenta are measured in coincidence with energy-analyzed ejected electrons, allowing us to estimate energy of the transient molecular ions. These measurements bring out the differences in kinematics of the fragmentation of transient molecular ions having different internal energies. Our analysis indicates that highly excited states decay primarily to their own asymptotic limits with only weak coupling to states decaying to lower asymptotes.

  8. Synthesis of triplet-triplet annihilation upconversion nanocapsules under protective conditions.

    PubMed

    Katta, Kartheek; Busko, Dmitry; Avlasevich, Yuri; Muñoz-Espí, Rafael; Baluschev, Stanislav; Landfester, Katharina

    2015-06-01

    Triplet-triplet annihilation upconversion (TTA-UC) nanocapsules are synthesized under oxygen-protective conditions (i.e., complete darkness and argon atmosphere) by free-radical miniemulsion polymerization. These conditions help to exclude the oxidation of the emitter molecules caused by singlet oxygen, generated during the synthesis at daylight conditions and oxygen-rich environment. Subsequently, keeping all the other experimental conditions the same, samples synthesized at protective conditions demonstrate substantially increased UC efficiency. These experimental facts strongly support the hypothesis that posterior removing of oxygen from TTA-UC nanocapsules is not sufficient to obtain reproducible and sustainable UC results. The schematic representation shows the influence of sunlight on the formation of singlet oxygen and its effect on the triplet-triplet annihilation upconversion process. PMID:25630569

  9. Observation of mixed singlet-triplet Rb2 Rydberg molecules

    NASA Astrophysics Data System (ADS)

    Böttcher, F.; Gaj, A.; Westphal, K. M.; Schlagmüller, M.; Kleinbach, K. S.; Löw, R.; Liebisch, T. Cubel; Pfau, T.; Hofferberth, S.

    2016-03-01

    We present high-resolution spectroscopy of Rb2 ultralong-range Rydberg molecules bound by mixed singlet-triplet electron-neutral atom scattering. The mixing of the scattering channels is a consequence of the hyperfine interaction in the ground-state atom, as predicted recently by Anderson et al. [Phys. Rev. A 90, 062518 (2014), 10.1103/PhysRevA.90.062518]. Our experimental data enable the determination of the effective zero-energy singlet s -wave scattering length for Rb. We show that an external magnetic field can tune the contributions of the singlet and the triplet scattering channels and therefore the binding energies of the observed molecules. This mixing of molecular states via the magnetic field results in observed shifts of the molecular line which differ from the Zeeman shift of the asymptotic atomic states. Finally, we calculate molecular potentials using a full diagonalization approach including the p -wave contribution and all orders in the relative momentum k , and compare the obtained molecular binding energies to the experimental data.

  10. Quenching excited triplet C{sub 60} fullerene by tetracyanoethylene in benzonitrile

    SciTech Connect

    Nadtochenko, V.A.; Denisov, N.N.; Rubtsov, I.V.; Lobach, A.S.; Moravsky, A.P.

    1994-01-01

    The main photophysical properties of C{sub 60} fullerene: The absorption spectra of excited singlet C{sub 60}, the inter-combinational conversion time, the quantum yield of triplet C{sub 60}, the triplet-triplet absorption spectra, and the channels and rate constants of the deactivation of triplet C{sub 60} have been established. The photochemical properties of C{sub 60} fullerene have been investigated to a lesser degree. C{sub 60} is known to be readily reduced (E{sub 1/2} = {minus}0.4 in relation to Ag/Ag{sup +}), in particular, photochemically. For example, photoexcitation of charge-transfer complexes of C{sub 60} with amines gives the radical anion C{sup {minus}}{sub 60} which is also formed in reactions of photoexcited C{sub 60} fullerene. The formation of the radical cation C{sup +}{sub 60} under the action of light has been detected in the reaction with colloidal TiO{sub 2}. The radical ion C{sup +}{sub 60} has been obtained in a homogeneous photochemical process: the reaction of unexcited C{sub 60} with excited singlet N-methylacridinium hexafluorophosphate or with the biphenyl radical cation generated in the reaction with excited singlet N-methylacridinium hexafluorophosphate. The formation of C{sup +}{sub 60} with an electron acceptor in a homogeneous process has not so far been observed. The purpose of this work has been to study the quenching of triplet {sup 3}C{sub 60} with an electron acceptor, tetracyanoethylene (TCNE), which is known to oxidize unsaturated or aromatic hydrocarbons in photochemical reactions.

  11. 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. PMID:27220623

  12. Triplet correlation functions in the Lennard-Jones fluid: Tests against molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    McNeil, William J.; Madden, William G.; Haymet, A. D. J.; Rice, Stuart A.

    1983-01-01

    A recent theory of Haymet, Rice, and Madden (HRM) for the pair and triplet correlation functions is tested at liquid state densities against new molecular dynamics results for the Lennard-Jones (12,6) fluid. The HRM integral equation, based on the Born-Green equation and a topological reduction of the diagrammatic expansion of the triplet correlation function, has been solved for a high temperature state (T*=2.74, ρ*=0.80) and is found to give triplet correlation functions in good agreement with the molecular dynamics results. For a lower-temperature state (T*=0.73, ρ*=0.85), where numerical difficulties have thus far frustrated attempts to obtain a self-consistent solution of the HRM integral equation, direct tests of the HRM closure are made using molecular dynamics pair correlation functions to evaluate the diagrams. Although some striking qualitative features of the triplet correlations are correctly described by the HRM closure for this low-temperature state, the HRM approach is not in quantitative agreement with the molecular dynamics results. Test calculations indicate that the principle source of these errors is the neglect of important higher-order diagrams for the triplet correlation function. A reorganization of the diagrammatic series is suggested which may identify the most important of these neglected diagrams. Additional computer simulation results are also reported for the purely repulsive Weeks-Chandler-Andersen (WCA) ``reference'' fluid and for the underlying hard sphere fluid. The similarity of the pair structures of these fluids, noted by WCA, is also found to hold with high accuracy for the triplet structures. It is suggested that these similarities may be exploited in applying the methods of HRM to the hard sphere fluid.

  13. Composite spectra: XX. 45 Cancri. Two stars with very similar masses but quite different evolutionary states

    NASA Astrophysics Data System (ADS)

    Griffin, R. E. M.; Griffin, R. F.

    2015-02-01

    From accurate radial-velocity measurements covering 11 circuits of the orbit of the composite-spectrum binary 45 Cnc, together with high-resolution spectroscopy spanning nearly 3 circuits, we have (i) isolated cleanly the spectrum of the early-type secondary, (ii) classified the component spectra as G8 III and A3 III, (iii) derived the first double-lined orbit for the system and a mass ratio (M_1/M_2) of 1.035 ± 0.01, and (iv) extracted physical parameters for the component stars, deriving the masses and (log) luminosities of the G star and A star as 3.11 and 3.00 M⊙} R⊙, and 2.34 and 2.28 L⊙, respectively, with corresponding uncertainties of ±0.10 M⊙ R⊙ and ±0.09 L⊙. Since the mass ratio is close to unity, we argue that the more evolved component is unlikely to have been a red giant long enough to have made multiple ascents of the RGB, an argument that is supported somewhat by the rather high eccentricity of the orbit (e = 0.46) and the evolutionary time-scales of the two components, but chiefly by the presence of significant Li I in the spectrum of the cool giant.

  14. 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. PMID:24922118

  15. EASY-GOING deconvolution: Combining accurate simulation and evolutionary algorithms for fast deconvolution of solid-state quadrupolar NMR spectra

    NASA Astrophysics Data System (ADS)

    Grimminck, Dennis L. A. G.; Polman, Ben J. W.; Kentgens, Arno P. M.; Leo Meerts, W.

    2011-08-01

    A fast and accurate fit program is presented for deconvolution of one-dimensional solid-state quadrupolar NMR spectra of powdered materials. Computational costs of the synthesis of theoretical spectra are reduced by the use of libraries containing simulated time/frequency domain data. These libraries are calculated once and with the use of second-party simulation software readily available in the NMR community, to ensure a maximum flexibility and accuracy with respect to experimental conditions. EASY-GOING deconvolution ( EGdeconv) is equipped with evolutionary algorithms that provide robust many-parameter fitting and offers efficient parallellised computing. The program supports quantification of relative chemical site abundances and (dis)order in the solid-state by incorporation of (extended) Czjzek and order parameter models. To illustrate EGdeconv's current capabilities, we provide three case studies. Given the program's simple concept it allows a straightforward extension to include other NMR interactions. The program is available as is for 64-bit Linux operating systems.

  16. [Density functional theory study of surface-enhanced raman spectra and excited state of 1,4-benzenedithiol].

    PubMed

    Shao, Yang-Fan; Li, Chong-Yang; Feng, Yuan-Ming; Lin, Wang

    2014-02-01

    Raman scattering spectra and optimized geometries of the 1,4-benzenedithiol molecule and complexes have been calculated using density functional theory (DFT) with B3LYP functional at the level of 6-311G+(d) basis set for C, H, S atoms and LanL2DZ for Ag, Au atoms, respectively. The optimized 1,4-benzenedithiol molecule was non-planar structure and the angle between benzene ring plane and S-H is 20.20. By means of the simulation of molecule adsorbed on gold and silver cluster, we concluded that gold clusters are nearly parallel to the benzenedithiol molecule and silver clusters are almost perpendicular to the molecular surface. The authors studied the interaction between Raman intensity and molecular properties, such as static polarizablity and charge distribution. The Raman intensity of 1,4-BDT-Au2, 1,4-BDT-Ag2 and Ag2-1,4-BDT-Au2 were in good agreement with static polarizability. The excited states of Ag2-1,4-BDT-Au2 complex were calculated using time-dependent density functional theory (TDDFT). And the simulated absorption spectra and several allowed singlet excited states were analyzed to investigate the surface-enhanced Raman chemical enhancement mechanism. PMID:24822413

  17. Electronic spectra of azaindole and its excited state mixing: A symmetry-adapted cluster configuration interaction study.

    PubMed

    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(∗) 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, (1)Lb π-π(∗), (1)La 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. PMID:26627956

  18. 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.

  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. 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.

  1. 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)].

  2. λ7774 Oxygen Triplet in Open Cluster Dwarfs: Pleiades and M34,

    NASA Astrophysics Data System (ADS)

    Schuler, S. C.; King, J. R.; Hobbs, L. M.; Pinsonneault, M. H.

    2005-07-01

    We have undertaken a LTE analysis of the high-excitation 7774 Å O I triplet in high-resolution, moderate signal-to-noise spectra of 15 Pleiades (HET/HRS) and 8 M34 (Keck/HIRES) open cluster dwarfs. Effective temperatures range from 5048 - 6172 K for the Pleiades sample and from 5290 - 6130 K for the M34 sample. Relative O abundances have been derived using model atmospheres interpolated from four different sets of ATLAS9 grids: with convective overshoot, without convective overshoot, with the mixing length parameter set to 0.5, and with the convective treatment of Canuto, Goldman, & Mazzitelli. In contrast to existing NLTE predictions, a dramatic increase in O I triplet abundance with decreasing temperature is seen for both clusters, regardless of atmospheric model. S I abundances of three Pleiads derived from the high-excitation λ6052.67 feature mimic the O I abundance behavior. O abundances have also been derived from the 6300 Å [OI] feature in three Pleiads; the abundances exhibit a much lower mean value than the cool dwarf triplet results. These data suggest LTE abundances derived from the O I triplet for cool dwarfs (Teff˜5800 K) should be viewed with caution.

  3. A comparative study of triplet and radical-anion photoionization of propiophenone

    NASA Astrophysics Data System (ADS)

    Goez, Martin; Zubarev, Valentin

    2004-12-01

    The photoionization of propiophenone via two different routes was investigated by single-pulse and two-pulse laser-flash photolysis with observation of the hydrated electron and the respective photoionizable intermediate, the triplet or the radical anion. From the dependences of the absolute concentrations on the excitation intensity, kinetic constants and quantum yields were obtained. In the presence of a large surplus of a sacrificial electron donor (triethylamine or DABCO), the reaction is cyclic, with the radical anion of the ketone first formed by photoinduced electron transfer, and then ionized by another photon to regenerate the starting material, all within the same laser flash. The quantum yield of photoionization of the radical anion is 0.25 at 308 nm. In the absence of a donor, the ketone triplet is ionized. The intensity dependences indicate a more complex mechanism than a consecutive reaction and provide evidence for an additional photoreaction of the triplet, presumably regeneration of the starting material by reverse intersystem crossing via a chemical pathway. The quantum yield of photoionization of the triplet is 0.05 at 308 nm and 0.02 at 355 nm. As the electronic configurations of the autoionizing upper excited states are very similar, it is proposed that the lower quantum yield in the case of the triplet might be due to competing deactivation channels, which are not open to the upper excited radical anion.

  4. Radical-mediated dehydrogenation of bile acids by means of hydrogen atom transfer to triplet carbonyls.

    PubMed

    Miro, P; Marin, M L; Miranda, M A

    2016-03-01

    The aim of the present paper is to explore the potential of radical-mediated dehydrogenation of bile salts (BSs), which is reminiscent of the enzymatic action of hydroxysteroid dehydrogenase enzymes (HSDH). The concept has been demonstrated using triplet carbonyls that can be efficiently generated upon selective UVA-excitation. Hydrogen atom transfer (HAT) from BSs to triplet benzophenone (BP) derivatives gave rise to radicals, ultimately leading to reduction of the BP chromophore with concomitant formation of the oxo-analogs of the corresponding BSs. The direct reactivity of triplet BP with BSs in the initial step was evaluated by determining the kinetic rate constants using laser flash photolysis (LFP). The BP triplet decay was monitored (λmax = 520 nm) upon addition of increasing BS concentrations, and the obtained rate constant values indicated a reactivity of the methine hydrogen atoms in the order of C-3 < C-12 < C-7. The steady-state kinetics of the overall process, monitored through the disappearance of the typical BP absorption band at 260 nm, was much faster under N2 than under O2, also supporting the role of the oxygen-quenchable triplet in the dehydrogenation process. Furthermore, irradiation of deaerated aqueous solutions of sodium cholate in the presence of KPMe provided the oxo-analogs, 3[O],7[O]-CA, 3[O]-CA and 7[O]-CA, arising from the HAT process. PMID:26833240

  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. Enhancement of Vibronic and Ground-State Vibrational Coherences in 2D Spectra of Photosynthetic Complexes

    PubMed Central

    Chenu, Aurélia; Christensson, Niklas; Kauffmann, Harald F.; Mančal, Tomáš

    2013-01-01

    A vibronic-exciton model is applied to investigate the recently proposed mechanism of enhancement of coherent oscillations due to mixing of electronic and nuclear degrees of freedom. We study a dimer system to elucidate the role of resonance coupling, site energies, vibrational frequency and energy disorder in the enhancement of vibronic-exciton and ground-state vibrational coherences, and to identify regimes where this enhancement is significant. For a heterodimer representing two coupled bachteriochloropylls of the FMO complex, long-lived vibronic coherences are found to be generated only when the frequency of the mode is in the vicinity of the electronic energy difference. Although the vibronic-exciton coherences exhibit a larger initial amplitude compared to the ground-state vibrational coherences, we conclude that, due to the dephasing of the former, both type of coherences have a similar magnitude at longer population time. PMID:23778355

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

    PubMed

    Das, Soumyajit; Wu, Jishan

    2015-12-01

    Recent developments of open-shell singlet diradicaloids motivated the search for stable singlet-triplet bistable nonalternant polycyclic hydrocarbons. During the synthesis of this type of molecule, such as the dibenzo-cyclohepta[def]fluorene 3, an unexpected azulene-to-naphthalene rearrangement was observed at room temperature, which resulted in new nonalternant hydrocarbons 8a/8b with a closed-shell singlet ground state. These studies provided insight into the unique chemistry of azulene and challenges for the synthesis of singlet-triplet bistable polycyclic hydrocarbons. PMID:26569547

  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. Electronic structure of some adenosine receptor antagonists. III. Quantitative investigation of the electronic absorption spectra of alkyl xanthines

    NASA Astrophysics Data System (ADS)

    Moustafa, H.; Shalaby, Samia H.; El-sawy, K. M.; Hilal, Rifaat

    2002-07-01

    Quantitative and comparative investigation of the electronic absorption spectra of theophylline, caffeine and their derivatives is reported. The spectra of theophylline, caffeine and theobromine were compared to establish the predominant tautomeric species in solution. This comparison, analysis of solvent effects and assignments of the observed transitions via MO computations indicate the exits of only one tautomeric species in solution that is the N7 form. A low-lying triplet state was identified which corresponds to a HOMO-LUMO transition. This relatively long-lived T 1 state is always less polar than the ground state and may very well underlie the photochemical reactivity of alkyl xanthines. Substituents of different electron donating or withdrawing strengths and solvent effects are investigated and analyzed. The present analysis is facilitated via computer deconvolution of the observed spectra and MO computation.

  11. Nonrecurrent quantum states: Systems with singular-continuous and discrete spectra

    SciTech Connect

    Lahiri, A. )

    1993-03-15

    The energy spectrum for a tight binding model with on-site potentials forming a Cantor set is seen to have a globally self-similar structure, and an exact correlation of the wave functions with the energies is pointed out. With periodic driving the quasienergy spectrum is obtained from an equivalent lattice problem and is seen to imply nonrecurrent time evolution of states. A model system with a discrete spectrum shows similar behavior. Implications for the problem of microwave ionization of hydrogen atoms are indicated.

  12. Delayed interval delivery in a triplet gestation

    PubMed Central

    Wooldridge, Rachel J; Oliver, Emily A; Singh, Tulika

    2012-01-01

    A 27-year-old Ghanaian primigravida with a known triamniotic trichorionic triplet pregnancy presented at 17 weeks gestation following a miscarriage of one triplet at home. Examination and investigation revealed no signs of imminent delivery or infection. After careful counselling with regard to prognosis and options available for management, the couple opted for intervention including rescue cerclage. The patient received antibiotic prophylaxis for five days and daily progesterone suppositories until delivery. An ultrasound scan was performed every three weeks to monitor fetal growth and cervical length. At 24 weeks corticosteroids for fetal lung maturity were given. At 31 weeks gestation she experienced spontaneous rupture of membranes followed by active labour and forceps delivery. There were no maternal complications. Both babies were born in a good condition, but required ventilatory support for 72 h. PMID:23188854

  13. Singlets and triplets in hybrid nanodevices

    NASA Astrophysics Data System (ADS)

    Agranovich, V. M.; Dubovskii, O. A.; La Rocca, G. C.

    2014-05-01

    An organic material thin layer can be used to resonantly absorb light and nonradiatively transfer excitation to an adjacent inorganic quantum well the optical nonlinearities of which can in this way be turned on more efficiently than by direct optical pumping. We theoretically consider this process in a hybrid structure based on crystalline tetracene in which the singlet exciton energy is close to twice the one of a triplet exciton and thermally activated singlet exciton fission into two triplets can be efficient. We investigate how the temperature dependence of the singlet exciton diffusion length affects the functional properties of such hybrid organic-inorganic nanostructures based on tetracene. We show how temperature activated fission opens a new possibility to turn on and off the indirect pumping due to energy transfer from the organic into the inorganic subsystem.

  14. Fermiophobia in a Higgs triplet model

    SciTech Connect

    Akeroyd, A. G.; Diaz, Marco A.; Romero Maltrana, D.; Rivera, Maximiliano A.

    2011-05-01

    A fermiophobic Higgs boson can arise in models with an extended Higgs sector, such as models with scalars in an isospin triplet representation. In a specific model with a scalar triplet and spontaneous violation of lepton number induced by a scalar singlet field, we show that fermiophobia is not a fine-tuned situation, unlike in two higgs doublet models. We study distinctive signals of fermiophobia which can be probed at the LHC. For the case of a small Higgs mass, a characteristic signal would be a moderate B(H{yields}{gamma}{gamma}) accompanied by a large B(H{yields}JJ) (where J is a Majoron), the latter being an invisible decay. For the case of a large Higgs mass there is the possibility of dominant H{yields}ZZ, WW and suppressed H{yields}JJ decay modes. In this situation, B(H{yields}ZZ) is larger than B(H{yields}WW), which differs from the SM prediction.

  15. 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

  16. Rapid acquisition of multidimensional solid-state NMR spectra of proteins facilitated by covalently bound paramagnetic tags.

    PubMed

    Nadaud, Philippe S; Helmus, Jonathan J; Sengupta, Ishita; Jaroniec, Christopher P

    2010-07-21

    We describe a condensed data collection approach that facilitates rapid acquisition of multidimensional magic-angle spinning solid-state nuclear magnetic resonance (SSNMR) spectra of proteins by combining rapid sample spinning, optimized low-power radio frequency pulse schemes and covalently attached paramagnetic tags to enhance protein (1)H spin-lattice relaxation. Using EDTA-Cu(2+)-modified K28C and N8C mutants of the B1 immunoglobulin binding domain of protein G as models, we demonstrate that high resolution and sensitivity 2D and 3D SSNMR chemical shift correlation spectra can be recorded in as little as several minutes and several hours, respectively, for samples containing approximately 0.1-0.2 micromol of (13)C,(15)N- or (2)H,(13)C,(15)N-labeled protein. This mode of data acquisition is naturally suited toward the structural SSNMR studies of paramagnetic proteins, for which the typical (1)H longitudinal relaxation time constants are inherently a factor of at least approximately 3-4 lower relative to their diamagnetic counterparts. To illustrate this, we demonstrate the rapid site-specific determination of backbone amide (15)N longitudinal paramagnetic relaxation enhancements using a pseudo-3D SSNMR experiment based on (15)N-(13)C correlation spectroscopy, and we show that such measurements yield valuable long-range (15)N-Cu(2+) distance restraints which report on the three-dimensional protein fold. PMID:20583834

  17. Quantum states for quantum processes: A toy model for ammonia inversion spectra

    SciTech Connect

    Arteca, Gustavo A.; Tapia, O.

    2011-07-15

    Chemical transformations are viewed here as quantum processes modulated by external fields, that is, as shifts in reactant to product amplitudes within a quantum state represented by a linear (coherent) superposition of electronuclear basis functions; their electronic quantum numbers identify the ''chemical species.'' This basis set can be mapped from attractors built from a unique electronic configurational space that is invariant with respect to the nuclear geometry. In turn, the quantum numbers that label these basis functions and the semiclassical potentials for the electronic attractors may be used to derive reaction coordinates to monitor progress as a function of the applied field. A generalization of Feynman's three-state model for the ammonia inversion process illustrates the scheme; to enforce symmetry for the entire inversion process model and ensure invariance with respect to nuclear configurations, the three attractors and their basis functions are computed with a grid of fixed floating Gaussian functions. The external-field modulation of the effective inversion barrier is discussed within this conceptual approach. This analysis brings the descriptions of chemical processes near modern technologies that employ molecules to encode information by means of confinement and external fields.

  18. EEG spectra, behavioral states and motor activity in rats exposed to acetylcholinesterase inhibitor chlorpyrifos.

    PubMed

    Timofeeva, Olga A; Gordon, Christopher J

    2002-06-01

    Exposure to organophosphates (OP) has been associated with sleep disorders such as insomnia and "excessive dreaming." The central mechanisms of these effects are not well understood. OPs inhibit acetylcholinesterase (AChE) activity, leading to a hyperactivity of the brain cholinergic systems that are involved in sleep regulation. We studied alterations in the EEG, behavioral states, motor activity and core temperature in rats orally administered with 10 or 40 mg/kg of the OP insecticide chlorpyrifos (CHP). Occipital EEG, motor activity and core temperature were recorded with telemetric transmitters. Behavioral sleep-wake states were visually scored. Both doses of CHP produced alterations of the EEG (decrease in power of sigma/beta and increase in slow theta and fast gamma bands) characteristic of arousal. EEG alterations were consistent with behavioral changes such as an increase in wakefulness and a decrease in sleep. Waking immobility was a prevalent behavior. We did not detect any overt signs of CHP toxicity, such as an abnormal posture or gait, suggesting that reduced locomotion can be a result of central effects of CHP (such as activation of cholinergic motor inhibitory system) rather than peripheral (such as an impairment of neuromuscular function). Changes in the EEG and behavior occurred independently of the decrease in core temperature. Increased wakefulness together with reduced motor activity after exposure to CHP seems to be a result of hyperactivity in brain cholinergic neuronal networks. PMID:12175464

  19. 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.

  20. 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.

  1. Broadband Emission Spectra from the Cygnus X-3 Jet in the Soft Spectral State

    NASA Astrophysics Data System (ADS)

    Zhang, Jian-Fu; Lu, Ju-Fu

    2015-02-01

    In order to understand the main observational characteristics of the Galactic X-ray binary Cygnus X-3, we propose a radiation model in which high-energy electrons accelerate in the dissipation zone of a jet and produce nonthermal broadband emissions. Broadband spectral energy distributions are computed to compare the AGILE and Fermi LAT data with the multi-band data during soft X-ray spectral states. By fitting observations at different locations of the jet, we find that the emission region is rather compact and should be located at a distance of about one orbital radius. Our results can explain the current multi-frequency observations and also predict the TeV band emission. The model could be tested by a polarization measurement at IR band, and/or by a correlation study between the GeV and TeV bands once very-high-energy observations are available.

  2. BROADBAND EMISSION SPECTRA FROM THE CYGNUS X-3 JET IN THE SOFT SPECTRAL STATE

    SciTech Connect

    Zhang, Jian-Fu; Lu, Ju-Fu E-mail: lujf@xmu.edu.cn

    2015-02-01

    In order to understand the main observational characteristics of the Galactic X-ray binary Cygnus X-3, we propose a radiation model in which high-energy electrons accelerate in the dissipation zone of a jet and produce nonthermal broadband emissions. Broadband spectral energy distributions are computed to compare the AGILE and Fermi LAT data with the multi-band data during soft X-ray spectral states. By fitting observations at different locations of the jet, we find that the emission region is rather compact and should be located at a distance of about one orbital radius. Our results can explain the current multi-frequency observations and also predict the TeV band emission. The model could be tested by a polarization measurement at IR band, and/or by a correlation study between the GeV and TeV bands once very-high-energy observations are available.

  3. 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.

  4. 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.}

  5. Final-State Projection Method in Charge-Transfer Multiplet Calculations: An Analysis of Ti L-Edge Absorption Spectra.

    PubMed

    Kroll, Thomas; Solomon, Edward I; de Groot, Frank M F

    2015-10-29

    A projection method to determine the final-state configuration character of all peaks in a charge transfer multiplet calculation of a 2p X-ray absorption spectrum is presented using a d(0) system as an example. The projection method is used to identify the most important influences on spectral shape and to map out the configuration weights. The spectral shape of a 2p X-ray absorption or L2,3-edge spectrum is largely determined by the ratio of the 2p core-hole interactions relative to the 2p3d atomic multiplet interaction. This leads to a nontrivial spectral assignment, which makes a detailed theoretical description of experimental spectra valuable for the analysis of bonding. PMID:26226507

  6. 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

  7. Correlations between metal spin states and vibrational spectra of a trinuclear Fe(II) complex exhibiting spin crossover

    NASA Astrophysics Data System (ADS)

    Gerasimova, Tatiana P.; Katsyuba, Sergey A.; Lavrenova, Ludmila G.; Pelmenschikov, Vladimir; Kaupp, Martin

    2015-12-01

    Combined IR spectroscopic/quantum-chemical analysis of a 4-propyl-1,2,4-triazole trinuclear Fe(II) complex capable of reversible thermal spin crossover has revealed mid-IR bands of the ligand sensitive to the Fe(II) spin state. The character of the correlations found between the intensity and peak position of the triazole bands and the spin state of the metal center depends neither on the identity of the metal nor on the nuclearity of the complex. The found spectral correlations therefore allow analysis of various similar complexes. This is illustrated by the example of experimental IR spectra reported earlier for Fe(II), Co(II), Ni(II), Cu(II) and Zn(II) complexes with triazole ligands. Quantum-chemical IR spectral simulations further suggest that certain ligand bands vary between the states with the same total molecular spin, but different distribution of the spin density between the metal centers. However these variations are too subtle to discriminate between the spin transitions of the central and peripheral Fe(II) ions. The experimentally revealed mid-IR markers are therefore conclusive only for the total molecular spin.

  8. Assigning States in the Jahn-Teller Coupled Infrared Spectra of CH_3O and CD_3O

    NASA Astrophysics Data System (ADS)

    Johnson, Britta; Sibert, Edwin

    2014-06-01

    The ground tilde{X}^2E vibrations of the methoxy radical have intrigued both experimentalists and theorists alike due to the presence of a conical intersection at the C3v molecular geometry. This conical intersection causes methoxy's vibrational spectrum to be strongly influenced by Jahn-Teller coupling, this leading to large amplitude vibrations and extensive mixing of the two lowest electronic states. This coupling combined with spin-orbit and Fermi couplings greatly complicates the assignments of states. In this talk we describe our efforts to assign the states of both CH_3O and CD_3O. Using the potential energy force field and calculated spectra of Nagesh and Sibert^1 as a starting point, vibrational mixing is considered using various zero-order representations. When the zero-order states are the diabatic normal mode states, there is sufficient mode mixing that the normal mode quantum numbers are no longer good labels. The mixing of the zero-order states can be reduced by including additional terms in the zero-order Hamiltonian, H^o. We consider the choice of including the first order Jahn-Teller coupling between one of the three degenerate normal modes. As the rocking motion has the largest Jahn-Teller coupling, this is the coupling that is included in H^o. Although the normal mode quantum numbers of the rocking basis functions are no longer good quantum numbers, due to the Jahn-Teller induced vibronic mixing, the zero-order states can be labeled with the linear Jahn-Teller quantum numbers.^2 This work extends these ideas by considering an H^o that includes linear Jahn-Teller coupling between two sets of degenerate vibrations. Plots of the resulting zero-order states are presented, and the spectral transitions recently observed3 for both CH_3O and CD_3O in a p-H_2 matrix are assigned using these basis functions. The extent of state-mixing found for the full Hamiltonian H for various choices of H^o is illustrated via the use of correlation diagrams obtained by

  9. 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

  10. 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

    2015-11-01

    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. PMID:26420663

  11. Microenvironmental effects in the excited state properties of p-dimethylaminobenzonitrile complexed to alpha- and beta-cyclodextrin.

    PubMed

    Monti, Sandra; Bortolus, Pietro; Manoli, Francesco; Marconi, Giancarlo; Grabner, Gottfried; Köhler, Gottfried; Mayer, Bernd; Boszczyk, Wojciech; Rotkiewicz, Krystyna

    2003-03-01

    The steady state and time resolved fluorescence and the triplet-triplet absorption of p-dimethylaminobenzonitrile (DMABN) in presence of alpha- and beta-cyclodextrin (CD) were investigated at various host and guest concentrations and temperatures. The formation of 1:1 and 1:2 DMABN:alpha-CD and 1:1 and 2:2 complexes DMABN:beta-CD complexes was ascertained by applying global analysis methods. The "pure" fluorescence spectra as well as the emission quantum yields and lifetimes and the triplet properties of the various associates were determined. The role of environmental features in the radiative and non-radiative deactivation of the LE and ICT excited states of the complexed DMABN was elucidated. PMID:12713218

  12. Singlet-triplet separations measured by [sup 31]P[l brace][sup 1]H[r brace] NMR: Applications to quadruply bonded dimolybdenum and ditungsten complexes

    SciTech Connect

    Cotton, F.A.; Eglin, J.L.; Bo Hong; James, C.A. )

    1993-05-12

    A series of quadruply bonded dimolybdenum and ditungsten compounds M[sub 2]X[sub 4](PP)[sub 2] (M = Mo, W; PP = bidentate phosphine ligands; X = Cl, Br, I) with internal rotational angles [chi] varying from 0.0 to 69.4[degrees] have been studied. Their [sup 31]P[l brace][sup 1]H[r brace] NMR spectra are characterized by their temperature-dependent shifts and line widths that broaden with increasing temperature. A nonlinear, least-squares fit of this temperature dependence of the paramagnetic shifts for their NMR signals allows the evaluation of the singlet-triplet energy separation ([minus]2J), the diamagnetic shift (H[sub dia]), and the electron-nucleus hyperfine coupling constant (A). The singlet-triplet energy separations for all the compounds investigated are found to be in the range 1200-3000 cm[sup [minus]1]. It is now clearly established that the ground state remains [sup 1]A[sub 1g] ([delta][sup 2]) even at [chi] = 45[degrees], where [sup 3]A[sub 2u] ([delta][delta]*) lies 1230 cm[sup [minus]1] above it. The [delta]-bond energy and electronic [delta]-barrier can also be experimentally estimated as 13.8[+-]0.5 kcal mol[sup [minus]1] and 10.3[+-]0.5 kcal mol[sup [minus]1], respectively. 32 refs., 3 figs., 1 tab.

  13. 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.

  14. 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

  15. The charge-trapping and triplet-triplet annihilation processes in organic light-emitting diodes: A duty cycle dependence study on magneto-electroluminescence

    NASA Astrophysics Data System (ADS)

    Peng, Qiming; Chen, Ping; Li, Feng

    2013-01-01

    We studied the magneto-electroluminescence (MEL) in tri-(8-hydroxyquinoline)-aluminum (Alq3)-based organic light-emitting devices through both steady-state and transient methods. As the magnetic field increases, the MEL exhibits a rapid rise, followed by the saturation tendency at all voltages in the steady-state measurement, but in the transient measurement it first increases to a maximum and then decreases to negative values when the driving voltages are higher than 8V. Furthermore, we found that the MEL strongly depends on the duty cycle of the pulse voltage. Finally, by employing the triplet-triplet annihilation model combined with the charge trapping effects, we explained the duty cycle dependence of MELs.

  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. Moderate Resolution Jet Cooled Cavity Ringdown Spectra of the tilde{A} State of NO_3 Radical

    NASA Astrophysics Data System (ADS)

    Codd, Terrance J.; Chen, Ming-Wei; Roudjane, Mourad; Miller, Terry A.

    2012-06-01

    The tilde{A}-tilde{X} spectrum of NO_3 has been previously observed using cavity ringdown spectroscopy (CRDS) by Andrei Deev et. al under ambient conditions. There the authors assigned a number of vibronic bands in the spectrum. However, under these conditions, hot-bands may be present and the spectrum becomes very congested at frequencies higher than ˜8700 cm-1 due to the density of vibronic states and the overlap of their rotational contours. In order to obtain more information about the tilde{A} state of NO_3 we recently obtained spectra from 7550 cm-1 to over 10000 cm-1 using our moderate resolution (≃ 0.05 cm-1) jet cooled CRDS apparatus. Jet cooling in our apparatus reduces the rotational temperature to <30 K and eliminates vibrational hot bands greatly simplifying the spectrum. We are able to resolve and assign more than 15 vibronic features including a new assignment of the 31_0 band. Analysis of the ν_4 progression shows weak Jahn-Teller coupling in this mode. Anomalous band contours and anharmonic spacings are observed for the ν_1ν_4 combination bands and the cause is being investigated. We also see some features that could belong to vibronically forbidden transitions which may be magnetic dipole allowed. A. Deev, J. Sommar, and M. Okumura, J. Chem. Phys. 122, 224305 (2005)

  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. Five-order-of-magnitude reduction of the triplet lifetimes of N-heterocycles by complexation to a trinuclear mercury complex.

    PubMed

    Burress, Charlotte; Elbjeirami, Oussama; Omary, Mohammad A; Gabbaï, François P

    2005-09-01

    The complexation of N-methylcarbazole and N-methylindole by trimeric perfluoro-o-phenylene mercury (1), which can be readily observed in CH2Cl2 solution, leads to the formation of [1.N-methylindole] (2) and [1.N-methylcarbazole] (3) as solid adducts. The solid-state photoluminescence spectra of these adducts show intense emission bands attributed to monomer phosphorescence of N-methylindole and N-methylcarbazole, respectively, with microsecond lifetimes. Remarkably, the triplet lifetimes of the heterocycles in 2 and 3 are shortened by 5 orders of magnitude when compared to those of the free heterocycles. These results are rationalized by invoking the combined external and internal spin-orbit coupling perturbation provided by the mercury and nitrogen atoms. PMID:16131162

  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. PMID:24929382

  1. 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.

  2. Ultrafast electronic and vibrational dynamics in brominated aluminum corroles: Energy relaxation and triplet formation.

    PubMed

    Stensitzki, T; Yang, Y; Berg, A; Mahammed, A; Gross, Z; Heyne, K

    2016-07-01

    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

  3. 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

  4. A new medium for triplet-triplet annihilated upconversion and photocatalytic application.

    PubMed

    Ye, Changqing; Wang, Jingjing; Wang, Xiaomei; Ding, Ping; Liang, Zuoqin; Tao, Xutang

    2016-02-01

    Since the triplet-triplet annihilated upconversion (TTA-UC) materials work efficiently only in degassing organic solvents, it is of significance to find a new medium without toxicity and volatility and that promotes TTA-UC. Here, we firstly reported the effect of an OH-containing medium on low power upconversion and found that in alcohol solvent containing β-cyclodextrin (β-CD), the phosphorescence lifetime (τp) of the sensitizer (PdTPP) and the fluorescence quantum yield (Φf) of the acceptor (DPA) were enhanced with the increase in the number of OH-groups of the medium. A large triplet-triplet quenching constant (kq, 1.91 × 10(9) M(-1) s(-1)) and high upconversion efficiency (ΦUC, ∼ 36%) of PdTPP/DPA were obtained under the excitation of a diode laser (532 nm, 60 mW cm(-2)). Under our green-to-blue upconversion irradiation, in a demonstration experiment the photocurrent was recorded at 0.09 μA cm(-2), resulting from photocatalytic water splitting by a Cd0.7Zn0.3S photoanode and a Pt counter-electrode in a photoelectrochemical cell. The importance of this study suggests that upconversion-powered photoelectrochemistry possesses potential application for hydrogen generation from water under excitation of sun energy. PMID:26580451

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

    NASA Astrophysics Data System (ADS)

    Bittner, Eric R.; Burghardt, Irene; Friend, Richard H.

    2009-02-01

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

  6. Triplet Pairing in Electron Systems with Hexagonal Symmetry

    NASA Astrophysics Data System (ADS)

    Tanaka, Akihiro; Hu, Xiao

    2004-03-01

    Inspired by the recently discovered superconductor Na_xCoO_2otyH_2O[1], we discuss how a novel triplet pairing state can occur from fermi surface effects/electron correlations in 2d electron systems with hexagonal symmetry[2]. This would serve as a complementary approach to studies based on the RVB picture, which basically concentrate on singlet pairing correlations. Spin and charge transports arising from the nontrivial topology (Chern numbers etc.) in k-space are investigated, and compared with the case of the square lattice. [1] K. Takada et al, Nature vol. 422, 53 (2003). [2] A. Tanaka and X. Hu, Phys. Rev. Lett., in press (cond-mat/0304409).

  7. How to calculate linear absorption spectra with lifetime broadening using fewest switches surface hopping trajectories: A simple generalization of ground-state Kubo theory

    SciTech Connect

    Petit, Andrew S.; Subotnik, Joseph E.

    2014-07-07

    In this paper, we develop a surface hopping approach for calculating linear absorption spectra using ensembles of classical trajectories propagated on both the ground and excited potential energy surfaces. We demonstrate that our method allows the dipole-dipole correlation function to be determined exactly for the model problem of two shifted, uncoupled harmonic potentials with the same harmonic frequency. For systems where nonadiabatic dynamics and electronic relaxation are present, preliminary results show that our method produces spectra in better agreement with the results of exact quantum dynamics calculations than spectra obtained using the standard ground-state Kubo formalism. As such, our proposed surface hopping approach should find immediate use for modeling condensed phase spectra, especially for expensive calculations using ab initio potential energy surfaces.

  8. Solid-state effects and atomiclike effects on shallow inner-shell-electron energy-loss spectra of a cation p or d hole in sulfides

    NASA Astrophysics Data System (ADS)

    Ohno, Youichi

    1994-03-01

    Inner-shell-electron energy-loss spectroscopy studies have been done for the systems in which a shallow p or d core hole exists in the final state of a cation. Optically allowed and forbidden transitions have been distinguished from spectral variations due to the breakdown of dipole selection rules. The Ti and V M2,3 spectra and the Zr, Nb, and Mo M4,5 spectra in layered transition-metal disulfides and related misfit-layer compounds are well explained in terms of the energy-band structures. The overall structures of the Pb and Bi O4,5 spectra are understood within the atomic model containing j-j coupling. The Sn N4,5 spectra in SnS and SnS2 are intermediate between them. A reasonable explanation is given by both the atomic model and the band-structure model.

  9. Electron, Hole, Singlet, and Triplet Energy Transfer in Photoexcited Porphyrin-Naphthalenediimide Dyads.

    PubMed

    Yushchenko, Oleksandr; Hangarge, Rahul V; Mosquera-Vazquez, Sandra; Boshale, Sheshanath V; Vauthey, Eric

    2015-06-18

    The excited-state dynamics of two molecular dyads, consisting of zinc (1) and free-base (2) porphyrin connected via a peptide linker to a core-substituted naphthalenediimide (NDI) have been investigated using optical spectroscopy. These dyads exhibit rich photophysics because of the large number of electronic excited states below 3 eV. In the case of 1 in apolar solvents, excitation energy transfer from the vibrationally hot singlet excited porphyrin to the NDI takes place with a 500 fs time constant. Electronic energy ends up in the NDI-localized triplet state, which decays to the ground state on a microsecond timescale. In polar solvents, ground-state recovery is faster by 5 orders of magnitude because of the occurrence of charge separation followed by recombination. On the other hand, excitation energy transfer in 2 takes place in the opposite direction, namely from the NDI to the porphyrin, which then undergoes intersystem crossing to the triplet state, followed by triplet energy transfer back to the NDI. Therefore, four distinct local electronic excited states are consecutively populated after excitation of the NDI unit of 2, with the energy shuttling between the two ends of the dyad. PMID:25418961

  10. Reaction of Triplet Phenylnitrene with Molecular Oxygen.

    PubMed

    Mieres-Pérez, Joel; Mendez-Vega, Enrique; Velappan, Kavitha; Sander, Wolfram

    2015-12-18

    Triplet carbenes react with molecular oxygen with rates that approach diffusion control to carbonyl O-oxides, whereas triplet nitrenes react much slower. For investigating the reaction of phenylnitrene with O2, the nitrene was generated by flash vacuum thermolysis (FVT) of phenylazide and subsequently isolated in O2-doped matrices. FVT of the azide produces the nitrene in high yield and with only minor contaminations of the rearranged products that are frequently observed if the nitrene is produced by photolysis. The phenylnitrene was isolated in solid Ar, Xe, mixtures of these rare gases with O2, and even in pure solid O2. At temperatures between 30 and 35 K an extremely slow thermal reaction between the nitrene and O2 was observed, whereas at higher temperatures, solid Ar and O2 rapidly evaporate. Only O2-doped Xe matrices allowed us to anneal at temperatures above 40 K, and at these temperatures, the nitrene reacts with O2 to produce nitroso O-oxide mainly in its syn conformation. Upon visible light irradiation (450 nm), the nitroso oxide rapidly rearranges to nitrobenzene. PMID:26524191

  11. Mechanism for singlet fission in pentacene and tetracene: from single exciton to two triplets.

    PubMed

    Zimmerman, Paul M; Bell, Franziska; Casanova, David; Head-Gordon, Martin

    2011-12-14

    Singlet fission (SF) could dramatically increase the efficiency of organic solar cells by producing two triplet excitons from each absorbed photon. While this process has been known for decades, most descriptions have assumed the necessity of a charge-transfer intermediate. This ab initio study characterizes the low-lying excited states in acene molecular crystals in order to describe how SF occurs in a realistic crystal environment. Intermolecular interactions are shown to localize the initially delocalized bright state onto a pair of monomers. From this localized state, nonadiabatic coupling mediated by intermolecular motion between the optically allowed exciton and a dark multi-exciton state facilitates SF without the need for a nearby low-lying charge-transfer intermediate. An estimate of the crossing rate shows that this direct quantum mechanical process occurs in well under 1 ps in pentacene. In tetracene, the dark multi-exciton state is uphill from the lowest singlet excited state, resulting in a dynamic interplay between SF and triplet-triplet annihilation. PMID:22084927

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

    SciTech Connect

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

    2003-01-23

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

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

    PubMed Central

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

    2015-01-01

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

  14. 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.

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

    PubMed

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

    2015-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-02-01

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

  17. Noise filtering of composite pulses for singlet-triplet qubits.

    PubMed

    Yang, Xu-Chen; Wang, Xin

    2016-01-01

    Semiconductor quantum dot spin qubits are promising candidates for quantum computing. In these systems, the dynamically corrected gates offer considerable reduction of gate errors and are therefore of great interest both theoretically and experimentally. They are, however, designed under the static-noise model and may be considered as low-frequency filters. In this work, we perform a comprehensive theoretical study of the response of a type of dynamically corrected gates, namely the supcode for singlet-triplet qubits, to realistic 1/f noises with frequency spectra 1/ω(α). Through randomized benchmarking, we have found that supcode offers improvement of the gate fidelity for α  1 and the improvement becomes exponentially more pronounced with the increase of the noise exponent in the range 1  α ≤ 3 studied. On the other hand, for small α, supcode will not offer any improvement. The δJ-supcode, specifically designed for systems where the nuclear noise is absent, is found to offer additional error reduction than the full supcode for charge noises. The computed filter transfer functions of the supcode gates are also presented. PMID:27383129

  18. Noise filtering of composite pulses for singlet-triplet qubits

    PubMed Central

    Yang, Xu-Chen; Wang, Xin

    2016-01-01

    Semiconductor quantum dot spin qubits are promising candidates for quantum computing. In these systems, the dynamically corrected gates offer considerable reduction of gate errors and are therefore of great interest both theoretically and experimentally. They are, however, designed under the static-noise model and may be considered as low-frequency filters. In this work, we perform a comprehensive theoretical study of the response of a type of dynamically corrected gates, namely the supcode for singlet-triplet qubits, to realistic 1/f noises with frequency spectra 1/ωα. Through randomized benchmarking, we have found that supcode offers improvement of the gate fidelity for α  1 and the improvement becomes exponentially more pronounced with the increase of the noise exponent in the range 1  α ≤ 3 studied. On the other hand, for small α, supcode will not offer any improvement. The δJ-supcode, specifically designed for systems where the nuclear noise is absent, is found to offer additional error reduction than the full supcode for charge noises. The computed filter transfer functions of the supcode gates are also presented. PMID:27383129

  19. Memory of spin polarization in triplet-doublet systems

    SciTech Connect

    Imamura, T.; Onitsuka, O.; Obi, K.

    1986-12-18

    The interaction between triplet molecules and nitroxide radicals is studied in solution by the time-resolved ESR technique. Spin polarization induced in the radical reflects that of the triplet molecule which is an encounter partner. The spin-polarized ESR signals observed in nitroxide radicals are interpreted in terms of electron and/or spin exchange mechanisms.

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

    NASA Astrophysics Data System (ADS)

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

    2015-07-01

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

  1. Photoelectron spectra of 2-thiouracil, 4-thiouracil, and 2,4-dithiouracil

    NASA Astrophysics Data System (ADS)

    Ruckenbauer, Matthias; Mai, Sebastian; Marquetand, Philipp; González, Leticia

    2016-02-01

    Ground- and excited-state UV photoelectron spectra of thiouracils (2-thiouracil, 4-thiouracil, and 2,4-dithiouracil) have been simulated using multireference configuration interaction calculations and Dyson norms as a measure for the photoionization intensity. Except for a constant shift, the calculated spectrum of 2-thiouracil agrees very well with experiment, while no experimental spectra are available for the two other compounds. For all three molecules, the photoelectron spectra show distinct bands due to ionization of the sulphur and oxygen lone pairs and the pyrimidine π system. The excited-state photoelectron spectra of 2-thiouracil show bands at much lower energies than in the ground state spectrum, allowing to monitor the excited-state population in time-resolved UV photoelectron spectroscopy experiments. However, the results also reveal that single-photon ionization probe schemes alone will not allow monitoring all photodynamic processes existing in 2-thiouracil. Especially, due to overlapping bands of singlet and triplet states the clear observation of intersystem crossing will be hampered.

  2. 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).

  3. 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. PMID:20643051

  4. 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.

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

    PubMed

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

    2015-01-13

    New materials for OLED applications with low singlet-triplet energy splitting have been recently synthesized in order to allow for the conversion of triplet into singlet excitons (emitting light) via a Thermally Activated Delayed Fluorescence (TADF) process, which involves excited-states with a non-negligible amount of Charge-Transfer (CT). The accurate modeling of these states with Time-Dependent Density Functional Theory (TD-DFT), the most used method so far because of the favorable trade-off between accuracy and computational cost, is however particularly challenging. We carefully address this issue here by considering materials with small (high) singlet-triplet gap acting as emitter (host) in OLEDs and by comparing the accuracy of TD-DFT and the corresponding Tamm-Dancoff Approximation (TDA), which is found to greatly reduce error bars with respect to experiments thanks to better estimates for the lowest singlet-triplet transition. Finally, we quantitatively correlate the singlet-triplet splitting values with the extent of CT, using for it a simple metric extracted from calculations with double-hybrid functionals, that might be applied in further molecular engineering studies. PMID:26574215

  6. 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. PMID:24333386

  7. Photon upconversion: from two-photon absorption (TPA) to triplet-triplet annihilation (TTA).

    PubMed

    Ye, Changqing; Zhou, Liwei; Wang, Xiaomei; Liang, Zuoqin

    2016-04-20

    Organic upconversion is a unique process in which low-energy light (usually NIR light) is converted to high-energy light through either the two-photon absorption (TPA) mechanism or the triplet-triplet annihilation (TTA) mechanism. Both TPA upconversion (TPA-UC) and TTA upconversion (TTA-UC) have been actively investigated in recent years due to their intriguing applications in optics, biophotonics, and solar energy utilization. Although they show some similarity (i.e., belonging to the nonlinear two-quantum process and needing focused excitation light), TPA-UC and TTA-UC are very different, such as in mechanism, characteristics involved, molecular design and potential applications. Here, we collectively reviewed these two kinds of upconversion processes and compared their respective characteristics and merits. We also present recent advances made in the areas of TPA- and TTA-UC, the remaining challenges and opportunities, with particular emphasis on molecular engineering of these two active upconversion materials. PMID:26843136

  8. 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. PMID:24733519

  9. Drug-Drug Interactions within Protein Cavities Probed by Triplet-Triplet Energy Transfer.

    PubMed

    Nuin, Edurne; Jiménez, M Consuelo; Sastre, Germán; Andreu, Inmaculada; Miranda, Miguel A

    2013-05-16

    A new direct and noninvasive methodology based on transient absorption spectroscopy has been developed to probe the feasibility of drug-drug interactions within a common protein binding site. The simultaneous presence of (R)-cinacalcet (CIN) and (S)-propranolol (PPN) within human or bovine α1-acid glycoproteins (AAGs) is revealed by detection of (3)CIN* as the only transient species after laser flash photolysis of CIN/PPN/AAG mixtures at 308 nm. This is the result of triplet-triplet energy transfer from (3)PPN* to CIN, which requires close contact between the two drugs within the same biological compartment. Similar results are obtained with nabumetone and CIN as donor/acceptor partners. This new methodology can, in principle, be extended to a variety of drug/drug/biomolecule combinations. PMID:26282966

  10. Spontaneous Heterotopic Triplet Pregnancy With Tubal Rupture

    PubMed Central

    Danso, Dennis

    2014-01-01

    The recent increase in heterotopic pregnancies has been largely attributed to the increased use of assisted reproduction technologies. We report the rare case of a multiparous woman with a spontaneous conception resulting in a triplet heterotopic pregnancy: a twin intrauterine pregnancy and a single right tubal ectopic pregnancy. Heterotopic pregnancy is a rare and potentially life-threatening condition in which simultaneous gestations occur at 2 or more implantation sites. It is infrequent in natural conception cycles, occurring in 1:30 000 pregnancies. However, the prevalence is rising with the increased use of assisted reproduction techniques to that of 1:100 to 1:500 in these patient subgroups, highlighting the need to incorporate it into a clinician’s diagnostic algorithm. PMID:26425603

  11. Zeaxanthin protects plant photosynthesis by modulating chlorophyll triplet yield in specific light-harvesting antenna subunits.

    PubMed

    Dall'Osto, Luca; Holt, Nancy E; Kaligotla, Shanti; Fuciman, Marcel; Cazzaniga, Stefano; Carbonera, Donatella; Frank, Harry A; Alric, Jean; Bassi, Roberto

    2012-12-01

    Plants are particularly prone to photo-oxidative damage caused by excess light. Photoprotection is essential for photosynthesis to proceed in oxygenic environments either by scavenging harmful reactive intermediates or preventing their accumulation to avoid photoinhibition. Carotenoids play a key role in protecting photosynthesis from the toxic effect of over-excitation; under excess light conditions, plants accumulate a specific carotenoid, zeaxanthin, that was shown to increase photoprotection. In this work we genetically dissected different components of zeaxanthin-dependent photoprotection. By using time-resolved differential spectroscopy in vivo, we identified a zeaxanthin-dependent optical signal characterized by a red shift in the carotenoid peak of the triplet-minus-singlet spectrum of leaves and pigment-binding proteins. By fractionating thylakoids into their component pigment binding complexes, the signal was found to originate from the monomeric Lhcb4-6 antenna components of Photosystem II and the Lhca1-4 subunits of Photosystem I. By analyzing mutants based on their sensitivity to excess light, the red-shifted triplet-minus-singlet signal was tightly correlated with photoprotection in the chloroplasts, suggesting the signal implies an increased efficiency of zeaxanthin in controlling chlorophyll triplet formation. Fluorescence-detected magnetic resonance analysis showed a decrease in the amplitude of signals assigned to chlorophyll triplets belonging to the monomeric antenna complexes of Photosystem II upon zeaxanthin binding; however, the amplitude of carotenoid triplet signal does not increase correspondingly. Results show that the high light-induced binding of zeaxanthin to specific proteins plays a major role in enhancing photoprotection by modulating the yield of potentially dangerous chlorophyll-excited states in vivo and preventing the production of singlet oxygen. PMID:23066020

  12. Zeaxanthin Protects Plant Photosynthesis by Modulating Chlorophyll Triplet Yield in Specific Light-harvesting Antenna Subunits*

    PubMed Central

    Dall'Osto, Luca; Holt, Nancy E.; Kaligotla, Shanti; Fuciman, Marcel; Cazzaniga, Stefano; Carbonera, Donatella; Frank, Harry A.; Alric, Jean; Bassi, Roberto

    2012-01-01

    Plants are particularly prone to photo-oxidative damage caused by excess light. Photoprotection is essential for photosynthesis to proceed in oxygenic environments either by scavenging harmful reactive intermediates or preventing their accumulation to avoid photoinhibition. Carotenoids play a key role in protecting photosynthesis from the toxic effect of over-excitation; under excess light conditions, plants accumulate a specific carotenoid, zeaxanthin, that was shown to increase photoprotection. In this work we genetically dissected different components of zeaxanthin-dependent photoprotection. By using time-resolved differential spectroscopy in vivo, we identified a zeaxanthin-dependent optical signal characterized by a red shift in the carotenoid peak of the triplet-minus-singlet spectrum of leaves and pigment-binding proteins. By fractionating thylakoids into their component pigment binding complexes, the signal was found to originate from the monomeric Lhcb4–6 antenna components of Photosystem II and the Lhca1–4 subunits of Photosystem I. By analyzing mutants based on their sensitivity to excess light, the red-shifted triplet-minus-singlet signal was tightly correlated with photoprotection in the chloroplasts, suggesting the signal implies an increased efficiency of zeaxanthin in controlling chlorophyll triplet formation. Fluorescence-detected magnetic resonance analysis showed a decrease in the amplitude of signals assigned to chlorophyll triplets belonging to the monomeric antenna complexes of Photosystem II upon zeaxanthin binding; however, the amplitude of carotenoid triplet signal does not increase correspondingly. Results show that the high light-induced binding of zeaxanthin to specific proteins plays a major role in enhancing photoprotection by modulating the yield of potentially dangerous chlorophyll-excited states in vivo and preventing the production of singlet oxygen. PMID:23066020

  13. 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

  14. Benzophenone Ultrafast Triplet Population: Revisiting the Kinetic Model by Surface-Hopping Dynamics.

    PubMed

    Marazzi, Marco; Mai, Sebastian; Roca-Sanjuán, Daniel; Delcey, Mickaël G; Lindh, Roland; González, Leticia; Monari, Antonio

    2016-02-18

    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

  15. Fluorescence excitation and ultraviolet absorption spectra and theoretical calculations for benzocyclobutane: Vibrations and structure of its excited S{sub 1}(π,π{sup *}) electronic state

    SciTech Connect

    Shin, Hee Won; Ocola, Esther J.; Laane, Jaan; Kim, Sunghwan

    2014-01-21

    The fluorescence excitation spectra of jet-cooled benzocyclobutane have been recorded and together with its ultraviolet absorption spectra have been used to assign the vibrational frequencies for this molecule in its S{sub 1}(π,π{sup *}) electronic excited state. Theoretical calculations at the CASSCF(6,6)/aug-cc-pVTZ level of theory were carried out to compute the structure of the molecule in its excited state. The calculated structure was compared to that of the molecule in its electronic ground state as well as to the structures of related molecules in their S{sub 0} and S{sub 1}(π,π{sup *}) electronic states. In each case the decreased π bonding in the electronic excited states results in longer carbon-carbon bonds in the benzene ring. The skeletal vibrational frequencies in the electronic excited state were readily assigned and these were compared to the ground state and to the frequencies of five similar molecules. The vibrational levels in both S{sub 0} and S{sub 1}(π,π{sup *}) states were remarkably harmonic in contrast to the other bicyclic molecules. The decreases in the frequencies of the out-of-plane skeletal modes reflect the increased floppiness of these bicyclic molecules in their S{sub 1}(π,π{sup *}) excited state.

  16. 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.

  17. Potential energy surface of triplet N2O2

    NASA Astrophysics Data System (ADS)

    Varga, Zoltan; Meana-Pañeda, Rubén; Song, Guoliang; Paukku, Yuliya; Truhlar, Donald G.

    2016-01-01

    We present a global ground-state triplet potential energy surface for the N2O2 system that is suitable for treating high-energy vibrational-rotational energy transfer and collision-induced dissociation. The surface is based on multi-state complete-active-space second-order perturbation theory/minimally augmented correlation-consistent polarized valence triple-zeta electronic structure calculations plus dynamically scaled external correlation. In the multireference calculations, the active space has 14 electrons in 12 orbitals. The calculations cover nine arrangements corresponding to dissociative diatom-diatom collisions of N2, O2, and nitric oxide (NO), the interaction of a triatomic molecule (N2O and NO2) with the fourth atom, and the interaction of a diatomic molecule with a single atom (i.e., the triatomic subsystems). The global ground-state potential energy surface was obtained by fitting the many-body interaction to 54 889 electronic structure data points with a fitting function that is a permutationally invariant polynomial in terms of bond-order functions of the six interatomic distances.

  18. Potential energy surface of triplet N2O2.

    PubMed

    Varga, Zoltan; Meana-Pañeda, Rubén; Song, Guoliang; Paukku, Yuliya; Truhlar, Donald G

    2016-01-14

    We present a global ground-state triplet potential energy surface for the N2O2 system that is suitable for treating high-energy vibrational-rotational energy transfer and collision-induced dissociation. The surface is based on multi-state complete-active-space second-order perturbation theory/minimally augmented correlation-consistent polarized valence triple-zeta electronic structure calculations plus dynamically scaled external correlation. In the multireference calculations, the active space has 14 electrons in 12 orbitals. The calculations cover nine arrangements corresponding to dissociative diatom-diatom collisions of N2, O2, and nitric oxide (NO), the interaction of a triatomic molecule (N2O and NO2) with the fourth atom, and the interaction of a diatomic molecule with a single atom (i.e., the triatomic subsystems). The global ground-state potential energy surface was obtained by fitting the many-body interaction to 54 889 electronic structure data points with a fitting function that is a permutationally invariant polynomial in terms of bond-order functions of the six interatomic distances. PMID:26772574

  19. Triplet correlations among similarly tuned cells impact population coding

    PubMed Central

    Cayco-Gajic, Natasha A.; Zylberberg, Joel; Shea-Brown, Eric

    2015-01-01

    Which statistical features of spiking activity matter for how stimuli are encoded in neural populations? A vast body of work has explored how firing rates in individual cells and correlations in the spikes of cell pairs impact coding. Recent experiments have shown evidence for the existence of higher-order spiking correlations, which describe simultaneous firing in triplets and larger ensembles of cells; however, little is known about their impact on encoded stimulus information. Here, we take a first step toward closing this gap. We vary triplet correlations in small (approximately 10 cell) neural populations while keeping single cell and pairwise statistics fixed at typically reported values. This connection with empirically observed lower-order statistics is important, as it places strong constraints on the level of triplet correlations that can occur. For each value of triplet correlations, we estimate the performance of the neural population on a two-stimulus discrimination task. We find that the allowed changes in the level of triplet correlations can significantly enhance coding, in particular if triplet correlations differ for the two stimuli. In this scenario, triplet correlations must be included in order to accurately quantify the functionality of neural populations. When both stimuli elicit similar triplet correlations, however, pairwise models provide relatively accurate descriptions of coding accuracy. We explain our findings geometrically via the skew that triplet correlations induce in population-wide distributions of neural responses. Finally, we calculate how many samples are necessary to accurately measure spiking correlations of this type, providing an estimate of the necessary recording times in future experiments. PMID:26042024

  20. Magnetic dipolar interaction between correlated triplets created by singlet fission in tetracene crystals.

    PubMed

    Wang, Rui; Zhang, Chunfeng; Zhang, Bo; Liu, Yunlong; Wang, Xiaoyong; Xiao, Min

    2015-01-01

    Singlet fission can potentially break the Shockley-Queisser efficiency limit in single-junction solar cells by splitting one photoexcited singlet exciton (S1) into two triplets (2T1) in organic semiconductors. A dark multiexciton state has been proposed as the intermediate connecting S1 to 2T1. However, the exact nature of this multiexciton state, especially how the doubly excited triplets interact, remains elusive. Here we report a quantitative study on the magnetic dipolar interaction between singlet-fission-induced correlated triplets in tetracene crystals by monitoring quantum beats relevant to the multiexciton sublevels at room temperature. The resonances of multiexciton sublevels approached by tuning an external magnetic field are observed to be avoided, which agrees well with the theoretical predictions considering a magnetic dipolar interaction of ∼ 0.008 GHz. Our work quantifies the magnetic dipolar interaction in certain organic materials and marks an important step towards understanding the underlying physics of the multiexciton state in singlet fission. PMID:26456368